Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… ·...

96
Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with ECLIPSE By Chuck Kossack Schlumberger Advisor Denver, Colorado NTNU - In-Situ Combustion SIS Training April 10 Schlumberger Private 2 Outline of the Lecture Where does In-situ Combustion Simulation fit in? Review of Thermal Reservoir Simulation Basic theory of chemical reactions In-situ combustion – overview ECLIPSE Thermal treatment of chemical reactions Simulation of in-situ combustion with ECLIPSE Thermal – Example Simulation – Wet Forward Combustion – Sensitivity to Water Air Ratio

Transcript of Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… ·...

Page 1: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

Schlumberger - NTNU Ambassador Lecture Series

In-Situ Combustion Simulation with ECLIPSE

ByChuck Kossack

Schlumberger AdvisorDenver Colorado

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

2

Outline of the Lecture

Where does In-situ Combustion Simulation fit inReview of Thermal Reservoir SimulationBasic theory of chemical reactionsIn-situ combustion ndash overviewECLIPSE Thermal treatment of chemical reactionsSimulation of in-situ combustion with ECLIPSE Thermal ndash

Example Simulation ndash Wet Forward Combustion ndashSensitivity to Water Air Ratio

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Where does In-situ Combustion Simulation fit in

simple rarr complex rarr more complex rarr most complex

Black oil rarr Compositional rarr Thermal rarr In-situ Combustion

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Black Oil - Simple

Unknowns Po Sw Sg

Oil

Water

Gas

Oil

Water

Gas

grid block

PVT ndash Bo Bg Rs Rv table look up on pressure

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Compositional - Complex

Unknowns Po Sw zi (i=12hellipnc)

Liquid and vapor phases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Flash with Equation of State

Liquid and vapor phases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

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Thermal ndash More Complex

Unknowns Po Sw zi (i=12hellipnc) e

Enthalpy eLiquid and vapor phases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Thermal Flash with K(PT)

Enthalpy eLiquid and vapor phases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

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In-situ Combustion ndash Most Complex

Unknowns Po SH2O zi (i = N2 O2 CO2 C6 C10 C20 C30) e

Enthalpy eLiquid and vapor phases containing

Methane

Hexane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Thermal Flash with K(PT)

Enthalpy eLiquid and vapor phases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

Reactions

C6H8 + 8O2 rarr 6CO2 + 4H20 + HEAT

C10H12 + 13O2 rarr 10CO2 + 6H20 + HEAT

C20H22 +255O2 rarr 20CO2 +11H20 + HEAT

C30H32 + 38O2 rarr 30CO2 + 16H20 + HEAT

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Review of Thermal Reservoir Simulation

Key Points From Last Yearrsquos Lecture

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ECLIPSE Thermal Simulator - Energy

In principle there are 2 methods of energy transferConvection ndash with fluid flowConduction ndash in fluid phases and in rock

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Comparison of Black Oil Compositional and Thermal Models

Unknowns(Nc+3) variables per grid block

ECLIPSE Thermal Live Oil

⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

ezzP

iw

i = 1 Nc (molar density)

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Conservation Equations - Energy

( ) eHLeebe QQCFeVdtdR ++++=

The energy conservation equation solved in each grid block at each timestep

blocks grid gneighborin into rate flowenthalpy convective

ebulk volum residuallinear -non

===

e

b

e

FVRwhere

timestep theduring wellsinto rate flowenthalpy net theloss)(heat rocks gsurroundin the to

rate flowenergy conductive blocks grid gneighborin into

rate flowenergy conductive

=

=

=

e

HL

e

Q

Q

C

NTNU - In-Situ Combustion

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Thermodynamic Equilibrium Flash

Three phases in thermodynamic equilibrium ndash determined by K=values

ww

wwg

co

ccg

xTPKy

xTPKy

sdot=

sdot=

)(

)(

NTNU - In-Situ Combustion

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In-Situ Combustion Simulation

NTNU - In-Situ Combustion

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Overview of the Lecture and Basic Chemical Reaction Theory

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Pre-requisites

Most chemical engineers - 1 or more courses in Chemical Reactions and Chemical Kinetics ndash so this is a reviewMost petroleum engineers mechanical engineers

mathematicians - not had such a courseThe following lecture gives a brief overview of Chemical

Reactions and Chemical KineticsWith this knowledge one will be able to understand

ECLIPSE Chemical Reactions theory and applications

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Overview of the lecture

Chemical reactions exist in ECLIPSE Thermal ndash can simulate

bull Combustionbull Biodegradationbull Decay of radioactive tracersbull Non-equilibrium reactions

Allows one component to react with another and create a third and give off or consume energy

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Outline ndash Section 1

IntroductionKeys To Understanding Chemical Reactions

ndash Reaction typesndash Reaction mechanismsndash Activation energyndash Stoichiometryndash Reaction Rate Rate Equation Rate Lawndash Heat of reactionndash Order of reactionndash Products and Ratesndash Thermochemistry

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Chemical Reaction

A chemical reaction is a process that results in the inter-conversion of chemical substancesChemical reactions encompass changes that strictly

involve the motion of electrons in the forming and breaking of chemical bonds

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Reaction Types

Direct combination - synthesis

322 23 NHHN rarr+

Chemical decomposition - analysis

222 22 OHOH +rarr

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Reaction Types

Single displacement - substitution

2222 HNaClHClNa +rarr+

Double displacement

AgClNaNOAgNONaCl +rarr+ 33

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Reaction types

Combustion - any combustible substance combines with an oxidizing element usually oxygen to generate heat and form oxidized products

OHCOOHC 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementary reactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformationndash Transition state ndash where bonds are brokenndash What order bonds are broken and formedndash Relative rates of each stepndash Function of catalystndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H2(g)+N2(g)rarr2NH3(g)

Intermediate stepsN2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)N(adsorbed) + 3H(adsorbed)rarr NH3(adsorbed)NH3(adsorbed) rarr NH3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occurbull Determines initial and final states of the reaction mixture

(products)Chemical kinetics

bull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how the concentration or pressure of the involved substances changes with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phasendash Combustion of liquid fuelndash As fuel heats up some components vaporizendash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surfacendash If reactants are in different phases (one in gas other

solid)ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow laterA short summary isMost reactions are either

ndash Zero Order ndash reaction rate is independent of reactants concentration

ndash First Order ndash reaction rate is dependent on a concentration to 1st power

ndash Second Order - reaction rate is dependent on a concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927 Sweden Nobel Prize in 1903) studied the dependence of the reaction rate versus temperature and proposed a phenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined as the energy that must be overcome in order for a chemical reaction to occurAs previously stated reaction proceed from

ndash Reactants rarr transition state rarr productsndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating two minima of potential energy (of the reactants and of the products of reaction) For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energy equal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take placendash molecules must collide to reactndash must be enough energy (energy of activation) for the two

molecules to reactndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes fromndash Heat of the systemndash From translational vibrational and rotational energy of

each moleculendash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between the activation energy and the reaction rate

⎟⎠⎞

⎜⎝⎛minus=

AkRTEa ln

Where k = reaction rate or rate constant or reaction rate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime also called reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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111

Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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120

Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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125

Saturations and Temperature Profiles in Dry Forward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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146

Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

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Page 2: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

NTNU - In-Situ Combustion

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Where does In-situ Combustion Simulation fit in

simple rarr complex rarr more complex rarr most complex

Black oil rarr Compositional rarr Thermal rarr In-situ Combustion

NTNU - In-Situ Combustion

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Black Oil - Simple

Unknowns Po Sw Sg

Oil

Water

Gas

Oil

Water

Gas

grid block

PVT ndash Bo Bg Rs Rv table look up on pressure

NTNU - In-Situ Combustion

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Compositional - Complex

Unknowns Po Sw zi (i=12hellipnc)

Liquid and vapor phases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Flash with Equation of State

Liquid and vapor phases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

NTNU - In-Situ Combustion

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Thermal ndash More Complex

Unknowns Po Sw zi (i=12hellipnc) e

Enthalpy eLiquid and vapor phases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Thermal Flash with K(PT)

Enthalpy eLiquid and vapor phases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

NTNU - In-Situ Combustion

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In-situ Combustion ndash Most Complex

Unknowns Po SH2O zi (i = N2 O2 CO2 C6 C10 C20 C30) e

Enthalpy eLiquid and vapor phases containing

Methane

Hexane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Thermal Flash with K(PT)

Enthalpy eLiquid and vapor phases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

Reactions

C6H8 + 8O2 rarr 6CO2 + 4H20 + HEAT

C10H12 + 13O2 rarr 10CO2 + 6H20 + HEAT

C20H22 +255O2 rarr 20CO2 +11H20 + HEAT

C30H32 + 38O2 rarr 30CO2 + 16H20 + HEAT

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Review of Thermal Reservoir Simulation

Key Points From Last Yearrsquos Lecture

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ECLIPSE Thermal Simulator - Energy

In principle there are 2 methods of energy transferConvection ndash with fluid flowConduction ndash in fluid phases and in rock

NTNU - In-Situ Combustion

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Comparison of Black Oil Compositional and Thermal Models

Unknowns(Nc+3) variables per grid block

ECLIPSE Thermal Live Oil

⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

ezzP

iw

i = 1 Nc (molar density)

NTNU - In-Situ Combustion

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Conservation Equations - Energy

( ) eHLeebe QQCFeVdtdR ++++=

The energy conservation equation solved in each grid block at each timestep

blocks grid gneighborin into rate flowenthalpy convective

ebulk volum residuallinear -non

===

e

b

e

FVRwhere

timestep theduring wellsinto rate flowenthalpy net theloss)(heat rocks gsurroundin the to

rate flowenergy conductive blocks grid gneighborin into

rate flowenergy conductive

=

=

=

e

HL

e

Q

Q

C

NTNU - In-Situ Combustion

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Thermodynamic Equilibrium Flash

Three phases in thermodynamic equilibrium ndash determined by K=values

ww

wwg

co

ccg

xTPKy

xTPKy

sdot=

sdot=

)(

)(

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In-Situ Combustion Simulation

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14

Overview of the Lecture and Basic Chemical Reaction Theory

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Pre-requisites

Most chemical engineers - 1 or more courses in Chemical Reactions and Chemical Kinetics ndash so this is a reviewMost petroleum engineers mechanical engineers

mathematicians - not had such a courseThe following lecture gives a brief overview of Chemical

Reactions and Chemical KineticsWith this knowledge one will be able to understand

ECLIPSE Chemical Reactions theory and applications

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Overview of the lecture

Chemical reactions exist in ECLIPSE Thermal ndash can simulate

bull Combustionbull Biodegradationbull Decay of radioactive tracersbull Non-equilibrium reactions

Allows one component to react with another and create a third and give off or consume energy

NTNU - In-Situ Combustion

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Outline ndash Section 1

IntroductionKeys To Understanding Chemical Reactions

ndash Reaction typesndash Reaction mechanismsndash Activation energyndash Stoichiometryndash Reaction Rate Rate Equation Rate Lawndash Heat of reactionndash Order of reactionndash Products and Ratesndash Thermochemistry

NTNU - In-Situ Combustion

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Chemical Reaction

A chemical reaction is a process that results in the inter-conversion of chemical substancesChemical reactions encompass changes that strictly

involve the motion of electrons in the forming and breaking of chemical bonds

NTNU - In-Situ Combustion

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19

Reaction Types

Direct combination - synthesis

322 23 NHHN rarr+

Chemical decomposition - analysis

222 22 OHOH +rarr

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Reaction Types

Single displacement - substitution

2222 HNaClHClNa +rarr+

Double displacement

AgClNaNOAgNONaCl +rarr+ 33

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Reaction types

Combustion - any combustible substance combines with an oxidizing element usually oxygen to generate heat and form oxidized products

OHCOOHC 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementary reactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformationndash Transition state ndash where bonds are brokenndash What order bonds are broken and formedndash Relative rates of each stepndash Function of catalystndash All products formed and their amount

NTNU - In-Situ Combustion

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Intermediate Reactions

Overall Reaction3H2(g)+N2(g)rarr2NH3(g)

Intermediate stepsN2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)N(adsorbed) + 3H(adsorbed)rarr NH3(adsorbed)NH3(adsorbed) rarr NH3(g)

NTNU - In-Situ Combustion

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occurbull Determines initial and final states of the reaction mixture

(products)Chemical kinetics

bull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how the concentration or pressure of the involved substances changes with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phasendash Combustion of liquid fuelndash As fuel heats up some components vaporizendash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surfacendash If reactants are in different phases (one in gas other

solid)ndash Surface area interface between reactants is the key to

the rate

NTNU - In-Situ Combustion

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Order of Reaction

A detailed discuss of Order of Reaction will follow laterA short summary isMost reactions are either

ndash Zero Order ndash reaction rate is independent of reactants concentration

ndash First Order ndash reaction rate is dependent on a concentration to 1st power

ndash Second Order - reaction rate is dependent on a concentration to 2nd power or product of 2 concentrations

NTNU - In-Situ Combustion

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927 Sweden Nobel Prize in 1903) studied the dependence of the reaction rate versus temperature and proposed a phenomenological law

NTNU - In-Situ Combustion

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined as the energy that must be overcome in order for a chemical reaction to occurAs previously stated reaction proceed from

ndash Reactants rarr transition state rarr productsndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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32

Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating two minima of potential energy (of the reactants and of the products of reaction) For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energy equal or greater than the activation energy

NTNU - In-Situ Combustion

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take placendash molecules must collide to reactndash must be enough energy (energy of activation) for the two

molecules to reactndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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35

Activation energy - threshold energy - Ea

Energy comes fromndash Heat of the systemndash From translational vibrational and rotational energy of

each moleculendash Higher the temperature pressure ndash higher the energy

NTNU - In-Situ Combustion

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between the activation energy and the reaction rate

⎟⎠⎞

⎜⎝⎛minus=

AkRTEa ln

Where k = reaction rate or rate constant or reaction rate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime also called reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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39

Stoichiometry

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40

Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

NTNU - In-Situ Combustion

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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42

Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

NTNU - In-Situ Combustion

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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44

Reaction Rate Rate Equation Rate Law

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45

Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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46

Some Reactions are Slow ndash oxidation of Iron

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47

Some Reaction are Fast ndash oxidation of wood

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48

Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

NTNU - In-Situ Combustion

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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50

Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

NTNU - In-Situ Combustion

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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53

Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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54

Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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55

Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

NTNU - In-Situ Combustion

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56

Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

NTNU - In-Situ Combustion

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57

Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

NTNU - In-Situ Combustion

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

NTNU - In-Situ Combustion

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65

Reaction Order

NTNU - In-Situ Combustion

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

NTNU - In-Situ Combustion

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

NTNU - In-Situ Combustion

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

NTNU - In-Situ Combustion

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

NTNU - In-Situ Combustion

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

NTNU - In-Situ Combustion

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

NTNU - In-Situ Combustion

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

NTNU - In-Situ Combustion

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

NTNU - In-Situ Combustion

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 3: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Compositional - Complex

Unknowns Po Sw zi (i=12hellipnc)

Liquid and vapor phases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Flash with Equation of State

Liquid and vapor phases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

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Thermal ndash More Complex

Unknowns Po Sw zi (i=12hellipnc) e

Enthalpy eLiquid and vapor phases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Thermal Flash with K(PT)

Enthalpy eLiquid and vapor phases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

NTNU - In-Situ Combustion

SIS Training

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In-situ Combustion ndash Most Complex

Unknowns Po SH2O zi (i = N2 O2 CO2 C6 C10 C20 C30) e

Enthalpy eLiquid and vapor phases containing

Methane

Hexane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Thermal Flash with K(PT)

Enthalpy eLiquid and vapor phases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

Reactions

C6H8 + 8O2 rarr 6CO2 + 4H20 + HEAT

C10H12 + 13O2 rarr 10CO2 + 6H20 + HEAT

C20H22 +255O2 rarr 20CO2 +11H20 + HEAT

C30H32 + 38O2 rarr 30CO2 + 16H20 + HEAT

NTNU - In-Situ Combustion

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Review of Thermal Reservoir Simulation

Key Points From Last Yearrsquos Lecture

NTNU - In-Situ Combustion

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ECLIPSE Thermal Simulator - Energy

In principle there are 2 methods of energy transferConvection ndash with fluid flowConduction ndash in fluid phases and in rock

NTNU - In-Situ Combustion

SIS Training

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Comparison of Black Oil Compositional and Thermal Models

Unknowns(Nc+3) variables per grid block

ECLIPSE Thermal Live Oil

⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

ezzP

iw

i = 1 Nc (molar density)

NTNU - In-Situ Combustion

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Conservation Equations - Energy

( ) eHLeebe QQCFeVdtdR ++++=

The energy conservation equation solved in each grid block at each timestep

blocks grid gneighborin into rate flowenthalpy convective

ebulk volum residuallinear -non

===

e

b

e

FVRwhere

timestep theduring wellsinto rate flowenthalpy net theloss)(heat rocks gsurroundin the to

rate flowenergy conductive blocks grid gneighborin into

rate flowenergy conductive

=

=

=

e

HL

e

Q

Q

C

NTNU - In-Situ Combustion

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Thermodynamic Equilibrium Flash

Three phases in thermodynamic equilibrium ndash determined by K=values

ww

wwg

co

ccg

xTPKy

xTPKy

sdot=

sdot=

)(

)(

NTNU - In-Situ Combustion

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In-Situ Combustion Simulation

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14

Overview of the Lecture and Basic Chemical Reaction Theory

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15

Pre-requisites

Most chemical engineers - 1 or more courses in Chemical Reactions and Chemical Kinetics ndash so this is a reviewMost petroleum engineers mechanical engineers

mathematicians - not had such a courseThe following lecture gives a brief overview of Chemical

Reactions and Chemical KineticsWith this knowledge one will be able to understand

ECLIPSE Chemical Reactions theory and applications

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Overview of the lecture

Chemical reactions exist in ECLIPSE Thermal ndash can simulate

bull Combustionbull Biodegradationbull Decay of radioactive tracersbull Non-equilibrium reactions

Allows one component to react with another and create a third and give off or consume energy

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Outline ndash Section 1

IntroductionKeys To Understanding Chemical Reactions

ndash Reaction typesndash Reaction mechanismsndash Activation energyndash Stoichiometryndash Reaction Rate Rate Equation Rate Lawndash Heat of reactionndash Order of reactionndash Products and Ratesndash Thermochemistry

NTNU - In-Situ Combustion

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Chemical Reaction

A chemical reaction is a process that results in the inter-conversion of chemical substancesChemical reactions encompass changes that strictly

involve the motion of electrons in the forming and breaking of chemical bonds

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Reaction Types

Direct combination - synthesis

322 23 NHHN rarr+

Chemical decomposition - analysis

222 22 OHOH +rarr

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Reaction Types

Single displacement - substitution

2222 HNaClHClNa +rarr+

Double displacement

AgClNaNOAgNONaCl +rarr+ 33

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Reaction types

Combustion - any combustible substance combines with an oxidizing element usually oxygen to generate heat and form oxidized products

OHCOOHC 222810 41012 +rarr+

NTNU - In-Situ Combustion

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Reaction Mechanisms

Definition ndash the step by step sequence of elementary reactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformationndash Transition state ndash where bonds are brokenndash What order bonds are broken and formedndash Relative rates of each stepndash Function of catalystndash All products formed and their amount

NTNU - In-Situ Combustion

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Intermediate Reactions

Overall Reaction3H2(g)+N2(g)rarr2NH3(g)

Intermediate stepsN2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)N(adsorbed) + 3H(adsorbed)rarr NH3(adsorbed)NH3(adsorbed) rarr NH3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occurbull Determines initial and final states of the reaction mixture

(products)Chemical kinetics

bull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how the concentration or pressure of the involved substances changes with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phasendash Combustion of liquid fuelndash As fuel heats up some components vaporizendash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surfacendash If reactants are in different phases (one in gas other

solid)ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow laterA short summary isMost reactions are either

ndash Zero Order ndash reaction rate is independent of reactants concentration

ndash First Order ndash reaction rate is dependent on a concentration to 1st power

ndash Second Order - reaction rate is dependent on a concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927 Sweden Nobel Prize in 1903) studied the dependence of the reaction rate versus temperature and proposed a phenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined as the energy that must be overcome in order for a chemical reaction to occurAs previously stated reaction proceed from

ndash Reactants rarr transition state rarr productsndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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32

Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating two minima of potential energy (of the reactants and of the products of reaction) For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energy equal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take placendash molecules must collide to reactndash must be enough energy (energy of activation) for the two

molecules to reactndash molecules must be orientated with respect to each other

correctly

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34

Activation energy - threshold energy - Ea

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35

Activation energy - threshold energy - Ea

Energy comes fromndash Heat of the systemndash From translational vibrational and rotational energy of

each moleculendash Higher the temperature pressure ndash higher the energy

NTNU - In-Situ Combustion

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between the activation energy and the reaction rate

⎟⎠⎞

⎜⎝⎛minus=

AkRTEa ln

Where k = reaction rate or rate constant or reaction rate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime also called reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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38

Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

NTNU - In-Situ Combustion

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39

Stoichiometry

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40

Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

NTNU - In-Situ Combustion

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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42

Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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44

Reaction Rate Rate Equation Rate Law

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45

Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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46

Some Reactions are Slow ndash oxidation of Iron

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47

Some Reaction are Fast ndash oxidation of wood

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48

Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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53

Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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54

Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

NTNU - In-Situ Combustion

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55

Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

NTNU - In-Situ Combustion

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56

Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

NTNU - In-Situ Combustion

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57

Effect of Catalyst on Reaction

NTNU - In-Situ Combustion

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

NTNU - In-Situ Combustion

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59

Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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60

Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

NTNU - In-Situ Combustion

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

NTNU - In-Situ Combustion

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

NTNU - In-Situ Combustion

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65

Reaction Order

NTNU - In-Situ Combustion

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

NTNU - In-Situ Combustion

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

NTNU - In-Situ Combustion

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

NTNU - In-Situ Combustion

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

NTNU - In-Situ Combustion

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

NTNU - In-Situ Combustion

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

NTNU - In-Situ Combustion

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

NTNU - In-Situ Combustion

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

NTNU - In-Situ Combustion

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

NTNU - In-Situ Combustion

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

NTNU - In-Situ Combustion

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80

First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

NTNU - In-Situ Combustion

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

NTNU - In-Situ Combustion

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

NTNU - In-Situ Combustion

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

NTNU - In-Situ Combustion

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

NTNU - In-Situ Combustion

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

NTNU - In-Situ Combustion

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

NTNU - In-Situ Combustion

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 4: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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In-situ Combustion ndash Most Complex

Unknowns Po SH2O zi (i = N2 O2 CO2 C6 C10 C20 C30) e

Enthalpy eLiquid and vapor phases containing

Methane

Hexane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Thermal Flash with K(PT)

Enthalpy eLiquid and vapor phases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

Reactions

C6H8 + 8O2 rarr 6CO2 + 4H20 + HEAT

C10H12 + 13O2 rarr 10CO2 + 6H20 + HEAT

C20H22 +255O2 rarr 20CO2 +11H20 + HEAT

C30H32 + 38O2 rarr 30CO2 + 16H20 + HEAT

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Review of Thermal Reservoir Simulation

Key Points From Last Yearrsquos Lecture

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ECLIPSE Thermal Simulator - Energy

In principle there are 2 methods of energy transferConvection ndash with fluid flowConduction ndash in fluid phases and in rock

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Comparison of Black Oil Compositional and Thermal Models

Unknowns(Nc+3) variables per grid block

ECLIPSE Thermal Live Oil

⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

ezzP

iw

i = 1 Nc (molar density)

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Conservation Equations - Energy

( ) eHLeebe QQCFeVdtdR ++++=

The energy conservation equation solved in each grid block at each timestep

blocks grid gneighborin into rate flowenthalpy convective

ebulk volum residuallinear -non

===

e

b

e

FVRwhere

timestep theduring wellsinto rate flowenthalpy net theloss)(heat rocks gsurroundin the to

rate flowenergy conductive blocks grid gneighborin into

rate flowenergy conductive

=

=

=

e

HL

e

Q

Q

C

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Thermodynamic Equilibrium Flash

Three phases in thermodynamic equilibrium ndash determined by K=values

ww

wwg

co

ccg

xTPKy

xTPKy

sdot=

sdot=

)(

)(

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In-Situ Combustion Simulation

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Overview of the Lecture and Basic Chemical Reaction Theory

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Pre-requisites

Most chemical engineers - 1 or more courses in Chemical Reactions and Chemical Kinetics ndash so this is a reviewMost petroleum engineers mechanical engineers

mathematicians - not had such a courseThe following lecture gives a brief overview of Chemical

Reactions and Chemical KineticsWith this knowledge one will be able to understand

ECLIPSE Chemical Reactions theory and applications

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Overview of the lecture

Chemical reactions exist in ECLIPSE Thermal ndash can simulate

bull Combustionbull Biodegradationbull Decay of radioactive tracersbull Non-equilibrium reactions

Allows one component to react with another and create a third and give off or consume energy

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Outline ndash Section 1

IntroductionKeys To Understanding Chemical Reactions

ndash Reaction typesndash Reaction mechanismsndash Activation energyndash Stoichiometryndash Reaction Rate Rate Equation Rate Lawndash Heat of reactionndash Order of reactionndash Products and Ratesndash Thermochemistry

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Chemical Reaction

A chemical reaction is a process that results in the inter-conversion of chemical substancesChemical reactions encompass changes that strictly

involve the motion of electrons in the forming and breaking of chemical bonds

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Reaction Types

Direct combination - synthesis

322 23 NHHN rarr+

Chemical decomposition - analysis

222 22 OHOH +rarr

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Reaction Types

Single displacement - substitution

2222 HNaClHClNa +rarr+

Double displacement

AgClNaNOAgNONaCl +rarr+ 33

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Reaction types

Combustion - any combustible substance combines with an oxidizing element usually oxygen to generate heat and form oxidized products

OHCOOHC 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementary reactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformationndash Transition state ndash where bonds are brokenndash What order bonds are broken and formedndash Relative rates of each stepndash Function of catalystndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H2(g)+N2(g)rarr2NH3(g)

Intermediate stepsN2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)N(adsorbed) + 3H(adsorbed)rarr NH3(adsorbed)NH3(adsorbed) rarr NH3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occurbull Determines initial and final states of the reaction mixture

(products)Chemical kinetics

bull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how the concentration or pressure of the involved substances changes with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phasendash Combustion of liquid fuelndash As fuel heats up some components vaporizendash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surfacendash If reactants are in different phases (one in gas other

solid)ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow laterA short summary isMost reactions are either

ndash Zero Order ndash reaction rate is independent of reactants concentration

ndash First Order ndash reaction rate is dependent on a concentration to 1st power

ndash Second Order - reaction rate is dependent on a concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927 Sweden Nobel Prize in 1903) studied the dependence of the reaction rate versus temperature and proposed a phenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined as the energy that must be overcome in order for a chemical reaction to occurAs previously stated reaction proceed from

ndash Reactants rarr transition state rarr productsndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating two minima of potential energy (of the reactants and of the products of reaction) For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energy equal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take placendash molecules must collide to reactndash must be enough energy (energy of activation) for the two

molecules to reactndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes fromndash Heat of the systemndash From translational vibrational and rotational energy of

each moleculendash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between the activation energy and the reaction rate

⎟⎠⎞

⎜⎝⎛minus=

AkRTEa ln

Where k = reaction rate or rate constant or reaction rate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime also called reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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47

Some Reaction are Fast ndash oxidation of wood

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48

Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 5: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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ECLIPSE Thermal Simulator - Energy

In principle there are 2 methods of energy transferConvection ndash with fluid flowConduction ndash in fluid phases and in rock

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Comparison of Black Oil Compositional and Thermal Models

Unknowns(Nc+3) variables per grid block

ECLIPSE Thermal Live Oil

⎟⎟⎟⎟⎟

⎜⎜⎜⎜⎜

ezzP

iw

i = 1 Nc (molar density)

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Conservation Equations - Energy

( ) eHLeebe QQCFeVdtdR ++++=

The energy conservation equation solved in each grid block at each timestep

blocks grid gneighborin into rate flowenthalpy convective

ebulk volum residuallinear -non

===

e

b

e

FVRwhere

timestep theduring wellsinto rate flowenthalpy net theloss)(heat rocks gsurroundin the to

rate flowenergy conductive blocks grid gneighborin into

rate flowenergy conductive

=

=

=

e

HL

e

Q

Q

C

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Thermodynamic Equilibrium Flash

Three phases in thermodynamic equilibrium ndash determined by K=values

ww

wwg

co

ccg

xTPKy

xTPKy

sdot=

sdot=

)(

)(

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In-Situ Combustion Simulation

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Overview of the Lecture and Basic Chemical Reaction Theory

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Pre-requisites

Most chemical engineers - 1 or more courses in Chemical Reactions and Chemical Kinetics ndash so this is a reviewMost petroleum engineers mechanical engineers

mathematicians - not had such a courseThe following lecture gives a brief overview of Chemical

Reactions and Chemical KineticsWith this knowledge one will be able to understand

ECLIPSE Chemical Reactions theory and applications

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Overview of the lecture

Chemical reactions exist in ECLIPSE Thermal ndash can simulate

bull Combustionbull Biodegradationbull Decay of radioactive tracersbull Non-equilibrium reactions

Allows one component to react with another and create a third and give off or consume energy

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Outline ndash Section 1

IntroductionKeys To Understanding Chemical Reactions

ndash Reaction typesndash Reaction mechanismsndash Activation energyndash Stoichiometryndash Reaction Rate Rate Equation Rate Lawndash Heat of reactionndash Order of reactionndash Products and Ratesndash Thermochemistry

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Chemical Reaction

A chemical reaction is a process that results in the inter-conversion of chemical substancesChemical reactions encompass changes that strictly

involve the motion of electrons in the forming and breaking of chemical bonds

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Reaction Types

Direct combination - synthesis

322 23 NHHN rarr+

Chemical decomposition - analysis

222 22 OHOH +rarr

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Reaction Types

Single displacement - substitution

2222 HNaClHClNa +rarr+

Double displacement

AgClNaNOAgNONaCl +rarr+ 33

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Reaction types

Combustion - any combustible substance combines with an oxidizing element usually oxygen to generate heat and form oxidized products

OHCOOHC 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementary reactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformationndash Transition state ndash where bonds are brokenndash What order bonds are broken and formedndash Relative rates of each stepndash Function of catalystndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H2(g)+N2(g)rarr2NH3(g)

Intermediate stepsN2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)N(adsorbed) + 3H(adsorbed)rarr NH3(adsorbed)NH3(adsorbed) rarr NH3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occurbull Determines initial and final states of the reaction mixture

(products)Chemical kinetics

bull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how the concentration or pressure of the involved substances changes with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phasendash Combustion of liquid fuelndash As fuel heats up some components vaporizendash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surfacendash If reactants are in different phases (one in gas other

solid)ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow laterA short summary isMost reactions are either

ndash Zero Order ndash reaction rate is independent of reactants concentration

ndash First Order ndash reaction rate is dependent on a concentration to 1st power

ndash Second Order - reaction rate is dependent on a concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927 Sweden Nobel Prize in 1903) studied the dependence of the reaction rate versus temperature and proposed a phenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined as the energy that must be overcome in order for a chemical reaction to occurAs previously stated reaction proceed from

ndash Reactants rarr transition state rarr productsndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating two minima of potential energy (of the reactants and of the products of reaction) For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energy equal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take placendash molecules must collide to reactndash must be enough energy (energy of activation) for the two

molecules to reactndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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35

Activation energy - threshold energy - Ea

Energy comes fromndash Heat of the systemndash From translational vibrational and rotational energy of

each moleculendash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between the activation energy and the reaction rate

⎟⎠⎞

⎜⎝⎛minus=

AkRTEa ln

Where k = reaction rate or rate constant or reaction rate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime also called reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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47

Some Reaction are Fast ndash oxidation of wood

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48

Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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120

Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 6: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Conservation Equations - Energy

( ) eHLeebe QQCFeVdtdR ++++=

The energy conservation equation solved in each grid block at each timestep

blocks grid gneighborin into rate flowenthalpy convective

ebulk volum residuallinear -non

===

e

b

e

FVRwhere

timestep theduring wellsinto rate flowenthalpy net theloss)(heat rocks gsurroundin the to

rate flowenergy conductive blocks grid gneighborin into

rate flowenergy conductive

=

=

=

e

HL

e

Q

Q

C

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Thermodynamic Equilibrium Flash

Three phases in thermodynamic equilibrium ndash determined by K=values

ww

wwg

co

ccg

xTPKy

xTPKy

sdot=

sdot=

)(

)(

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In-Situ Combustion Simulation

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Overview of the Lecture and Basic Chemical Reaction Theory

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Pre-requisites

Most chemical engineers - 1 or more courses in Chemical Reactions and Chemical Kinetics ndash so this is a reviewMost petroleum engineers mechanical engineers

mathematicians - not had such a courseThe following lecture gives a brief overview of Chemical

Reactions and Chemical KineticsWith this knowledge one will be able to understand

ECLIPSE Chemical Reactions theory and applications

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Overview of the lecture

Chemical reactions exist in ECLIPSE Thermal ndash can simulate

bull Combustionbull Biodegradationbull Decay of radioactive tracersbull Non-equilibrium reactions

Allows one component to react with another and create a third and give off or consume energy

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Outline ndash Section 1

IntroductionKeys To Understanding Chemical Reactions

ndash Reaction typesndash Reaction mechanismsndash Activation energyndash Stoichiometryndash Reaction Rate Rate Equation Rate Lawndash Heat of reactionndash Order of reactionndash Products and Ratesndash Thermochemistry

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Chemical Reaction

A chemical reaction is a process that results in the inter-conversion of chemical substancesChemical reactions encompass changes that strictly

involve the motion of electrons in the forming and breaking of chemical bonds

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Reaction Types

Direct combination - synthesis

322 23 NHHN rarr+

Chemical decomposition - analysis

222 22 OHOH +rarr

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Reaction Types

Single displacement - substitution

2222 HNaClHClNa +rarr+

Double displacement

AgClNaNOAgNONaCl +rarr+ 33

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Reaction types

Combustion - any combustible substance combines with an oxidizing element usually oxygen to generate heat and form oxidized products

OHCOOHC 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementary reactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformationndash Transition state ndash where bonds are brokenndash What order bonds are broken and formedndash Relative rates of each stepndash Function of catalystndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H2(g)+N2(g)rarr2NH3(g)

Intermediate stepsN2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)N(adsorbed) + 3H(adsorbed)rarr NH3(adsorbed)NH3(adsorbed) rarr NH3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occurbull Determines initial and final states of the reaction mixture

(products)Chemical kinetics

bull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how the concentration or pressure of the involved substances changes with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phasendash Combustion of liquid fuelndash As fuel heats up some components vaporizendash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surfacendash If reactants are in different phases (one in gas other

solid)ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow laterA short summary isMost reactions are either

ndash Zero Order ndash reaction rate is independent of reactants concentration

ndash First Order ndash reaction rate is dependent on a concentration to 1st power

ndash Second Order - reaction rate is dependent on a concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927 Sweden Nobel Prize in 1903) studied the dependence of the reaction rate versus temperature and proposed a phenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined as the energy that must be overcome in order for a chemical reaction to occurAs previously stated reaction proceed from

ndash Reactants rarr transition state rarr productsndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating two minima of potential energy (of the reactants and of the products of reaction) For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energy equal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take placendash molecules must collide to reactndash must be enough energy (energy of activation) for the two

molecules to reactndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes fromndash Heat of the systemndash From translational vibrational and rotational energy of

each moleculendash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between the activation energy and the reaction rate

⎟⎠⎞

⎜⎝⎛minus=

AkRTEa ln

Where k = reaction rate or rate constant or reaction rate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime also called reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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47

Some Reaction are Fast ndash oxidation of wood

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48

Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 7: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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In-Situ Combustion Simulation

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Overview of the Lecture and Basic Chemical Reaction Theory

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Pre-requisites

Most chemical engineers - 1 or more courses in Chemical Reactions and Chemical Kinetics ndash so this is a reviewMost petroleum engineers mechanical engineers

mathematicians - not had such a courseThe following lecture gives a brief overview of Chemical

Reactions and Chemical KineticsWith this knowledge one will be able to understand

ECLIPSE Chemical Reactions theory and applications

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Overview of the lecture

Chemical reactions exist in ECLIPSE Thermal ndash can simulate

bull Combustionbull Biodegradationbull Decay of radioactive tracersbull Non-equilibrium reactions

Allows one component to react with another and create a third and give off or consume energy

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Outline ndash Section 1

IntroductionKeys To Understanding Chemical Reactions

ndash Reaction typesndash Reaction mechanismsndash Activation energyndash Stoichiometryndash Reaction Rate Rate Equation Rate Lawndash Heat of reactionndash Order of reactionndash Products and Ratesndash Thermochemistry

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Chemical Reaction

A chemical reaction is a process that results in the inter-conversion of chemical substancesChemical reactions encompass changes that strictly

involve the motion of electrons in the forming and breaking of chemical bonds

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Reaction Types

Direct combination - synthesis

322 23 NHHN rarr+

Chemical decomposition - analysis

222 22 OHOH +rarr

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Reaction Types

Single displacement - substitution

2222 HNaClHClNa +rarr+

Double displacement

AgClNaNOAgNONaCl +rarr+ 33

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Reaction types

Combustion - any combustible substance combines with an oxidizing element usually oxygen to generate heat and form oxidized products

OHCOOHC 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementary reactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformationndash Transition state ndash where bonds are brokenndash What order bonds are broken and formedndash Relative rates of each stepndash Function of catalystndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H2(g)+N2(g)rarr2NH3(g)

Intermediate stepsN2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)N(adsorbed) + 3H(adsorbed)rarr NH3(adsorbed)NH3(adsorbed) rarr NH3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occurbull Determines initial and final states of the reaction mixture

(products)Chemical kinetics

bull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how the concentration or pressure of the involved substances changes with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phasendash Combustion of liquid fuelndash As fuel heats up some components vaporizendash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surfacendash If reactants are in different phases (one in gas other

solid)ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow laterA short summary isMost reactions are either

ndash Zero Order ndash reaction rate is independent of reactants concentration

ndash First Order ndash reaction rate is dependent on a concentration to 1st power

ndash Second Order - reaction rate is dependent on a concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927 Sweden Nobel Prize in 1903) studied the dependence of the reaction rate versus temperature and proposed a phenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined as the energy that must be overcome in order for a chemical reaction to occurAs previously stated reaction proceed from

ndash Reactants rarr transition state rarr productsndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating two minima of potential energy (of the reactants and of the products of reaction) For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energy equal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take placendash molecules must collide to reactndash must be enough energy (energy of activation) for the two

molecules to reactndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes fromndash Heat of the systemndash From translational vibrational and rotational energy of

each moleculendash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between the activation energy and the reaction rate

⎟⎠⎞

⎜⎝⎛minus=

AkRTEa ln

Where k = reaction rate or rate constant or reaction rate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime also called reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 8: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Pre-requisites

Most chemical engineers - 1 or more courses in Chemical Reactions and Chemical Kinetics ndash so this is a reviewMost petroleum engineers mechanical engineers

mathematicians - not had such a courseThe following lecture gives a brief overview of Chemical

Reactions and Chemical KineticsWith this knowledge one will be able to understand

ECLIPSE Chemical Reactions theory and applications

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Overview of the lecture

Chemical reactions exist in ECLIPSE Thermal ndash can simulate

bull Combustionbull Biodegradationbull Decay of radioactive tracersbull Non-equilibrium reactions

Allows one component to react with another and create a third and give off or consume energy

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Outline ndash Section 1

IntroductionKeys To Understanding Chemical Reactions

ndash Reaction typesndash Reaction mechanismsndash Activation energyndash Stoichiometryndash Reaction Rate Rate Equation Rate Lawndash Heat of reactionndash Order of reactionndash Products and Ratesndash Thermochemistry

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Chemical Reaction

A chemical reaction is a process that results in the inter-conversion of chemical substancesChemical reactions encompass changes that strictly

involve the motion of electrons in the forming and breaking of chemical bonds

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Reaction Types

Direct combination - synthesis

322 23 NHHN rarr+

Chemical decomposition - analysis

222 22 OHOH +rarr

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Reaction Types

Single displacement - substitution

2222 HNaClHClNa +rarr+

Double displacement

AgClNaNOAgNONaCl +rarr+ 33

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Reaction types

Combustion - any combustible substance combines with an oxidizing element usually oxygen to generate heat and form oxidized products

OHCOOHC 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementary reactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformationndash Transition state ndash where bonds are brokenndash What order bonds are broken and formedndash Relative rates of each stepndash Function of catalystndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H2(g)+N2(g)rarr2NH3(g)

Intermediate stepsN2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)N(adsorbed) + 3H(adsorbed)rarr NH3(adsorbed)NH3(adsorbed) rarr NH3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occurbull Determines initial and final states of the reaction mixture

(products)Chemical kinetics

bull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how the concentration or pressure of the involved substances changes with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phasendash Combustion of liquid fuelndash As fuel heats up some components vaporizendash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surfacendash If reactants are in different phases (one in gas other

solid)ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow laterA short summary isMost reactions are either

ndash Zero Order ndash reaction rate is independent of reactants concentration

ndash First Order ndash reaction rate is dependent on a concentration to 1st power

ndash Second Order - reaction rate is dependent on a concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927 Sweden Nobel Prize in 1903) studied the dependence of the reaction rate versus temperature and proposed a phenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined as the energy that must be overcome in order for a chemical reaction to occurAs previously stated reaction proceed from

ndash Reactants rarr transition state rarr productsndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating two minima of potential energy (of the reactants and of the products of reaction) For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energy equal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take placendash molecules must collide to reactndash must be enough energy (energy of activation) for the two

molecules to reactndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes fromndash Heat of the systemndash From translational vibrational and rotational energy of

each moleculendash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between the activation energy and the reaction rate

⎟⎠⎞

⎜⎝⎛minus=

AkRTEa ln

Where k = reaction rate or rate constant or reaction rate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime also called reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 9: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Outline ndash Section 1

IntroductionKeys To Understanding Chemical Reactions

ndash Reaction typesndash Reaction mechanismsndash Activation energyndash Stoichiometryndash Reaction Rate Rate Equation Rate Lawndash Heat of reactionndash Order of reactionndash Products and Ratesndash Thermochemistry

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Chemical Reaction

A chemical reaction is a process that results in the inter-conversion of chemical substancesChemical reactions encompass changes that strictly

involve the motion of electrons in the forming and breaking of chemical bonds

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Reaction Types

Direct combination - synthesis

322 23 NHHN rarr+

Chemical decomposition - analysis

222 22 OHOH +rarr

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Reaction Types

Single displacement - substitution

2222 HNaClHClNa +rarr+

Double displacement

AgClNaNOAgNONaCl +rarr+ 33

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Reaction types

Combustion - any combustible substance combines with an oxidizing element usually oxygen to generate heat and form oxidized products

OHCOOHC 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementary reactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformationndash Transition state ndash where bonds are brokenndash What order bonds are broken and formedndash Relative rates of each stepndash Function of catalystndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H2(g)+N2(g)rarr2NH3(g)

Intermediate stepsN2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)N(adsorbed) + 3H(adsorbed)rarr NH3(adsorbed)NH3(adsorbed) rarr NH3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occurbull Determines initial and final states of the reaction mixture

(products)Chemical kinetics

bull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how the concentration or pressure of the involved substances changes with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phasendash Combustion of liquid fuelndash As fuel heats up some components vaporizendash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surfacendash If reactants are in different phases (one in gas other

solid)ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow laterA short summary isMost reactions are either

ndash Zero Order ndash reaction rate is independent of reactants concentration

ndash First Order ndash reaction rate is dependent on a concentration to 1st power

ndash Second Order - reaction rate is dependent on a concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927 Sweden Nobel Prize in 1903) studied the dependence of the reaction rate versus temperature and proposed a phenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined as the energy that must be overcome in order for a chemical reaction to occurAs previously stated reaction proceed from

ndash Reactants rarr transition state rarr productsndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating two minima of potential energy (of the reactants and of the products of reaction) For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energy equal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take placendash molecules must collide to reactndash must be enough energy (energy of activation) for the two

molecules to reactndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes fromndash Heat of the systemndash From translational vibrational and rotational energy of

each moleculendash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between the activation energy and the reaction rate

⎟⎠⎞

⎜⎝⎛minus=

AkRTEa ln

Where k = reaction rate or rate constant or reaction rate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime also called reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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47

Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 10: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Reaction Types

Direct combination - synthesis

322 23 NHHN rarr+

Chemical decomposition - analysis

222 22 OHOH +rarr

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Reaction Types

Single displacement - substitution

2222 HNaClHClNa +rarr+

Double displacement

AgClNaNOAgNONaCl +rarr+ 33

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Reaction types

Combustion - any combustible substance combines with an oxidizing element usually oxygen to generate heat and form oxidized products

OHCOOHC 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementary reactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformationndash Transition state ndash where bonds are brokenndash What order bonds are broken and formedndash Relative rates of each stepndash Function of catalystndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H2(g)+N2(g)rarr2NH3(g)

Intermediate stepsN2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)N(adsorbed) + 3H(adsorbed)rarr NH3(adsorbed)NH3(adsorbed) rarr NH3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occurbull Determines initial and final states of the reaction mixture

(products)Chemical kinetics

bull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how the concentration or pressure of the involved substances changes with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phasendash Combustion of liquid fuelndash As fuel heats up some components vaporizendash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surfacendash If reactants are in different phases (one in gas other

solid)ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow laterA short summary isMost reactions are either

ndash Zero Order ndash reaction rate is independent of reactants concentration

ndash First Order ndash reaction rate is dependent on a concentration to 1st power

ndash Second Order - reaction rate is dependent on a concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927 Sweden Nobel Prize in 1903) studied the dependence of the reaction rate versus temperature and proposed a phenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined as the energy that must be overcome in order for a chemical reaction to occurAs previously stated reaction proceed from

ndash Reactants rarr transition state rarr productsndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating two minima of potential energy (of the reactants and of the products of reaction) For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energy equal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take placendash molecules must collide to reactndash must be enough energy (energy of activation) for the two

molecules to reactndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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35

Activation energy - threshold energy - Ea

Energy comes fromndash Heat of the systemndash From translational vibrational and rotational energy of

each moleculendash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between the activation energy and the reaction rate

⎟⎠⎞

⎜⎝⎛minus=

AkRTEa ln

Where k = reaction rate or rate constant or reaction rate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime also called reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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39

Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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47

Some Reaction are Fast ndash oxidation of wood

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48

Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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120

Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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122

Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 11: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Reaction types

Combustion - any combustible substance combines with an oxidizing element usually oxygen to generate heat and form oxidized products

OHCOOHC 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementary reactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformationndash Transition state ndash where bonds are brokenndash What order bonds are broken and formedndash Relative rates of each stepndash Function of catalystndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H2(g)+N2(g)rarr2NH3(g)

Intermediate stepsN2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)N(adsorbed) + 3H(adsorbed)rarr NH3(adsorbed)NH3(adsorbed) rarr NH3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occurbull Determines initial and final states of the reaction mixture

(products)Chemical kinetics

bull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how the concentration or pressure of the involved substances changes with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phasendash Combustion of liquid fuelndash As fuel heats up some components vaporizendash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surfacendash If reactants are in different phases (one in gas other

solid)ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow laterA short summary isMost reactions are either

ndash Zero Order ndash reaction rate is independent of reactants concentration

ndash First Order ndash reaction rate is dependent on a concentration to 1st power

ndash Second Order - reaction rate is dependent on a concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927 Sweden Nobel Prize in 1903) studied the dependence of the reaction rate versus temperature and proposed a phenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined as the energy that must be overcome in order for a chemical reaction to occurAs previously stated reaction proceed from

ndash Reactants rarr transition state rarr productsndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating two minima of potential energy (of the reactants and of the products of reaction) For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energy equal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take placendash molecules must collide to reactndash must be enough energy (energy of activation) for the two

molecules to reactndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes fromndash Heat of the systemndash From translational vibrational and rotational energy of

each moleculendash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between the activation energy and the reaction rate

⎟⎠⎞

⎜⎝⎛minus=

AkRTEa ln

Where k = reaction rate or rate constant or reaction rate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime also called reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 12: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Intermediate Reactions

Overall Reaction3H2(g)+N2(g)rarr2NH3(g)

Intermediate stepsN2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)N(adsorbed) + 3H(adsorbed)rarr NH3(adsorbed)NH3(adsorbed) rarr NH3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occurbull Determines initial and final states of the reaction mixture

(products)Chemical kinetics

bull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how the concentration or pressure of the involved substances changes with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phasendash Combustion of liquid fuelndash As fuel heats up some components vaporizendash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surfacendash If reactants are in different phases (one in gas other

solid)ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow laterA short summary isMost reactions are either

ndash Zero Order ndash reaction rate is independent of reactants concentration

ndash First Order ndash reaction rate is dependent on a concentration to 1st power

ndash Second Order - reaction rate is dependent on a concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927 Sweden Nobel Prize in 1903) studied the dependence of the reaction rate versus temperature and proposed a phenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined as the energy that must be overcome in order for a chemical reaction to occurAs previously stated reaction proceed from

ndash Reactants rarr transition state rarr productsndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating two minima of potential energy (of the reactants and of the products of reaction) For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energy equal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take placendash molecules must collide to reactndash must be enough energy (energy of activation) for the two

molecules to reactndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes fromndash Heat of the systemndash From translational vibrational and rotational energy of

each moleculendash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between the activation energy and the reaction rate

⎟⎠⎞

⎜⎝⎛minus=

AkRTEa ln

Where k = reaction rate or rate constant or reaction rate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime also called reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 13: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Chemical Kinetics

Rate of a chemical reaction - measure of how the concentration or pressure of the involved substances changes with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phasendash Combustion of liquid fuelndash As fuel heats up some components vaporizendash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surfacendash If reactants are in different phases (one in gas other

solid)ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow laterA short summary isMost reactions are either

ndash Zero Order ndash reaction rate is independent of reactants concentration

ndash First Order ndash reaction rate is dependent on a concentration to 1st power

ndash Second Order - reaction rate is dependent on a concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927 Sweden Nobel Prize in 1903) studied the dependence of the reaction rate versus temperature and proposed a phenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined as the energy that must be overcome in order for a chemical reaction to occurAs previously stated reaction proceed from

ndash Reactants rarr transition state rarr productsndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating two minima of potential energy (of the reactants and of the products of reaction) For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energy equal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take placendash molecules must collide to reactndash must be enough energy (energy of activation) for the two

molecules to reactndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes fromndash Heat of the systemndash From translational vibrational and rotational energy of

each moleculendash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between the activation energy and the reaction rate

⎟⎠⎞

⎜⎝⎛minus=

AkRTEa ln

Where k = reaction rate or rate constant or reaction rate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime also called reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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47

Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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111

Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 14: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Chemical Kinetics

Some reactions occur in gas phasendash Combustion of liquid fuelndash As fuel heats up some components vaporizendash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surfacendash If reactants are in different phases (one in gas other

solid)ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow laterA short summary isMost reactions are either

ndash Zero Order ndash reaction rate is independent of reactants concentration

ndash First Order ndash reaction rate is dependent on a concentration to 1st power

ndash Second Order - reaction rate is dependent on a concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927 Sweden Nobel Prize in 1903) studied the dependence of the reaction rate versus temperature and proposed a phenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined as the energy that must be overcome in order for a chemical reaction to occurAs previously stated reaction proceed from

ndash Reactants rarr transition state rarr productsndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating two minima of potential energy (of the reactants and of the products of reaction) For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energy equal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take placendash molecules must collide to reactndash must be enough energy (energy of activation) for the two

molecules to reactndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes fromndash Heat of the systemndash From translational vibrational and rotational energy of

each moleculendash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between the activation energy and the reaction rate

⎟⎠⎞

⎜⎝⎛minus=

AkRTEa ln

Where k = reaction rate or rate constant or reaction rate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime also called reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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141

Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 15: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927 Sweden Nobel Prize in 1903) studied the dependence of the reaction rate versus temperature and proposed a phenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined as the energy that must be overcome in order for a chemical reaction to occurAs previously stated reaction proceed from

ndash Reactants rarr transition state rarr productsndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating two minima of potential energy (of the reactants and of the products of reaction) For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energy equal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take placendash molecules must collide to reactndash must be enough energy (energy of activation) for the two

molecules to reactndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes fromndash Heat of the systemndash From translational vibrational and rotational energy of

each moleculendash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between the activation energy and the reaction rate

⎟⎠⎞

⎜⎝⎛minus=

AkRTEa ln

Where k = reaction rate or rate constant or reaction rate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime also called reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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120

Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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122

Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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125

Saturations and Temperature Profiles in Dry Forward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 16: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating two minima of potential energy (of the reactants and of the products of reaction) For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energy equal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take placendash molecules must collide to reactndash must be enough energy (energy of activation) for the two

molecules to reactndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes fromndash Heat of the systemndash From translational vibrational and rotational energy of

each moleculendash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between the activation energy and the reaction rate

⎟⎠⎞

⎜⎝⎛minus=

AkRTEa ln

Where k = reaction rate or rate constant or reaction rate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime also called reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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39

Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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47

Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take placendash molecules must collide to reactndash must be enough energy (energy of activation) for the two

molecules to reactndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes fromndash Heat of the systemndash From translational vibrational and rotational energy of

each moleculendash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between the activation energy and the reaction rate

⎟⎠⎞

⎜⎝⎛minus=

AkRTEa ln

Where k = reaction rate or rate constant or reaction rate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime also called reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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64

Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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111

Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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120

Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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122

Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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125

Saturations and Temperature Profiles in Dry Forward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 18: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Activation energy - threshold energy - Ea

Energy comes fromndash Heat of the systemndash From translational vibrational and rotational energy of

each moleculendash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between the activation energy and the reaction rate

⎟⎠⎞

⎜⎝⎛minus=

AkRTEa ln

Where k = reaction rate or rate constant or reaction rate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime also called reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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39

Stoichiometry

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40

Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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45

Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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47

Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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99

In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Arrhenius Equation

To give the reaction rate (or rate constant)

RTEaAek minus=A is pre-exponential factor (sometime called reaction rate constant) ndash units same as rate constant ndash varies ndash depends on order of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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54

Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 20: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion (element) and metriā (measure from metron)Stoichiometry ndash based on

ndash law of conservation of massndash the law of definite proportions (ie the law of constant

composition)ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 21: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Stoichiometry

Chemical reactions combine in definite ratios of chemicals Chemical reactions

ndash neither create nor destroy matter ndash nor transmute one element into anotherndash the amount of each element must be the same

throughout the overall reaction bull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

OHOH 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atoms on products side

2 Oxygen atoms on the reactants side - 2 Oxygen atoms on the products side

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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141

Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 22: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Stoichiometry

Example thermite reaction

FeOAlAlOFe 22 3232 +rarr+2 Iron atoms on reactants side ndash 2 Iron atoms on products side

3 Oxygen atoms on the reactants side - 3 Oxygen atoms on the products side

2 Aluminum atoms on the reactants side - 2 Aluminum atoms on the products side

A thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 24: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndashwithout appreciable build-up of reaction intermediates

qQpPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 25: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Reaction Rate

[ ] [ ] [ ] [ ]dtQd

qdtPd

pdtBd

bdtAd

av 1111

==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration as described by the rate law and explained by collision theory

As reactant concentration increases the frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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111

Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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120

Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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122

Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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125

Saturations and Temperature Profiles in Dry Forward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 26: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that form solids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing more collisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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120

Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 27: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect the reaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases with pressure which is in fact equivalent to an increase in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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111

Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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120

Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 28: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make a reaction spontaneous

Provides the particles of the reactants with more energy

This energy - may break bonds promote molecules to electronically or vibrationally excited states - creating intermediate species that react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate by providing an alternative pathway with a lower activation energy

Catalyst can increase rate in both the forward and reverse reactions

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Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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141

Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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172

Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 29: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface area increases

Powders react faster than solid blocks - greater surface area = faster rate

Surface example - heterogeneous catalysis ndash see next slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium and Rhodium) in you car

Three main reactions are catalyzed by Catalytic converters(1) The oxidation of carbon monoxide to carbon dioxide

2CO(g) + O2(g) rarr 2CO2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalytic converters

(2) The reduction of nitrogen monoxide back to nitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO2(g)

(3) Oxidation of un-combusted hydrocarbonsC6H6(g) + 7frac12O2 rarr 6CO2(g) +3H2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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125

Saturations and Temperature Profiles in Dry Forward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 31: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how the reactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ] )( mn BATkr =

Where k(T) is the reaction rate coefficient or rate constant ndash not constant ndash function of temperature and other parameters except for concentration

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 32: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Rate Equation

[ ] [ ] )( mn BATkr =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (to be discussed) and depend on the reaction mechanism

Sometimes are the same as the stoichiometric coefficients (n and m) of A and B but not necessarily

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Rate Equation

[ ] [ ] )( mn BATkr =Concentration

Higher concentrated = faster rate Note in some cases the rate may be unaffected by the concentration of a particular reactant provided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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126

Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 33: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentration term in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A]1[B]2

Double the concentration of A for this reaction then we would double the rate

But doubling the concentration of B would quadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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120

Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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122

Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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125

Saturations and Temperature Profiles in Dry Forward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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172

Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 35: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Reaction Order

Not necessary that the order of a reaction is a whole number

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only by experiment

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Zero Order Reactions

A zero-order reaction - rate - independent of the concentration of the reactant(s)

Increasing the concentration of the reacting species will not speed up the rate of the reaction

Zero-order reactions are typically found when a material required for the reaction to proceed such as a surface or a catalyst is saturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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111

Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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122

Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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146

Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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161

Exothermic

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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172

Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 36: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k0 is the reaction rate coefficient k0 (reaction rate constant) has units of concentrationtime

0kr =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k[A]-[A]yieldsn integratio

][

00

0

=

=minus= kdtAdr

Assumptions ndash closed system no build-up of intermediates

[A]0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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120

Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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122

Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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125

Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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146

Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 37: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Excel Calculation of Reaction Rate ndash Zero First Second Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 38: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and products ndash proportional to a derivative of a concentration

Rate of reaction = r

Rate Law is

dtAdr ][

minus=

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 39: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Derivation of First Order Equations

For a First Order Reaction

1time of units thehas constant) rate(reaction k

][][is balance mass thesystem closed ain or

][

1

1

1

AkdtAdr

Akr

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeist where

][][

sexpression combining

][][have we

1

1

tkAAd

AkdtAdr

minus=

=minus=

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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125

Saturations and Temperature Profiles in Dry Forward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 40: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Derivation of First Order Equations

law rate thegintegratin[A] isA ofion concentrat 0at t

][][

0

1

=

minus= tkAAd

For a First Order Reaction we have

tke 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentration of only one reactant

Other reactants can be present but each will be zero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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120

Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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122

Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 41: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l) rarr 2H2O(l) + O2(g) ndash decomposition of Hydrogen PeroxideSO2Cl2(l) rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir in polar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 42: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on the concentrations of one second-order reactant or two first-order reactants

]][[or

][

2

22

BAkr

Akr

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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161

Exothermic

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 43: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][][ Ak

dtAd

sdot=minus

Second order reaction rate constant k2 in mol-1 s-1

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Simple Second Order Reactions

dtkAAd

sdot=minus 22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 44: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Second Order Reactions (Simple Second Order)

02

0

20

][1][][

][1

][1

AtkAA

tkAA

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreases according to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

112 ][][][ BAk

dtAd

sdot=minus

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 45: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Mixed Second Order Reactions Reaction (1)

ktBAeBA

BA )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A]0 ne [B]0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of Nitrogen dioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and a poison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 46: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Time (Days)

Rea

ctan

t Con

cent

ratio

n (lb

mol

ecu

bic

ft)

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 47: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when three species come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][3 CBAk

dtCd

dtBd

dtAd

minus===

Third order reactions are rare so no further analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 48: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Example of Third Order Reaction

In the atmosphere

2NO + O2 rarr 2NO2

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Units of k (rate constant)

Zero Order ndash mole V-1sec-1

First Order ndash sec-1

Second Order ndash Vmole-1sec-1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 49: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 50: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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In-situ Combustion(In situ = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oil toward producing wells

ndash Production increased and heat was noted ndash at first not attributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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History

Russians ndash first planned work on subsurface combustionndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steam and gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 53: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combustion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producerInject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 54: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

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Overview

Vaporizing zone contains combustion products light hydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to difference between gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow (without gas saturation nothing will move gas injectivity limited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 56: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysis available on in-situ combustion

ndash Dry forward combustionndash Wet combustionndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

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The Fuel

Usual way to determine fuel would be burned ndash by experiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest

ndash Amount of air required to burn a unit bulk volume of reservoir rock

ndash Amount of crude available for displacement from the burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperaturendash HTO ndash high temperature oxidation = burningndash LTO ndash low temperature oxidation = smolderingndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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122

Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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125

Saturations and Temperature Profiles in Dry Forward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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146

Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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April 10

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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April 10

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End of Lecture

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbons creates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O

ndash Note in simulations ndash will ignore formation of COndash Small effect on energy balance fluid flowndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidation products

ndash Carboxylic acidsndash Aldehydesndash Keytonesndash Alcoholsndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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122

Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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125

Saturations and Temperature Profiles in Dry Forward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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130

Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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146

Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 59: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forward combustionLTO ndash found

ndash Under bypass conditions ndash fluids bypass the combustion zone in high permeability layers

ndash In wet combustionndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Producedndash Hydrocarbon gasesndash N2ndash CO2ndash COndash O2ndash H2ndash Arndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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130

Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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April 10

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132

Temperature and Saturation during Reverse Combustion

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SIS Training

April 10

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

NTNU - In-Situ Combustion

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April 10

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134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

NTNU - In-Situ Combustion

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

NTNU - In-Situ Combustion

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April 10

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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146

Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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161

Exothermic

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 60: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O2

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Heat of Combustion

air Btuscf250501

231967094xm

xmha +minus+minus

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

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April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

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Kinetics

During low temperature oxidation ndash fuel is crude itselfAt higher temperatures ndash cracking of heavy and

intermediate MW crude form coke (solid) ndash combustion involves burning of coke

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Kinetics

In Thermal simulations have various approximationsndash React the crude with O2 to produce H2O and CO2ndash Crack high MW crude to coke + light oil then burn coke

and burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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125

Saturations and Temperature Profiles in Dry Forward Combustion

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126

Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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146

Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) modelndash One dimensional view

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125

Saturations and Temperature Profiles in Dry Forward Combustion

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126

Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

NTNU - In-Situ Combustion

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

NTNU - In-Situ Combustion

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April 10

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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146

Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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SIS Training

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

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End of Lecture

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Saturations and Temperature Profiles in Dry Forward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during Reverse Combustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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April 10

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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April 10

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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Wet Combustion

Process where water passes through combustion front with airApplied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situ combustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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130

Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

NTNU - In-Situ Combustion

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143

CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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146

Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500 o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 65: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperature Higher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steam zone ndash more rapid displacement of oil ndash reduction in fuel burned

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Saturation and Temperatures during Wet Combustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during Reverse Combustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

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April 10

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134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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161

Exothermic

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REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

NTNU - In-Situ Combustion

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

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189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during Reverse Combustion

NTNU - In-Situ Combustion

SIS Training

April 10

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

135

THAI Process Concept

NTNU - In-Situ Combustion

SIS Training

April 10

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136

End of Section 2

NTNU - In-Situ Combustion

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137

ECLIPSE Thermal Treatment of Chemical Reactions

NTNU - In-Situ Combustion

SIS Training

April 10

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

NTNU - In-Situ Combustion

SIS Training

April 10

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139

Chemical Reaction in ECLIPSE

NTNU - In-Situ Combustion

SIS Training

April 10

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

NTNU - In-Situ Combustion

SIS Training

April 10

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141

Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

NTNU - In-Situ Combustion

SIS Training

April 10

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142

Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

143

CVTYPE

NTNU - In-Situ Combustion

SIS Training

April 10

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144

Phases corresponding to each volatility type

NTNU - In-Situ Combustion

SIS Training

April 10

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

NTNU - In-Situ Combustion

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146

Chemical Reaction Keywords

NTNU - In-Situ Combustion

SIS Training

April 10

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147

RUNSPEC and PROPS Keywords

NTNU - In-Situ Combustion

SIS Training

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148

RUNSPEC Keywords

NTNU - In-Situ Combustion

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

NTNU - In-Situ Combustion

SIS Training

April 10

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REACTION Example

REACTION4

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151

PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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153

Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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154

Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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157

REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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158

REACENTH ndash typical values

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159

REACENTH ndash more typical values

NTNU - In-Situ Combustion

SIS Training

April 10

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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161

Exothermic

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

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April 10

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174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion using vertical wells

ndash Communication between injector and producerndash Movement of oil bank and combustion gases thru cold

heavy oil regionProblems overcome with a long horizontal producer

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producerHigh temperatures ndash 400 to 700 o C results in partially

upgrading crude oilbitumen in-situCoke is deposited at the combustion front ndash from

intensive cracking of the bitumen residue

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

135

THAI Process Concept

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

136

End of Section 2

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

137

ECLIPSE Thermal Treatment of Chemical Reactions

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

139

Chemical Reaction in ECLIPSE

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

141

Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

142

Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

143

CVTYPE

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

144

Phases corresponding to each volatility type

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

NTNU - In-Situ Combustion

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April 10

Schlumberger Private

146

Chemical Reaction Keywords

NTNU - In-Situ Combustion

SIS Training

April 10

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147

RUNSPEC and PROPS Keywords

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April 10

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148

RUNSPEC Keywords

NTNU - In-Situ Combustion

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

NTNU - In-Situ Combustion

SIS Training

April 10

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REACTION Example

REACTION4

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151

PROPS Keywords

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April 10

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

NTNU - In-Situ Combustion

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April 10

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153

Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

154

Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

NTNU - In-Situ Combustion

SIS Training

April 10

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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157

REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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April 10

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158

REACENTH ndash typical values

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April 10

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159

REACENTH ndash more typical values

NTNU - In-Situ Combustion

SIS Training

April 10

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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161

Exothermic

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

NTNU - In-Situ Combustion

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163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

NTNU - In-Situ Combustion

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165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

NTNU - In-Situ Combustion

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April 10

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

NTNU - In-Situ Combustion

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April 10

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

NTNU - In-Situ Combustion

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April 10

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

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April 10

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174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

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April 10

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

NTNU - In-Situ Combustion

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April 10

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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THAI Process Concept

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April 10

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

139

Chemical Reaction in ECLIPSE

NTNU - In-Situ Combustion

SIS Training

April 10

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

NTNU - In-Situ Combustion

SIS Training

April 10

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141

Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

NTNU - In-Situ Combustion

SIS Training

April 10

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142

Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

143

CVTYPE

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SIS Training

April 10

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144

Phases corresponding to each volatility type

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

NTNU - In-Situ Combustion

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April 10

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146

Chemical Reaction Keywords

NTNU - In-Situ Combustion

SIS Training

April 10

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147

RUNSPEC and PROPS Keywords

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

148

RUNSPEC Keywords

NTNU - In-Situ Combustion

SIS Training

April 10

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

NTNU - In-Situ Combustion

SIS Training

April 10

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REACTION Example

REACTION4

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151

PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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153

Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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154

Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

NTNU - In-Situ Combustion

SIS Training

April 10

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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157

REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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158

REACENTH ndash typical values

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159

REACENTH ndash more typical values

NTNU - In-Situ Combustion

SIS Training

April 10

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

NTNU - In-Situ Combustion

SIS Training

April 10

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161

Exothermic

NTNU - In-Situ Combustion

SIS Training

April 10

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

NTNU - In-Situ Combustion

SIS Training

April 10

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163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

NTNU - In-Situ Combustion

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165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

NTNU - In-Situ Combustion

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April 10

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

NTNU - In-Situ Combustion

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

Page 69: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

137

ECLIPSE Thermal Treatment of Chemical Reactions

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

139

Chemical Reaction in ECLIPSE

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

141

Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

142

Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

143

CVTYPE

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

144

Phases corresponding to each volatility type

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

146

Chemical Reaction Keywords

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

147

RUNSPEC and PROPS Keywords

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

148

RUNSPEC Keywords

NTNU - In-Situ Combustion

SIS Training

April 10

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACTION Example

REACTION4

NTNU - In-Situ Combustion

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April 10

Schlumberger Private

151

PROPS Keywords

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

NTNU - In-Situ Combustion

SIS Training

April 10

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153

Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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SIS Training

April 10

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

NTNU - In-Situ Combustion

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157

REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

NTNU - In-Situ Combustion

SIS Training

April 10

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158

REACENTH ndash typical values

NTNU - In-Situ Combustion

SIS Training

April 10

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159

REACENTH ndash more typical values

NTNU - In-Situ Combustion

SIS Training

April 10

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

NTNU - In-Situ Combustion

SIS Training

April 10

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161

Exothermic

NTNU - In-Situ Combustion

SIS Training

April 10

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

NTNU - In-Situ Combustion

SIS Training

April 10

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163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

NTNU - In-Situ Combustion

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April 10

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165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

NTNU - In-Situ Combustion

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April 10

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

NTNU - In-Situ Combustion

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April 10

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

NTNU - In-Situ Combustion

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April 10

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

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172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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April 10

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174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

NTNU - In-Situ Combustion

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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SIS Training

April 10

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189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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139

Chemical Reaction in ECLIPSE

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SIS Training

April 10

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140

Reactants and Products

Need components forndash Injection gases ndash air oxygen nitrogenndash Oil components ndash liquid fuel produced oilndash Coke ndash solid fuelndash Combustion products ndash gases and sometime coke

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141

Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

NTNU - In-Situ Combustion

SIS Training

April 10

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142

Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

143

CVTYPE

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April 10

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144

Phases corresponding to each volatility type

NTNU - In-Situ Combustion

SIS Training

April 10

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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146

Chemical Reaction Keywords

NTNU - In-Situ Combustion

SIS Training

April 10

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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153

Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

NTNU - In-Situ Combustion

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April 10

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154

Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

NTNU - In-Situ Combustion

SIS Training

April 10

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

NTNU - In-Situ Combustion

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April 10

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157

REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

NTNU - In-Situ Combustion

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April 10

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158

REACENTH ndash typical values

NTNU - In-Situ Combustion

SIS Training

April 10

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159

REACENTH ndash more typical values

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

161

Exothermic

NTNU - In-Situ Combustion

SIS Training

April 10

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

NTNU - In-Situ Combustion

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April 10

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163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

NTNU - In-Situ Combustion

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165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

NTNU - In-Situ Combustion

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April 10

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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SIS Training

April 10

Schlumberger Private

174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

Page 71: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

141

Reactants and Products

Reactants ndash need for combustionndash Oxygenndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of the combustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

142

Reactants and Products

Products of the oxidation of oil or coke arendash Water ndash in the vapor phase until it contacts cold rock or oilndash Oxides of carbon ndash CO2 and CO

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

143

CVTYPE

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

144

Phases corresponding to each volatility type

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

146

Chemical Reaction Keywords

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

147

RUNSPEC and PROPS Keywords

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

148

RUNSPEC Keywords

NTNU - In-Situ Combustion

SIS Training

April 10

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACTION Example

REACTION4

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151

PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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153

Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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154

Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

NTNU - In-Situ Combustion

SIS Training

April 10

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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157

REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

NTNU - In-Situ Combustion

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April 10

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158

REACENTH ndash typical values

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159

REACENTH ndash more typical values

NTNU - In-Situ Combustion

SIS Training

April 10

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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161

Exothermic

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April 10

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

NTNU - In-Situ Combustion

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April 10

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

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April 10

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170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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SIS Training

April 10

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171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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SIS Training

April 10

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172

Reaction Rate Units in ECLIPSE Thermal

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SIS Training

April 10

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

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SIS Training

April 10

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189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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CVTYPE

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144

Phases corresponding to each volatility type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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146

Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

NTNU - In-Situ Combustion

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April 10

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153

Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

NTNU - In-Situ Combustion

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April 10

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154

Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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SIS Training

April 10

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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157

REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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April 10

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158

REACENTH ndash typical values

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April 10

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159

REACENTH ndash more typical values

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SIS Training

April 10

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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SIS Training

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161

Exothermic

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April 10

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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April 10

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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April 10

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

NTNU - In-Situ Combustion

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April 10

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146

Chemical Reaction Keywords

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April 10

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147

RUNSPEC and PROPS Keywords

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April 10

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

NTNU - In-Situ Combustion

SIS Training

April 10

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REACTION Example

REACTION4

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151

PROPS Keywords

NTNU - In-Situ Combustion

SIS Training

April 10

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

153

Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

154

Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

NTNU - In-Situ Combustion

SIS Training

April 10

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

NTNU - In-Situ Combustion

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157

REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

NTNU - In-Situ Combustion

SIS Training

April 10

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158

REACENTH ndash typical values

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SIS Training

April 10

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159

REACENTH ndash more typical values

NTNU - In-Situ Combustion

SIS Training

April 10

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

NTNU - In-Situ Combustion

SIS Training

April 10

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161

Exothermic

NTNU - In-Situ Combustion

SIS Training

April 10

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

NTNU - In-Situ Combustion

SIS Training

April 10

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163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

NTNU - In-Situ Combustion

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April 10

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165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

NTNU - In-Situ Combustion

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April 10

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

NTNU - In-Situ Combustion

SIS Training

April 10

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

NTNU - In-Situ Combustion

SIS Training

April 10

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

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174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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April 10

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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153

Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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April 10

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154

Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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SIS Training

April 10

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

157

REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

158

REACENTH ndash typical values

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

159

REACENTH ndash more typical values

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

NTNU - In-Situ Combustion

SIS Training

April 10

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161

Exothermic

NTNU - In-Situ Combustion

SIS Training

April 10

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

NTNU - In-Situ Combustion

SIS Training

April 10

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163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

NTNU - In-Situ Combustion

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April 10

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165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

NTNU - In-Situ Combustion

SIS Training

April 10

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

NTNU - In-Situ Combustion

SIS Training

April 10

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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SIS Training

April 10

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACTION Example

REACTION4

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April 10

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151

PROPS Keywords

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April 10

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

153

Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

NTNU - In-Situ Combustion

SIS Training

April 10

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154

Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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April 10

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157

REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

158

REACENTH ndash typical values

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

159

REACENTH ndash more typical values

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

161

Exothermic

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

NTNU - In-Situ Combustion

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April 10

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

NTNU - In-Situ Combustion

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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April 10

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

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170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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April 10

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174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORDStoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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153

Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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April 10

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154

Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

NTNU - In-Situ Combustion

SIS Training

April 10

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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April 10

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159

REACENTH ndash more typical values

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SIS Training

April 10

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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161

Exothermic

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April 10

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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April 10

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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April 10

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

NTNU - In-Situ Combustion

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April 10

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

NTNU - In-Situ Combustion

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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SIS Training

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

172

Reaction Rate Units in ECLIPSE Thermal

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SIS Training

April 10

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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April 10

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174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

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182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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153

Reaction Rate - ECLIPSE Nomenclature and Variables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE)ndash The porosity order nrp (REACPORD)ndash The component concentrations to the power of the index or order nri

(REACCORD)ndash The component concentration cri in reacting phase (REACPHA)ndash The activation energy Er (REACACT)ndash The gas constant Rndash The temperature Tndash The bulk volume Vb

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154

Reaction Rate ndash ECLIPSE Nomenclature

rinrirrbr cRTEAVR Πsdotminussdotsdot= ))(exp(

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April 10

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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157

REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

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158

REACENTH ndash typical values

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159

REACENTH ndash more typical values

NTNU - In-Situ Combustion

SIS Training

April 10

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

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161

Exothermic

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April 10

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162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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April 10

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

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April 10

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

NTNU - In-Situ Combustion

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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SIS Training

April 10

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176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

Page 78: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp(RTER r

r minusprop

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

157

REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

158

REACENTH ndash typical values

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

159

REACENTH ndash more typical values

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

161

Exothermic

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

157

REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

158

REACENTH ndash typical values

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

159

REACENTH ndash more typical values

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

161

Exothermic

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

Page 80: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

159

REACENTH ndash more typical values

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlb mol)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

161

Exothermic

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

161

Exothermic

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

162

REACCORD

Order of component terms in chemical reaction rates

Gives the order of reaction nc

If Rr is the reaction rate

And mc is the concentration of component c in the reacting phase

Then nc (REACCORD) is the index or order of the reactants

cncr mR )(prop

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2OAll reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase reactndash OIL - if only the oil phase reactsndash GAS ndash if only the gas phase reactsndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressurendash WAT ndash if the component is water in the water phasendash NONE ndash if the reaction rate is independent of the componentndash Default is ALLndash Phases are ignored for components with reaction order = 0

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined by REACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentration order (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

170

Reaction Rate Constant

As previously statedndash Units depend on order of reactionndash Values should be determined experimentallyndash Values vary widelyndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

Page 86: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

172

Reaction Rate Units in ECLIPSE Thermal

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

Page 87: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

174

STOPROD

Stoichiometric coefficient for productsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

176

STOPROD and STOREAC Example

If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

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NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or blockndash FREAC_1 for reaction 1 in LB-MDAY for Fieldndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for fieldndash FREAT_1 for reaction 1 in LB-MOLES

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

Page 91: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

182

Example Exercise Wet Forward Combustion SimulationSensitivity Study of Water Air Ratio (WAR)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

Page 92: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Objective

Determine the optimum Water Air Ratio to maximize the oil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx = Δy = Δz = 2 feetPorosity = 025Permeability = 2000 mD

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

Page 93: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600 o F air (and) water for 3 daysInject 100 o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

FloViz View of the Grid

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

Page 94: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Temperature ndash hot at the inlet (500 o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C2006 ndash C3600 ndash H2O

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

Page 95: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

189

Sensitivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture

Page 96: Schlumberger - NTNU Ambassador Lecture Serieskleppe/TPG4160/Kossack-In-SituCombustionLecture.… · Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

NTNU - In-Situ Combustion

SIS Training

April 10

Schlumberger Private

End of Lecture