Download - Oil Shale Pyrolysis Model
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Oil Shale Pyrolysis Modeling
Ramesh Sarathi
28th Oil Shale SymposiumColorado School of Mines, Golden, CO
October 13-17 2008
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Overview
• Background– Pyrolysis process– Previous studies
• Model Description• Results• Conclusions
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Background
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Pyrolysis: (1) Heat Transfer
• Hot gases heat the surface of the particle
• Heat is conducted from the surface to the interior
r
Hot sweep gases
Surface heats first
qHeat is conducted to the interior
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Pyrolysis: (2) Chemical Reaction
• Temperature rise induces chemical reactions
• Endothermic reactions consume heat
• Rate of temperature rise slows
• Porosity is created as solid reactants form gaseous products
r
Hot sweep gases
Reactions start at surface
qReactions progress to interior
No sharp front
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Pyrolysis: (3) Mass & Momentum Transfer
• Momentum Transfer– Pressure buildup inside
particle causes gas to flow out
• Mass Transfer– Concentration gradients
cause products to diffuse out of particle
– Sweep gases diffuse into particle
– Thermal diffusion causes heavier molecules to diffuse toward cooler regions
r
Hot sweep gases
Low pressure, low species concentration at surface
Products flow out of particle
High pressure, high species concentration in interior
Civi
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Previous Studies• Experimental Studies
– Kerogen Pyrolysis• Campbell et al. [1978]
– Gas Evolution• Campbell et al. [1980] (2)• Huss & Burnham [1982]
– Oil Coking• Campbell et al. [1977]
– Oil Cracking• Bissell et al. [1983]
– Char Gasification• Burnham [1979] (3)• Thomson et al. [1983]
– Carbonate Minerals• Campbell [1978]
• Modeling Studies– Particle
• Johnson et al. [1975]• Campbell et al. [1977]• Shih & Sohn [1978]• Gregg et al. [1981]• Burnham & Braun [1985]• Wang & Lee [1986]
– Retort• Braun & Chin [1977/1981]• Tyner & Hommert [1978]• Crowl et al. [1979]• Parker & Zhang [2006]
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Model Description
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All models are wrong, some are useful.
~ George Box
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Objective
• Review previous studies
• Develop unified kinetic model
• Validate model with experimental data
Chemistry & Kinetics
Transport Phenomena(heat, mass)
Rock Mechanics
Phase Behavior
Production Rates & Yields
Heating Requirements
Process CostsLimiting Design Parameters
Model
Prediction
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Physical Model
r
Hot sweep gases
q
Civi
• Physical Model– Oil shale is heated in a furnace– Constant flow of inert gas
sweeps through reactor– Volatile products flow out of
reactor– Assume reactor is spatially
uniform• Chemistry
(adapted from LLNL studies)– Kerogen pyrolysis– Oil Coking, Cracking– Char pyrolysis– Char gasification, WGS– Carbonate decomposition
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Chemical Reactions
kerogen (5)
char
oil (11)
gas (2)
char’ char’’
CO2 CO
H2 H2O
dolomite
calcite
silicates
Pyrolysis
Carbonate Decomposition
Coking
Char Gasification
Cracking
Char Pyrolysis
gas
WGS
Solid GasKerogen (5) Oil vapor (11)
Char (3) CH4
Nahcolite CHx
Dawsonite H2
Dolomite H2O
Calcite CO
Silicates CO2
N2Char’ Pyrolysis
nahcolite
dawsonite
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KineticsReaction Kinetics Source
Kerogen Pyrolysis (5) 1st order Burnham & Braun [1985]Campbell et al. [1978]
Oil Coking (11) 1st order Burnham & Braun [1985]Campbell et al. [1977]
Oil Cracking (11) 1st order Burnham & Braun [1985]Bissell et al. [1983]
Char Pyrolysis (2) 1st orderGaussian-distributed Ea
Campbell et al. [1980]
Char Gasification (2) LHHW Burnham [1979] (3)*
Water-gas-shift 2nd order, reversible Braun & Chin [1981]
Carbonate Decomposition (7) 1st orderLHHW
Campbell [1978]
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Conservation Equations
VRfdt
dNj
jjis
is )1(,,, ε−⋅=∑
, , , , , , ,(1 )g i s i j s j g i j g jj j
N f R V f R Vε ε= ⋅ − + ⋅∑ ∑&
Solid Species Mole Balance
Gas Species Mole Balance
Accumulation Stoichiometry Reaction Volume ofRate Matrix Rate solid phase
⎧ ⎫ ⎧ ⎫ ⎧ ⎫ ⎧ ⎫=⎨ ⎬ ⎨ ⎬ ⎨ ⎬ ⎨ ⎬
⎩ ⎭ ⎩ ⎭ ⎩ ⎭ ⎩ ⎭
,, ,0 0 , ,
g ig i g i g i
dNC v C v N
dt= − + &
Accumulation Flow Flow Generation Rate In Out from reaction
⎧ ⎫ ⎧ ⎫ ⎧ ⎫ ⎧ ⎫= − +⎨ ⎬ ⎨ ⎬ ⎨ ⎬ ⎨ ⎬
⎩ ⎭ ⎩ ⎭ ⎩ ⎭ ⎩ ⎭
,0 ,T T g ii
F F N= +∑ &
0,0 0
T
T
F Tv vF T
⎛ ⎞⎛ ⎞= ⎜ ⎟⎜ ⎟⎜ ⎟⎝ ⎠⎝ ⎠
Inlet Molar Outlet Molar Generation Flowrate Flowrate from Reaction⎧ ⎫ ⎧ ⎫ ⎧ ⎫
= +⎨ ⎬ ⎨ ⎬ ⎨ ⎬⎩ ⎭ ⎩ ⎭ ⎩ ⎭
Inlet Volumetric Outlet Volumetric Ratio of Flowrate Flowrate Molar Flowrates⎧ ⎫ ⎧ ⎫⎧ ⎫
=⎨ ⎬ ⎨ ⎬⎨ ⎬⎩ ⎭ ⎩ ⎭⎩ ⎭
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Solution Method
• 0D Model– Each mole balance equation is an ODE– Furnace temperature increases linearly with
time– Retort sweep gas flow rate determines
product residence time– Integrate ODE system with MATLAB
ODE15s
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Results
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Oil Production
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Methane Production
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H2 Production
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CO2 Production
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Conclusions
• Kinetic model can reproduce trends in laboratory data
• Next Steps– Improve lumped species model for oil
composition– Perform sensitivity analyses– Develop particle model w/ mass and heat
transport
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Questions?
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Conservation Equations: 1D
( )_
, ,·n rxn
s p s s rxn j jj
Tc T h Rt
ρ λ∂= ∇ ∇ −
∂ ∑
( ), ,, , ,
,
·g i g ii m g i g i
g t
C CD p C R
t Cφ κ
μ−
+∂ ⎛ ⎞
= ∇ ∇ ∇ +⎜ ⎟⎜ ⎟∂ ⎝ ⎠&
( ),,
(1 ) s is i
CR
tφ∂ −
=∂
&
Solid-phase Mass Balance
Gas-phase Mass Balance
Particle Energy Balance
{ } { }Solid Accumulation Reaction=
{ } { } { } { }Gas Accumulation Diffusion Convection Reaction= + +
{ } { } { }Heat Acummulation Conduction Generation by Reaction= +