Post on 25-Apr-2018
Schlumberger - NTNU Ambassador Lecture Series
In-Situ Combustion Simulation with ECLIPSE
ByChuck Kossack
Schlumberger AdvisorDenver Colorado
NTNU - In-Situ Combustion
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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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SIS Training
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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
NTNU - In-Situ Combustion
SIS Training
April 10
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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)
NTNU - In-Situ Combustion
SIS Training
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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
SIS Training
April 10
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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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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
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April 10
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17
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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April 10
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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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April 10
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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
NTNU - In-Situ Combustion
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April 10
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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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April 10
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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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April 10
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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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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
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April 10
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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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April 10
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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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April 10
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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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44
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
=Δ
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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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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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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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
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
Review of Thermal Reservoir Simulation
Key Points From Last Yearrsquos Lecture
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
In-Situ Combustion Simulation
NTNU - In-Situ Combustion
SIS Training
April 10
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14
Overview of the Lecture and Basic Chemical Reaction Theory
NTNU - In-Situ Combustion
SIS Training
April 10
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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
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
16
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
SIS Training
April 10
Schlumberger Private
17
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
SIS Training
April 10
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18
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
SIS Training
April 10
Schlumberger Private
19
Reaction Types
Direct combination - synthesis
322 23 NHHN rarr+
Chemical decomposition - analysis
222 22 OHOH +rarr
NTNU - In-Situ Combustion
SIS Training
April 10
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20
Reaction Types
Single displacement - substitution
2222 HNaClHClNa +rarr+
Double displacement
AgClNaNOAgNONaCl +rarr+ 33
NTNU - In-Situ Combustion
SIS Training
April 10
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21
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
SIS Training
April 10
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22
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
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24
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
NTNU - In-Situ Combustion
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April 10
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25
Chemical Kinetics
Rate of a chemical reaction - measure of how the concentration or pressure of the involved substances changes with time
NTNU - In-Situ Combustion
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April 10
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26
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
NTNU - In-Situ Combustion
SIS Training
April 10
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27
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
SIS Training
April 10
Schlumberger Private
28
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
SIS Training
April 10
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29
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
SIS Training
April 10
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30
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
NTNU - In-Situ Combustion
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April 10
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31
Activation energy with and without catalyst
biological catalyst is termed an enzyme
NTNU - In-Situ Combustion
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April 10
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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
SIS Training
April 10
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33
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
NTNU - In-Situ Combustion
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April 10
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34
Activation energy - threshold energy - Ea
NTNU - In-Situ Combustion
SIS Training
April 10
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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
SIS Training
April 10
Schlumberger Private
36
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
NTNU - In-Situ Combustion
SIS Training
April 10
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37
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)
NTNU - In-Situ Combustion
SIS Training
April 10
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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
SIS Training
April 10
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39
Stoichiometry
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April 10
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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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April 10
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41
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
NTNU - In-Situ Combustion
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April 10
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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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April 10
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43
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
NTNU - In-Situ Combustion
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April 10
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44
Reaction Rate Rate Equation Rate Law
NTNU - In-Situ Combustion
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April 10
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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
NTNU - In-Situ Combustion
SIS Training
April 10
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46
Some Reactions are Slow ndash oxidation of Iron
NTNU - In-Situ Combustion
SIS Training
April 10
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47
Some Reaction are Fast ndash oxidation of wood
NTNU - In-Situ Combustion
SIS Training
April 10
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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
SIS Training
April 10
Schlumberger Private
49
Reaction Rate
[ ] [ ] [ ] [ ]dtQd
qdtPd
pdtBd
bdtAd
av 1111
==minus=minus=
NTNU - In-Situ Combustion
SIS Training
April 10
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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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51
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
NTNU - In-Situ Combustion
SIS Training
April 10
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52
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
NTNU - In-Situ Combustion
SIS Training
April 10
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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
NTNU - In-Situ Combustion
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April 10
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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
SIS Training
April 10
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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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April 10
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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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April 10
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57
Effect of Catalyst on Reaction
NTNU - In-Situ Combustion
SIS Training
April 10
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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
SIS Training
April 10
Schlumberger Private
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)
NTNU - In-Situ Combustion
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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)
NTNU - In-Situ Combustion
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61
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
NTNU - In-Situ Combustion
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April 10
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62
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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April 10
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63
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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April 10
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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
NTNU - In-Situ Combustion
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April 10
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65
Reaction Order
NTNU - In-Situ Combustion
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April 10
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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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April 10
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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
NTNU - In-Situ Combustion
SIS Training
April 10
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68
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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April 10
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69
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
NTNU - In-Situ Combustion
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April 10
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70
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
NTNU - In-Situ Combustion
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71
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
Excel Calculation of Reaction Rate ndash Zero First Second Orders
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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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April 10
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75
First Order Reactions
NTNU - In-Situ Combustion
SIS Training
April 10
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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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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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April 10
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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
SIS Training
April 10
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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
NTNU - In-Situ Combustion
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82
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
NTNU - In-Situ Combustion
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83
Second Order Reactions
NTNU - In-Situ Combustion
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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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
Simple Second Order Reactions
dtkAAd
sdot=minus 22][][
Separation of variables gives
NTNU - In-Situ Combustion
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April 10
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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
SIS Training
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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
SIS Training
April 10
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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
NTNU - In-Situ Combustion
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90
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
NTNU - In-Situ Combustion
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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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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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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
=Δ
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
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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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April 10
Schlumberger Private
Review of Thermal Reservoir Simulation
Key Points From Last Yearrsquos Lecture
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
In-Situ Combustion Simulation
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
14
Overview of the Lecture and Basic Chemical Reaction Theory
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
16
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
SIS Training
April 10
Schlumberger Private
17
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
SIS Training
April 10
Schlumberger Private
18
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
SIS Training
April 10
Schlumberger Private
19
Reaction Types
Direct combination - synthesis
322 23 NHHN rarr+
Chemical decomposition - analysis
222 22 OHOH +rarr
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
20
Reaction Types
Single displacement - substitution
2222 HNaClHClNa +rarr+
Double displacement
AgClNaNOAgNONaCl +rarr+ 33
NTNU - In-Situ Combustion
SIS Training
April 10
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21
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
SIS Training
April 10
Schlumberger Private
22
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
24
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
NTNU - In-Situ Combustion
SIS Training
April 10
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25
Chemical Kinetics
Rate of a chemical reaction - measure of how the concentration or pressure of the involved substances changes with time
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
26
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
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
27
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
SIS Training
April 10
Schlumberger Private
28
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
SIS Training
April 10
Schlumberger Private
29
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
SIS Training
April 10
Schlumberger Private
30
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
NTNU - In-Situ Combustion
SIS Training
April 10
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31
Activation energy with and without catalyst
biological catalyst is termed an enzyme
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April 10
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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
SIS Training
April 10
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33
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
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
34
Activation energy - threshold energy - Ea
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
36
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
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
37
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)
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
39
Stoichiometry
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SIS Training
April 10
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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
SIS Training
April 10
Schlumberger Private
41
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
NTNU - In-Situ Combustion
SIS Training
April 10
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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
SIS Training
April 10
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43
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
NTNU - In-Situ Combustion
SIS Training
April 10
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44
Reaction Rate Rate Equation Rate Law
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
46
Some Reactions are Slow ndash oxidation of Iron
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
47
Some Reaction are Fast ndash oxidation of wood
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
49
Reaction Rate
[ ] [ ] [ ] [ ]dtQd
qdtPd
pdtBd
bdtAd
av 1111
==minus=minus=
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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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April 10
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51
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
NTNU - In-Situ Combustion
SIS Training
April 10
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52
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
NTNU - In-Situ Combustion
SIS Training
April 10
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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
NTNU - In-Situ Combustion
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April 10
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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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
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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
SIS Training
April 10
Schlumberger Private
57
Effect of Catalyst on Reaction
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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)
NTNU - In-Situ Combustion
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April 10
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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)
NTNU - In-Situ Combustion
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April 10
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61
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
NTNU - In-Situ Combustion
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April 10
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62
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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April 10
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63
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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April 10
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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
NTNU - In-Situ Combustion
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April 10
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65
Reaction Order
NTNU - In-Situ Combustion
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April 10
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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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April 10
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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
NTNU - In-Situ Combustion
SIS Training
April 10
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68
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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April 10
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69
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
NTNU - In-Situ Combustion
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April 10
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70
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
NTNU - In-Situ Combustion
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April 10
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71
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
Excel Calculation of Reaction Rate ndash Zero First Second Orders
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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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April 10
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75
First Order Reactions
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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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April 10
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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
SIS Training
April 10
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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
NTNU - In-Situ Combustion
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82
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
NTNU - In-Situ Combustion
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83
Second Order Reactions
NTNU - In-Situ Combustion
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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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
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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
NTNU - In-Situ Combustion
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90
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
NTNU - In-Situ Combustion
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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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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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95
Example of Third Order Reaction
In the atmosphere
2NO + O2 rarr 2NO2
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96
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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97
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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101
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
NTNU - In-Situ Combustion
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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
=Δ
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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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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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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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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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
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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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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
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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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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
=Δ
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
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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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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
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36
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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37
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
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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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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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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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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
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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=
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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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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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
=Δ
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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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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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
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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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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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49
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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51
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
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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
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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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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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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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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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SIS Training
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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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SIS Training
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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
SIS Training
April 10
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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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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
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
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SIS Training
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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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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
=Δ
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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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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129
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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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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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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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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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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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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71
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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SIS Training
April 10
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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
SIS Training
April 10
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Excel Calculation of Reaction Rate ndash Zero First Second Orders
NTNU - In-Situ Combustion
SIS Training
April 10
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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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April 10
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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
SIS Training
April 10
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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
SIS Training
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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
SIS Training
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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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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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SIS Training
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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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SIS Training
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Simple Second Order Reactions
dtkAAd
sdot=minus 22][][
Separation of variables gives
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SIS Training
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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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SIS Training
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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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SIS Training
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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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SIS Training
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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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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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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
=Δ
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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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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129
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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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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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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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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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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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
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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
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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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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
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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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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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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
=Δ
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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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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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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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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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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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
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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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37
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
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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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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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49
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
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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
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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
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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
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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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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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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
=Δ
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
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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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34
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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36
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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SIS Training
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37
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
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SIS Training
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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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41
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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49
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
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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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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
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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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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
SIS Training
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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=
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
=
=
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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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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
=Δ
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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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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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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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
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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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62
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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SIS Training
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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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SIS Training
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Excel Calculation of Reaction Rate ndash Zero First Second Orders
NTNU - In-Situ Combustion
SIS Training
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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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SIS Training
April 10
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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=
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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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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SIS Training
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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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SIS Training
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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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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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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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Heat of Combustion
air Btuscf250501
231967094xm
xmha +minus+minus
=Δ
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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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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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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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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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
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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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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
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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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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
=Δ
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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125
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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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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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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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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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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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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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
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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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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
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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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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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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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Heat of Combustion
air Btuscf250501
231967094xm
xmha +minus+minus
=Δ
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
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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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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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SIS Training
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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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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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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
=Δ
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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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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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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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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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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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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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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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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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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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
=Δ
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
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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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36
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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37
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
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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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41
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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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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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
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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
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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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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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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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
=Δ
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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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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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
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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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75
First Order Reactions
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
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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
SIS Training
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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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SIS Training
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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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
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Simple Second Order Reactions
dtkAAd
sdot=minus 22][][
Separation of variables gives
NTNU - In-Situ Combustion
SIS Training
April 10
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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
SIS Training
April 10
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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
SIS Training
April 10
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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
NTNU - In-Situ Combustion
SIS Training
April 10
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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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SIS Training
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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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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
=Δ
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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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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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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129
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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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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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
NTNU - In-Situ Combustion
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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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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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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
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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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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
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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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37
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
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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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41
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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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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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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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
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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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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
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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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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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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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104
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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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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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
=Δ
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
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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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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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71
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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SIS Training
April 10
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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
SIS Training
April 10
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Excel Calculation of Reaction Rate ndash Zero First Second Orders
NTNU - In-Situ Combustion
SIS Training
April 10
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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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April 10
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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
SIS Training
April 10
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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
SIS Training
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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
SIS Training
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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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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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SIS Training
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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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SIS Training
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Simple Second Order Reactions
dtkAAd
sdot=minus 22][][
Separation of variables gives
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SIS Training
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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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SIS Training
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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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SIS Training
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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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SIS Training
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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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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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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
=Δ
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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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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129
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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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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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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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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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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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
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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
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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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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
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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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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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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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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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49
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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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
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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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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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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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106
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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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
=Δ
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
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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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63
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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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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68
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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71
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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SIS Training
April 10
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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
SIS Training
April 10
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Excel Calculation of Reaction Rate ndash Zero First Second Orders
NTNU - In-Situ Combustion
SIS Training
April 10
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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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April 10
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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
SIS Training
April 10
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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
SIS Training
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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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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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SIS Training
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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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SIS Training
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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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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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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
=Δ
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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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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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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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
NTNU - In-Situ Combustion
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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
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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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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
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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
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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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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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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
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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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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
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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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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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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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104
API Classifications
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105
Canada Forecast
In-situ = steam drive HampP in-situ combustion SAGD VAPEX
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106
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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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
=Δ
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
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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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71
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
SIS Training
April 10
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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
SIS Training
April 10
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Excel Calculation of Reaction Rate ndash Zero First Second Orders
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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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SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
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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
SIS Training
April 10
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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
NTNU - In-Situ Combustion
SIS Training
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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
=
=
NTNU - In-Situ Combustion
SIS Training
April 10
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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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SIS Training
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Simple Second Order Reactions
dtkAAd
sdot=minus 22][][
Separation of variables gives
NTNU - In-Situ Combustion
SIS Training
April 10
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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
SIS Training
April 10
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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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SIS Training
April 10
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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
NTNU - In-Situ Combustion
SIS Training
April 10
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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
SIS Training
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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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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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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
=Δ
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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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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129
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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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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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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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
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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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158
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
NTNU - In-Situ Combustion
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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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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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181
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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April 10
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FloViz View of the Grid
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April 10
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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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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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49
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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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
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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
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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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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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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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71
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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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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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
=Δ
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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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
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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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82
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
=Δ
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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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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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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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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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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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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190
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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51
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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52
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
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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
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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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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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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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62
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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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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SIS Training
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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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SIS Training
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Excel Calculation of Reaction Rate ndash Zero First Second Orders
NTNU - In-Situ Combustion
SIS Training
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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
SIS Training
April 10
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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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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
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
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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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SIS Training
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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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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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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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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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106
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
=Δ
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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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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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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129
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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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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143
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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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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190
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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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
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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
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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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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
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63
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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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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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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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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90
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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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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101
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
=Δ
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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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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70
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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71
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
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Excel Calculation of Reaction Rate ndash Zero First Second Orders
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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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SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
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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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SIS Training
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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
SIS Training
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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
NTNU - In-Situ Combustion
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83
Second Order Reactions
NTNU - In-Situ Combustion
SIS Training
April 10
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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
SIS Training
April 10
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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
SIS Training
April 10
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Simple Second Order Reactions
dtkAAd
sdot=minus 22][][
Separation of variables gives
NTNU - In-Situ Combustion
SIS Training
April 10
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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
SIS Training
April 10
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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
SIS Training
April 10
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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
NTNU - In-Situ Combustion
SIS Training
April 10
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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
SIS Training
April 10
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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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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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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
=Δ
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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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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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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129
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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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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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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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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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
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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
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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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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
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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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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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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
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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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190
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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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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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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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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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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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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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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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
=Δ
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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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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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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129
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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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
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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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100
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
=Δ
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
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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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April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
Excel Calculation of Reaction Rate ndash Zero First Second Orders
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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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SIS Training
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75
First Order Reactions
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SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
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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
SIS Training
April 10
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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
NTNU - In-Situ Combustion
SIS Training
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83
Second Order Reactions
NTNU - In-Situ Combustion
SIS Training
April 10
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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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
Simple Second Order Reactions
dtkAAd
sdot=minus 22][][
Separation of variables gives
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
NTNU - In-Situ Combustion
SIS Training
April 10
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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
SIS Training
April 10
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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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102
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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SIS Training
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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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SIS Training
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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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SIS Training
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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)
NTNU - In-Situ Combustion
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April 10
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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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SIS Training
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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
=Δ
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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123
Combustion Processes
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April 10
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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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129
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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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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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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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
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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
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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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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
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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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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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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
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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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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
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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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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
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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SIS Training
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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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SIS Training
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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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63
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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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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69
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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SIS Training
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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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SIS Training
April 10
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Excel Calculation of Reaction Rate ndash Zero First Second Orders
NTNU - In-Situ Combustion
SIS Training
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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
SIS Training
April 10
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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
SIS Training
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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
SIS Training
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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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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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SIS Training
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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
NTNU - In-Situ Combustion
SIS Training
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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
SIS Training
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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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SIS Training
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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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90
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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104
API Classifications
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105
Canada Forecast
In-situ = steam drive HampP in-situ combustion SAGD VAPEX
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106
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
=Δ
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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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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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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129
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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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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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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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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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
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65
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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104
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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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
=Δ
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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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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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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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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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
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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 =
NTNU - In-Situ Combustion
SIS Training
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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=
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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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
=Δ
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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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
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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SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
Schlumberger Private
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
SIS Training
April 10
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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
SIS Training
April 10
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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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SIS Training
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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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SIS Training
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Simple Second Order Reactions
dtkAAd
sdot=minus 22][][
Separation of variables gives
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SIS Training
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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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SIS Training
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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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SIS Training
April 10
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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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SIS Training
April 10
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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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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
=Δ
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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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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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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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
NTNU - In-Situ Combustion
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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
NTNU - In-Situ Combustion
SIS Training
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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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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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SIS Training
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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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SIS Training
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Initial Temperature ndash hot at the inlet (500 o F)
injection
production
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SIS Training
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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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71
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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SIS Training
April 10
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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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SIS Training
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Excel Calculation of Reaction Rate ndash Zero First Second Orders
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SIS Training
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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
SIS Training
April 10
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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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SIS Training
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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
SIS Training
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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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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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SIS Training
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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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SIS Training
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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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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
=Δ
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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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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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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129
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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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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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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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
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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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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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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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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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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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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
=Δ
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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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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129
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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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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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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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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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
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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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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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Heat of Combustion
air Btuscf250501
231967094xm
xmha +minus+minus
=Δ
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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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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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
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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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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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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
=Δ
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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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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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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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
=Δ
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
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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
=Δ
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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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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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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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
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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
=Δ
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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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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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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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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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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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
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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
=Δ
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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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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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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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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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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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
=Δ
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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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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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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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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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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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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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
=Δ
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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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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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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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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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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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
=Δ
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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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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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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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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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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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
=Δ
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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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
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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
=Δ
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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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
=Δ
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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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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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
=Δ
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
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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
=Δ
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
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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
=Δ
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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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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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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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
=Δ
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
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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
=Δ
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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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
=Δ
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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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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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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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
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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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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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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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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
=Δ
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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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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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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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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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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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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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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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
=Δ
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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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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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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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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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
=Δ
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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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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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
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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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STOPROD and STOREAC Example
If have seven components + waterndash CO2 ndash N2ndash C1ndash O2ndash C10ndash C20ndash C36
NTNU - In-Situ Combustion
SIS Training
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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
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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SIS Training
April 10
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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
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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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SIS Training
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Oil Recovery Factor for Various Water Air Ratios
Dry combustion
Increasing WAR
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SIS Training
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End of Lecture
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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
=Δ
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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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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April 10
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125
Saturations and Temperature Profiles in Dry Forward Combustion
NTNU - In-Situ Combustion
SIS Training
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126
Wet Combustion
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SIS Training
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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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129
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
NTNU - In-Situ Combustion
SIS Training
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130
Saturation and Temperatures during Wet Combustion
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SIS Training
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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
NTNU - In-Situ Combustion
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April 10
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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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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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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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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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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
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
NTNU - In-Situ Combustion
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FloViz View of the Grid
NTNU - In-Situ Combustion
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April 10
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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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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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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
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Schlumberger Private
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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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
=Δ
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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April 10
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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
NTNU - In-Situ Combustion
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April 10
Schlumberger Private
125
Saturations and Temperature Profiles in Dry Forward Combustion
NTNU - In-Situ 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
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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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129
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
NTNU - In-Situ Combustion
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April 10
Schlumberger Private
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
NTNU - In-Situ Combustion
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April 10
Schlumberger Private
132
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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143
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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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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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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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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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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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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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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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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172
Reaction Rate Units in ECLIPSE Thermal
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SIS Training
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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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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
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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
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
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FloViz View of the Grid
NTNU - In-Situ Combustion
SIS Training
April 10
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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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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
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190
Water Air Ratio
No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low
Temperature Oxidation)
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SIS Training
April 10
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Oil Recovery Factor for Various Water Air Ratios
Dry combustion
Increasing WAR
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SIS Training
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End of Lecture
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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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SIS Training
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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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129
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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SIS Training
April 10
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130
Saturation and Temperatures during Wet Combustion
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SIS Training
April 10
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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
NTNU - In-Situ Combustion
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April 10
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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
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SIS Training
April 10
Schlumberger Private
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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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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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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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
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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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158
REACENTH ndash typical values
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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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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
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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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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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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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
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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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
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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
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End of Lecture
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125
Saturations and Temperature Profiles in Dry Forward Combustion
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126
Wet Combustion
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April 10
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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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129
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
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
130
Saturation and Temperatures during Wet Combustion
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SIS Training
April 10
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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
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
132
Temperature and Saturation during Reverse Combustion
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
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136
End of Section 2
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SIS Training
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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
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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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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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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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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)
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
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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
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End of Lecture
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129
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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SIS Training
April 10
Schlumberger Private
130
Saturation and Temperatures during Wet Combustion
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
132
Temperature and Saturation during Reverse Combustion
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
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136
End of Section 2
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SIS Training
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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
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SIS Training
April 10
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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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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
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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
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SIS Training
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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
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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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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
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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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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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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
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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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
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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
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End of Lecture
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April 10
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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
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
132
Temperature and Saturation during Reverse Combustion
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
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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
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
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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
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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
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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
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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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158
REACENTH ndash typical values
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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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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
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
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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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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
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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
NTNU - In-Situ Combustion
SIS Training
April 10
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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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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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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
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
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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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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
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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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SIS Training
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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
SIS Training
April 10
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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
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
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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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SIS Training
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
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SIS Training
April 10
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148
RUNSPEC Keywords
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SIS Training
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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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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
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SIS Training
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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)
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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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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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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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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
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
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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
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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
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
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
Schlumberger Private
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
SIS Training
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
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
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
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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
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
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
Schlumberger Private
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
SIS Training
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
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
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
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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
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
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
Schlumberger Private
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
SIS Training
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
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
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
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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
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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
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
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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
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SIS Training
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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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SIS Training
April 10
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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
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
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
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SIS Training
April 10
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146
Chemical Reaction Keywords
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
147
RUNSPEC and PROPS Keywords
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SIS Training
April 10
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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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SIS Training
April 10
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151
PROPS Keywords
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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
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
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SIS Training
April 10
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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
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
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
Schlumberger Private
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
SIS Training
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
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
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
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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
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SIS Training
April 10
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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
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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
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
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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
Schlumberger Private
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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SIS Training
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
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
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
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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
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
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
Schlumberger Private
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
SIS Training
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
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
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
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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
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
NTNU - In-Situ Combustion
SIS Training
April 10
Schlumberger Private
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
SIS Training
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
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
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
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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
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
NTNU - In-Situ Combustion
SIS Training
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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