Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e...

142
Refinery Modeling Aaron Smith, Michael Frow, Joe Quddus, Donovan Howell, Thomas Reed, Clark Landrum, Brian Clifton May 2, 2006

Transcript of Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e...

Page 1: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Refinery Modeling

Aaron Smith, Michael Frow, Joe Quddus, Donovan Howell, Thomas Reed, Clark Landrum,

Brian CliftonMay 2, 2006

Page 2: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

The

Big

Black

Box

Page 3: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

The

Big

Black

Box

DemandCrude B

Crude C

Crude A

Costs

Profit

Page 4: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

The

Big

Black

Box

DemandCrude B

Crude C

Crude A

Costs

Profit

Page 5: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2
Page 6: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Hydrotreating

INPUT:TemperaturePressureH2/HC RatioSulfur %Nitrogen %

OUTPUT:Sulfur %Nitrogen %Aromatic %

MODEL:PBR

Page 7: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

http://www.osha.gov/dts/osta/otm/otm_iv/otm_iv_2fig25.gif

Page 8: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

A future of energy production…

Hydrotreating

• Removal of sulfur, nitrogen, and aromatics.

• Government regulations are leading to increased sulfur removal requirements.

Page 9: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Typical Processing

Conditions

35580020000.75-2.0Heavy Gas

Oil

42570015000.7-1.5Light Gas

Oil

3304008001.0-4.0Middle

Distillate

2902003001.0-5.0Naptha

Temperature (oC)

H2 Pressure

(psia)H2/HCSpace velocity

Page 10: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Hydrotreating

• Cracking is assumed to be insignificant.– Therefore, properties such as density and

molecular weight are assumed to be constant.

Page 11: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Hydrotreating

• Cracking is assumed to be insignificant.– Therefore, properties such as density and

molecular weight are assumed to be constant.

Page 12: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Hydrotreating Model

• For MoCo catalyst reaction rates are:– Rates= ksCs

2CH2.75

– Raten= knCn1.4CH2

.6

– Ratear= karCarCH2

http://www.chem.wwu.edu/dept/facstaff/bussell/research/images/thio-HDS.jpg

Page 13: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2
Page 14: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Delayed Coking

INPUT:CCRPressure

OUTPUT:Gas OilCokeGasNaptha

MODEL:Correlation

Page 15: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Delayed Coking

• Used to process bottoms from the vacuum distillate.

• Breaks down this portion into usable napthas, gas, and gas oil.

Page 16: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Delayed Coking

• Coke Products– Shot Coke– Sponge Coke – Needle Coke

Page 17: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Delayed Coking Model

• Most important parameter is the ConradsonCarbon Residue.– Coke = 1.6 x CCR– Gas = 7.8 + .144 x CCR– Naptha = 11.29 + .343 x CCR– Gas oil = 100 – Coke – Gas - Naptha

• This is an estimate from Gary and Handwerk

Page 18: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Effect of Pressure on

Product

44.951.243.1Gas Oil Yield

1512.517.5Naptha Yield

9.99.110.4Gas Yield

30.227.229Coke

35 psig15 psigCorrelation

18.1CCR (wt%)

Page 19: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Delayed Coking Model

• Modified Equations– Gas = (7.4 + (.1 x CCR)) + (.8 x (P-15)/20)– Naptha = (10.29 + (.2 x CCR)) + (2.5 x (P-15)/20)– Coke = (1.5 x CCR) + (3 x (P-15)/20)– Gas oil = 100 – Gas – Naptha - Coke

Page 20: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

New Correlation

44.951.243.449.7Gas Oil Yield

1512.516.413.9Naptha Yield

9.99.110.09.2Gas Yield

30.227.230.227.2Coke

35 psig15 psigCorrelation (35 psig)

Correlation (15 psig)

18.1CCR (wt%)

Page 21: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2
Page 22: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Catalytic Reforming

INPUT:TemperaturePressure% Napthenes% Aromatics% Paraffins

OUTPUT:HydrogenLPGReformate

MODEL:PBR

Page 23: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Catalytic Reforming

Page 24: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Catalytic ReformingHydrogen Intensive Process Units

Xylenes Isomerization

Boilers

Page 25: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Catalytic Reforming

• Simplified reactions and equations from Case Study 108 by Rase

( )( )( )( ) napthenesofingHydrocrack

paraffinsofingHydrocrack

HnapthenesParaffins

HaromaticsNapthenes

__4

__3

2

*31

2

2

+→←

+→←

Page 26: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Catalytic Reforming

( ) 5432122 151515151534 C

nC

nC

nC

nC

nH

nHC nn ++++→+

( ) 54321222 15151515153

33 C

nC

nC

nC

nC

nH

nHC nn ++++→

−++

( ) 22222 HHCHC nnnn +→←+

( ) 2622 31 HHCHC nnnn +→← −

Page 27: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Catalytic Reforming

[ ]( )( )( )atmcatlbhr

moles

TkP ._

,34750

21.23exp1 =

−=)

[ ]( )( )( )22._

,59600

98.35expatmcatlbhr

moles

TkP =

−=)

[ ]( )( )._,

6230097.42exp43 catlbhr

moles

Tkk PP =

−==))

[ ] 33

1 ,46045

15.46exp*

atmTP

PPK

N

HAP =

−==

[ ] 12 ,12.7

8000exp

*−=

−== atmTPP

PK

HN

PP

Page 28: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Catalytic Reforming

[ ] ( )( )._

____*

222 catlbhr

paraffinstoconvertednapthenemoles

K

PPPkr

P

PHNP =

−=−

))

[ ] ( )( )._

____33 catlbhr

inghydrocrackbyconvertedparaffinsmoles

P

Pkr P

P =

=−))

[ ] ( )( )._

____*

1

3

11 catlbhr

aromaticstoconvertednapthenemoles

K

PPPkr

P

HANP =

−=−

))

[ ] ( )( )._

____44 catlbhr

inghydrocrackbyconvertednapthenesmoles

P

Pkr N

P =

=−))

Page 29: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Catalytic Reforming

Page 30: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Catalytic Reforming

Page 31: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2
Page 32: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

XylenesIsomerization

INPUT:Temperature

OUTPUT:BenzeneTolueneO-XyleneP-XyleneEthyl-Benzene

MODEL:Correlation

Page 33: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Xylenes Isomerization

Page 34: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Xylenes IsomerizationParaffins & Napthenes - Blending

Mixed Aromatics –Fractionation

Page 35: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Xylenes Isomerization

Page 36: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Xylenes Isomerization

Benzene & Toluene –Solvent Quality

Xylenes –Isomerization

C9+ Aromatics –Blending

Page 37: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Xylenes Isomerization

Page 38: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Xylenes Isomerization

O-Xylene –Chemical Feedstock

Mixed Aromatics –Blending

P-Xylene –Chemical Feedstock

Page 39: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Xylenes Isomerization

• Reaction driven by equilibrium

• Temperature dependence of equilibrium modeled in Kirk-Othmer Encyclopedia of Chemical Technology

neEthylBenzeXylenepXyleneoXylenem →←−→←−→←−

Page 40: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Xylenes Isomerization

Page 41: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2
Page 42: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Solvent Extraction

INPUT:TemperatureS/F Ratio

OUTPUT:Lube OilAromatics

MODEL:Correlation

Page 43: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Solvent Extraction

Page 44: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Solvent ExtractionParaffinic Oils - Solvent Dewaxing

Mixed Aromatics –Blending

Page 45: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Solvent Extraction

• Furfural Extraction – Averaged K Values– Benzene from Cyclohexane– Benzene from Iso-octane– 1,6-diphenylhexane from Docosane

• Temperature (ºR) dependence of K correlated from this

∑=

−=N

n

nEExtracted

0

11%F

SKE *=

( ) 371.7*0259.0522 −+−= TETK

Page 46: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Solvent Extraction

• Correlations developed from Institut Françaisdu Pétrole data

( ) 9318.00426.0*% +−

=F

SieldRaffinateY

( ) 9229.0)0073.0(*0004.0*..2

+

=F

S

F

SGRaffinateS

Page 47: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Solvent Extraction

Page 48: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Solvent Extraction

Page 49: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2
Page 50: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Visbreaker

INPUT:Temperature

OUTPUT:GasGasolineGas OilResidue

MODEL:PFR

Page 51: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Visbreaking

Page 52: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Visbreaking

• Carbon chains cracking into smaller chains of varying carbon numbers

Page 53: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

A future of energy production…

Visbreaking

Si-2 + O2

Si-3 + O3

Si-j + Oj

S2 + Oi-2

S1 + Oi-1

Si

• Si forms all components with carbons less than i-1

Page 54: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

A future of energy production…

Visbreaking

• Si is formed from all components with carbons greater than i+1

Si-2 + O2

Si-3 + O3

Si-j + Oj

S2 + Oi-2

S1 + Oi-1

Sn

Sn-1

Sk

Si+3

Si+2

On-i

On-1-i

Ok-i

O3

O2

Si

• Si forms all components with carbons less than i-1

Page 55: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Visbreaking

• First order kinetics with molar concentrations

∑∑−

=+=

−=2

1,

2,

i

jjii

n

ikkiki KCsCsKrs ∑

+=−=

n

ijjijji CsKro

1,

ii rs

Fdz

dCs ρπφ 2

4

1=i

i roFdz

dCo ρπφ 2

4

1=

Page 56: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Visbreaking

• Rate Constant dependent on molecular weight

RTBjiji

jieAK /,,

,−= jiji PMbPMbbB ⋅+⋅+= 210,

[ ]( )

2

3

4

2

1

2210,

−−

⋅+⋅+=a

a

PMPM

iiji

ij

ePMaPMaaA11.35

146.95

32.06E+06

-4.51.90E+08

428941.51E+12

ba

Page 57: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Visbreaking

• Model inputs– Temperature and mass flow rate

• Model Product form– Weight percents

– Components are lumped into 4 categories• Gas: C1-C4• Gasoline: C5-C10• Gas Oil: C11-C21• Residue: C22-C45

Page 58: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2
Page 59: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Isomerization

INPUT:TemperatureH2/HC Ratio

OUTPUT:Hydrocarbons

C4-C6

MODEL:PFR

Page 60: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Isomerization

Page 61: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Isomerization

• Main reactants: n-Butane, n-Pentane, n-Hexane• Typically catalyzed-gas phase reaction• Low temperature favors isomer formation• Seven rate laws

– Only one of n-Pentanes isomers forms

n-Butane i-Butane

n-Pentane i-Pentane

3-MP 2,2-DMB

2-Mp 2,3-DMB

n-Hex.

Page 62: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

A future of energy production…

Isomerization

• n-Butane

• n-Pentane

• n-Hexane

2

4

2

4

214H

Ciso

H

CnCn P

PK

P

PKr −−

− ⋅+⋅−=

[ ] ( )[ ]55

125.0

2

525 10000197.0 CieqCneq

CnCn CKCKt

H

CKr −−

−− ⋅+−⋅

⋅−

⋅−=

∑∑==

+⋅

−=

5

1,

5

1,

jjjii

jiji CKCKr

Page 63: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

A future of energy production…

Isomerization

• Model inputs– Temperature, mass flow rate, and H2/HC ratio

• Model Product form– Weight percents of the individual isomers

Page 64: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2
Page 65: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Hydrocracking

INPUT:ºAPIKwH2 /BBL

OUTPUT:Naptha

LightHeavy

C3 Upi-Butanen-ButaneGas Oil

MODEL:Correlation

Page 66: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

A future of energy production…

Hydrocracking

• Convert higher boiling point petroleum fractions into lighter fuel products

Page 67: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Hydrocracking

• Complementary Reactions– Cracking reactions

• Provides olefins for hydrogenation

R-C-C-C-R + heat → R-C=C + C-R

– Hydrogenation reactions• Provides heat for cracking

R-C=C + H2→ R-C-C + heat

Page 68: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Hydrocracking

• Feedstocks- Heavy distillate stocks, aromatics, cycle oils, and coker oils

• Catalysts- zeolites

• Operating conditions-

500-30002000-3000Pressure (psi)

500-900750 -800Temperature (°F)

0.5-100.2-1LHSV (hr-1)

1000-24001200-1600Hydrogen Consumption (SCFB)

DistillateResiduum

Page 69: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Hydrocracking Model

Development

• Correlated data from “Oil and Gas Journal” W.L. Nelson

• Graphical correlated data was made continuous for hydrogen feed rate, Kwand API of the feed

• 3 inputs• 5 outputs

Page 70: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Hydrocracking Model

Page 71: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Hydrocracking Model

y = 0.84165e0.00096x

R2 = 0.99872

y = 0.91507e0.00099x

R2 = 0.99903

y = 1.03077e0.00102x

R2 = 0.99873

y = 1.17542e0.00105x

R2 = 0.99820

y = 1.35330e0.00110x

R2 = 0.99840

y = 1.48461e0.00120x

R2 = 0.99938

y = 1.64851e0.00129x

R2 = 0.99707

y = 1.80073e0.00143x

R2 = 0.98730

y = 2.20169e0.00147x

R2 = 0.98763

y = 2.67927e0.00153x

R2 = 0.98715

y = 3.40926e0.00157x

R2 = 0.98555

0

10

20

30

40

50

60

70

80

90

100

0 500 1000 1500 2000 2500 3000

Hydrogen Rate SCFB

32.5

30

27.5

25

22.5

20

17.5

15

12.5

10

7.5

Page 72: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Hydrocracking Model

y = 1.852E-05x4 - 1.206E-03x3 + 2.920E-02x2 -

2.531E-01x + 1.546E+00R2 = 9.992E-01

0

0.5

1

1.5

2

2.5

3

3.5

4

0 10 20 30 40

API of Feed

A C

on

stan

t

y = 6.024E-11x6 - 6.539E-09x5 + 2.738E-07x4 - 5.600E-06x3 + 5.935E-05x2 - 2.996E-

04x + 1.509E-03R2 = 9.982E-01

0

0.0002

0.0004

0.0006

0.0008

0.001

0.0012

0.0014

0.0016

0.0018

0 10 20 30 40

API of FeedB

Co

nst

ant

Page 73: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Hydrocracking Model

Vol% of light naptha

Hydrogen Rate(SCFB) 7.5 10 12.5 15 17.5 20 22.5 25

2500 Kw=12.1 9.25 11 13 16 21 30 45 80

diff. from Kw=10.9 0.75 1 1 1.25 1.75 2.5 5 7.5

8.11% 9.09% 7.69% 7.81% 8.33% 8.33% 11.11% 9.38%

1500 Kw=12.1 3.4 4 4.8 5.8 7.3 9.1 11.25 14.25

diff. from Kw=10.9 0.35 0.45 0.5 0.55 0.7 1 1.5 1.75

10.29% 11.25% 10.42% 9.48% 9.59% 10.99% 13.33% 12.28%

500 Kw=12.1 1.4 1.55 1.7 2 2.3 2.8 3.4 4.2

diff. from Kw=10.9 0.1 0.17 0.2 0.2 0.25 0.3 0.35 0.4

7.14% 10.97% 11.76% 10.00% 10.87% 10.71% 10.29% 9.52%

°API

Page 74: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Hydrocracking Model

y = -0.7691x + 11.739R2 = 0.9916

0

0.5

1

1.5

2

2.5

3

3.5

4

10.5 11 11.5 12 12.5

Kw

slo

pe

Page 75: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Hydrocracking Equations

HBw AeKpvol •−= )00833.000833.1(% 1

)%(11.739) + K0.7691- (% 1w2 pvolpvol ⋅=)%(0.337 % 13 pvolpvol =)%(0.186 % 14 pvolpvol =

)%(0.091 % 15 pvolpvol +=

Page 76: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Hydrocracking Model

Hydrogen(SCFB)

15 2500 12.1 16.4 39.9actual 15.0 40.5

20 750 10.9 3.3 11.0actual 3.5 10.0

30 1250 10.9 16.3 54.7actual 13.0 43.0

°API Kw vol% p1 vol% p2

9%

25%

7%

1%

27%

9%

Page 77: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2
Page 78: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

SolventDewaxing

INPUT:CompositionTemperature

OUTPUT:WaxLube Oil

MODEL:Correlation

Page 79: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

A future of energy production…

Solvent Dewaxing

• Separate high pour point waxes from lubricating oils

Page 80: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Solvent Dewaxing

• Feedstocks– Distillate and residual stocks – heavy gas oils– Solvents – Ketones (MEK) and Propane

• Operating conditions– Solvent to oil ratio 1:1 to 4:1– Desired pour point of product

Page 81: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Dewaxing Model

Development• Correlation from “Energy and Fuels”

Krishna et. al.• 3 experimentally determined parameters

• 3 inputs• 2 outputs

2/1)/100log(0 ACLAPCAPPT ++=

( )( ))(100

)(100%)(

productPC

feedPCwtOilYield

−−=

Page 82: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Dewaxing Model Error

BC2 NC6 NC7 NC8 NC9 NC10°C 375-500 375-400 400-425 425-450 450-475 475-500

wax wt% 46.8 44.88 47.28 48.41 48.72 47.05CL 26.89 24.13 25.13 27.14 29.05 31

PPT act. 48 39 45 48 51 57PPT pred. 48.0 41.0 44.0 48.9 52.8 55.9

error % 0.1% 5.0% 2.3% 1.8% 3.5% 1.9%

dewaxing model Desired PPT= 10PPT low 9.99 9.50 9.77 9.82 9.65 9.81PPT high 10.01 10.50 10.23 10.18 10.35 10.19wax wt% low 0.368 0.819 0.608 0.336 0.202 0.133wax wt% high 0.369 0.931 0.643 0.352 0.220 0.139yield low 0.5340 0.5558 0.5304 0.5176 0.5138 0.5302yield high 0.5340 0.5564 0.5306 0.5177 0.5139 0.5302

error % 0.001% 0.112% 0.036% 0.016% 0.019% 0.006%

Page 83: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2
Page 84: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Alkylation

INPUT:Iso-butaneButylene / PropyleneReaction time

OUTPUT:PropaneButaneAlkylate

MODEL:Correlation

Page 85: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Alkylation PFD

http://www.prod.exxonmobil.com/refiningtechnologies/pdf/AlkyforWR02.pdf

Exxon-Mobil Autorefrigeration H2SO4 alkylation

Page 86: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Alkylation

*Lots of side reactions

Page 87: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Alkylation

O

FE

SV

OIIF

)(100

)/(=

FOI )/(

=EI

=OSV )(

= volumetric isobutane/olefin ratio in feed

isobutane in reactor effluent, liquid volume %

F= Factor defined by A.V. Mrstik

olefin space velocity, v/hr/v

“Progress in Petroleum Technology” AV Mrstik et al. ACS Publications

Page 88: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2
Page 89: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Polymerization

INPUT:Iso-butaneButylene / Propylene

OUTPUT:GasolineDiesel

MODEL:Correlation

Page 90: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

PolymerizationPolymerizationPolymerizationPolymerization

• Converts Propylenes and butylenes into saturated carbon chains

• 1st used Catalytic Solid Phosphoric Acid (SPA) on silica fell out of popularity in 1960s.

• Now experimenting with Zeolites.

C C

C

C + C C

C

C→

C C

C

CC C

C

C

C C C + C C C → C C

C

CC C

- Polymerization reaction is highly exothermic and temperature iscontrolled either by injecting cold propane quench or by generating steam.- Propane is also recycled to help control temperature

CO School of Mines http://jechura.com/ChEN409/11%20Alkylation.pdf http://www.personal.psu.edu/users/w/y/wyg100/fsc432/Lecture%2015.htm

Page 91: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

ZeoliteZeoliteZeoliteZeolite PolymerizationPolymerizationPolymerizationPolymerization

• Converts propylenes and butylenes into saturated carbon chains by means of zeolite catalysis (ZSM-5)

Page 92: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

ZeoliteZeoliteZeoliteZeolite PolymerizationPolymerizationPolymerizationPolymerization

• Converts propylenes and butylenes into saturated carbon chains by means of zeolite catalysis (ZSM-5)

Page 93: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

ZeoliteZeoliteZeoliteZeolite PolymerizationPolymerizationPolymerizationPolymerization

• Converts propylenes and butylenes into saturated carbon chains by means of zeolite catalysis (ZSM-5)

79MON

92RON

Octane

0.73Specific Gravity

[Tabak, 1986]

Page 94: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

ZeoliteZeoliteZeoliteZeolite PolymerizationPolymerizationPolymerizationPolymerization

Charge• 17wt.% Propylene• 10.7 wt.% Propane• 36.1 wt.% 1-butene• 27.2 wt.% isobutane

Temperature = 550KTotal Pressure =

5430 kPa

Propylene partial pressure = 7~3470kPa.

*Depending on desired chain length

Page 95: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

ZeoliteZeoliteZeoliteZeolite PolymerizationPolymerizationPolymerizationPolymerization

Charge• 17wt.% Propylene• 10.7 wt.% Propane• 36.1 wt.% 1-butene• 27.2 wt.% isobutane

Temperature = 550KTotal Pressure =

5430 kPa

Propylene partial pressure = 7~3470kPa.

*Depending on desired chain length

Page 96: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Polymerization+ PBR-gas phase

- Solid catalysis

+ Produce either diesel or gasoline range chains

- Typical octane number = 92 (RON)

Alkylation- CSTR- liquid phase

+ Liquid catalysis

- Requires very vigorous agitation

- Typically .1lbm acid consumed per gallon product

++Typical octane number = 96(RON)

VS

Page 97: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2
Page 98: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Deasphalting

INPUT:%HeaviesTemperaturePressure

OUTPUT:%HeaviesLube oil

MODEL:Correlation

Page 99: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Propane Deasphalting - PFD

http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0104-66322000000300012&lng=pt&nrm=iso

Typical Propane Deasphalting

Page 100: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Propane Deasphalting

Types1. Sub Critical. (below 369K) Modeled first by

Robert E. Wilson in 1936. Hildebrand solubility parameters now used.

2. Super Critical. (above 369K) Now popular. High selectivity. No good model.

Both remove greater than 99% asphalt

Page 101: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Sub Critical Propane

Deasphalting

21

−∆=

V

TRH gδ

=δ=∆H

=gR

Hildebrand solubility

Solubility Parameter [J/mol]

Heat of vaporization [J/mol]

Universal gas Constant [8.314J/mol/K]T = Temperature [K]V = molar volume [L/mol]

Page 102: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Super Critical Propane

Deasphalting

Models typically break down near the critical point. Including Redlick-Kwong, Soave-Redlick-Kwong and Perturbed-Hard-Chain (PHC). Therefore correlations have to be used.

Typically operate atT=400K Pressure=55 bar Ratio= 4:1 propane to oil mixture

Pressure (bar)

“Phase Equilibria in Supercritical Propane Systems for Separation of Continuous Oil Mixtures” Radosz, Maciej et al. Ind. Eng. Chem. Res. 1987, 26, 731-737

Page 103: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2
Page 104: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Catalytic Cracking

INPUT:KwTemperature

OUTPUT:Gas OilGasolineLPGDry GasCoke

MODEL:PFR

Page 105: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Fluidized Catalytic Cracking

• Pretreated feedstock is fed into the bottom of the riser tube where it meets very hot regenerated catalyst.

• The feed vaporizes and is cracked as it passes up the riser. 1

http://www.uyseg.org/catalysis/petrol/petrol2.htm

Page 106: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Fluidized Catalytic Cracking

•Different yields of products will occur depending on:

� Temperature� Inlet Feed Properties

•Top of the riser, the catalyst separates from the mixture and is steam stripped

•The final product exits the top of the reactor

2

http://www.uyseg.org/catalysis/petrol/petrol2.htm

Page 107: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Fluidized Catalytic Cracking

• One product from catalytic cracking is “coke” or carbon that forms on the surface of the catalyst.

•To reactivate catalyst, it must be regenerated.

3

http://www.uyseg.org/catalysis/petrol/petrol2.htm

Page 108: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Fluidized Catalytic Cracking

• Catalysis is regenerated by entering a combustion chamber and mixed with superheated air

• Energy released from regenerating the catalysis is then coupled with the inlet feed at the bottom of the riser

�Cracking 4

http://www.uyseg.org/catalysis/petrol/petrol2.htm

Page 109: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

A B C

DE

Ancheyta-Juarez, Jorge, “Estimation of Kinetic Constants….”, Energy & Fuels, 2000, 14, 1226-1231

Fluidized Catalytic Cracking

Page 110: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

A B C

DE

Ancheyta-Juarez, Jorge, “Estimation of Kinetic Constants….”, Energy & Fuels, 2000, 14, 1226-1231

Fluidized Catalytic Cracking

Page 111: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

A B C

DE

Ancheyta-Juarez, Jorge, “Estimation of Kinetic Constants….”, Energy & Fuels, 2000, 14, 1226-1231

Fluidized Catalytic Cracking

Page 112: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

A B C

DE

Ancheyta-Juarez, Jorge, “Estimation of Kinetic Constants….”, Energy & Fuels, 2000, 14, 1226-1231

Fluidized Catalytic Cracking

Page 113: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

A B C

DE

• 8 kinetic constants

• One catalyst deactivation

• Gas Oil considered as a second order reactionAncheyta-Juarez, Jorge, “Estimation of Kinetic Constants….”, Energy & Fuels, 2000, 14, 1226-1231

Fluidized Catalytic Cracking

Page 114: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

• Assumptions– One-dimensional tubular reactor

• No radial and axial dispersion

– Cracking only takes place in the riser

– Dispersion/Adsorption inside catalyst is negligible

– Coke deposited does not affect the fluid flow

Fluidized Catalytic Cracking

Page 115: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

• Change– Temperature– Inlet Feed

Mass Balance:

dtdt

dCCC i

i *0 +=

Fluidized Catalytic Cracking

iC

Li rWHSVdz

dy ∗= )(1

ρρ

Page 116: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

• Change– Temperature– Inlet Feed

Mass Balance:

dtdt

dCCC i

i *0 +=

Fluidized Catalytic Cracking

iC

Li rWHSVdz

dy ∗= )(1

ρρ

TEMPERATURE:480, 500, 520 ºC

Page 117: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

• Constant C/O Ratio of 5• Varying space velocity (WHSV)

� 6 – 48 h-1

• Gas Oil Conversion ~ 70 %• Gasoline ~ 50%• LPG ~ 12 %

Fluidized Catalytic Cracking

Page 118: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

• Constant C/O Ratio of 5• Varying space velocity (WHSV)

� 6 – 48 h-1

• Gas Oil Conversion ~ 70 %• Gasoline ~ 50%• LPG ~ 12 %

Fluidized Catalytic Cracking

Page 119: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

• Constant C/O Ratio of 5• Varying space velocity (WHSV)

� 6 – 48 h-1

• Gas Oil Conversion ~ 70 %• Gasoline ~ 50%• LPG ~ 12 %

Fluidized Catalytic Cracking

Page 120: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2
Page 121: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Blending

INPUT:35 streams

OUTPUT:Gasoline

RegularPremium

LPGCokeLube OilWaxAsphalt

Page 122: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

A future of energy production…

Blending

• Final products are created by blending streams from refinery units

• 35 streams from 13 units are blended• 30 streams are used in gasoline• 5 streams are other products

– Propane gas, lube oil, asphalt, wax, and coke

Page 123: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Blending Indexes

• Most properties do not blend linearly• Empirical blending indexes are used to

linearize the blending behavior

∑=i

iimix BIxBI

icomponent offraction volume theis

Index Blending theis Where

ix

BI

Page 124: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Blending Indexes

= 08.0

1

pp TBIPour Point

νν10

10

log3

log

+=vBIViscosity Index

= 05.0

1

CLCL TBICloud Point

6.42

24141188.6log10 −

+−=F

F TBIFlash Point

( )[ ]APBI AP 00657.0exp124.1=Aniline Point

( ) 25.1RVPVPBI =Reid Vapor Pressure

Page 125: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Gasoline Blending

• Specifications:– Octane (normal 87, premium 91)– Reid Vapor Pressure (EPA mandated)– Maximum additive amounts

• Inputs:– Market conditions (Price, Demand)– Incoming streams from refinery units

• Objective: Maximize Profit

Page 126: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Gasoline Blending

• Vapor pressure blending can be improved by using thermodynamically based methods

• Raoult's Law

∑= *ii PxP

Page 127: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Blending

• Other possible products– Fuel oils

– Lube oils– Diesel fuel

• Blending requires data for aniline point, pour point, cloud point, flash point, and diesel index

Page 128: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Refinery Planning

• Addresses the planning of short-term crude oil purchasing and processing

• Does not address risk or uncertainty• Determine purchasing schedule to meet:

– Specification (Octane, n-Butane, etc.)– Demand with HIGHEST profit

• Decision Variables:– Crude oil purchase– Processing variables

• Temperatures, Pressures, Blending mixtures

Page 129: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

A future of energy production…

Page 130: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

A future of energy production…

Page 131: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

A future of energy production…

Page 132: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

A future of energy production…

Page 133: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Refinery Planning

•Max Profit

∑∑ ∑∑∑∑∈ ∈ ∈ ∈∈ ∈

∗−∗−∗=Tt Cc Tt Cc

tctctctctcTt Cc

tc

o pp

clALcoACcpMANU ,,,,,,

Pongsakdi, Arkadej, et. al, “Financial risk….”, Int. J. Production Economics, accepted 20 April 2005

Page 134: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Refinery Planning

•Max Profit

∑∑ ∑∑∑∑∈ ∈ ∈ ∈∈ ∈

∗−∗−∗=Tt Cc Tt Cc

tctctctctcTt Cc

tc

o pp

clALcoACcpMANU ,,,,,,

Product Sales

Amount of product producedin that time period multiplied by

unit sale price of product c

Pongsakdi, Arkadej, et. al, “Financial risk….”, Int. J. Production Economics, accepted 20 April 2005

Page 135: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Refinery Planning

•Max Profit

∑∑ ∑∑∑∑∈ ∈ ∈ ∈∈ ∈

∗−∗−∗=Tt Cc Tt Cc

tctctctctcTt Cc

tc

o pp

clALcoACcpMANU ,,,,,,

Product Sales

Amount of product producedin that time period multiplied by

unit sale price of product c

Crude Oil Costs

Amount of crude oil refined in that time period multiplied by

unit purchase price of crude oil

Pongsakdi, Arkadej, et. al, “Financial risk….”, Int. J. Production Economics, accepted 20 April 2005

Page 136: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Refinery Planning

•Max Profit

∑∑ ∑∑∑∑∈ ∈ ∈ ∈∈ ∈

∗−∗−∗=Tt Cc Tt Cc

tctctctctcTt Cc

tc

o pp

clALcoACcpMANU ,,,,,,

Product Sales

Amount of product producedin that time period multiplied by

unit sale price of product c

Crude Oil Costs

Amount of crude oil refined in that time period multiplied by

unit purchase price of crude oil

Discounted Expense

Amount of product volume that cannot satisfy demand

multiplied by discounted price

Pongsakdi, Arkadej, et. al, “Financial risk….”, Int. J. Production Economics, accepted 20 April 2005

Page 137: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Modeling

• A Visual Basic macro in Excel was used to help Solver find the optimal crude selection

Page 138: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Modeling

• A Visual Basic macro in Excel was used to help Solver find the optimal crude selection

Page 139: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Model Inputs

• Inputs:– Crude A: $71.88 / barrel (Australia)– Crude B: $72.00 / barrel (Kazakhstan)– Crude C: $71.20 / barrel (Saudi Arabia)– Regular Gasoline:

• $2.75 / gal ($2.12) • Demand: 310,000 bbl/month

– Premium Gasoline: • $3.00 / gal ($2.31)• Demand: 124,000 bbl/month

Energy Information Administration, U.S. Department of Energy http://www.eia.doe.gov/oil_gas/petroleum/info_glance/petroleum.html

Page 140: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Model Results

• Outputs:– Maximum Profit: $21 per barrel

– Crude Selection:• Crude A: 150,000 bbl/month• Crude B: 150,000 bbl/month• Crude C: 300,000 bbl/month

– Demand exactly met

Page 141: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Future Work

• Include storage of crude and products• Include risk and uncertainty• Demand changing over time• Wider variety of products: diesel,

solvents, fuel oils, lube oils, etc.

Page 142: Refinery Planning Presentation - University of Oklahoma Planning...HydrocrackingModel y = 0.84165e 0.00096x R2 = 0.99872 y = 0.91507e 0.00099x R2 = 0.99903 y = 1.03077e 0.00102x R2

Questions?