Shale oil composition and production kinetics
Oil Shale Symposium Colorado School of Mines
October 18-20, 2010
JWBA, Inc.
James W. Bunger, Ph.D.
Christopher P. Russell, Ph.D.
Donald E. Cogswell, M. S
Red Leaf Resources, Inc.
James W. Patten, Ph.D.
Topics
• Temperature – time conditions • Kinetic treatment • Product yields • Molecular compositions
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0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110
T av
g -d
eg F
days from start
Time-temperature history
Simulator (solid line)
7 days
Thru Feb 10
burner failure
start N2 inerting
Actual production (yellow data points)
losses to surroundingsequal to input
Observations • Long heatup times result in production chemistry
substantially different from traditional surface process times, as well as Fischer Assay chemistry.
• Understanding production kinetics is essential to process simulation and optimization
• Composition of resulting product is very different when oil shale is subjected to slow, indirect heat compared to fast, direct heat.
Property - units Measured input data for Z-BaSIC file construction
EcoShale 32
Utah
Unocal 23 Colorado
Estonia Kukersite 8
Carbon – wt% 85.26 85.87 88.31 Hydrogen – wt% 12.45 11.74 8.06 Nitrogen – wt% 1.55 1.30 0.1 Basic Nitrogen – wt% 1.08 0.73 NA Sulfur – wt% 0.249 0.918 0.557 Oxygen – wt% 1.24 0.17 2.98 Density @ 15.5 ºC – g/cc 0.8643 .9148 1.0189 API gravity - degrees 32.2 23.2 7.4 Additional property data on whole oils - Z-BaSIC output data
UOP K factor 11.55 11.3 10.3
Average MW - Dalton 198 245 226 Conradson Carbon wt % Non-detect 3.0 0.2 D-2887 distillation data 10% point ºF 330 384 528 50% point ºF 560 716 702 90% point ºF 801 935 915 Kinematic Viscosity @ 37.78 ºC - cSt
4.00 23.3 259
Kinematic Viscosity @ 50.0 ºC - cSt 3.04 NA NA Dynamic Viscosity @ 37.78 ºC - cP 3.39 21.5 266 Dynamic Viscosity @ 50.0 ºC -cP 2.55 14.4 136
ND = non-detect NA= not analyzed
10!
Boiling range distribution for Ecoshale 32 and WTI 42
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Wt percent over
T - d
egre
es F
ahre
nhei
t
C8
C21
EcoShale 32 API70% diesel range
WTI 42 API47% diesel range
Diesel Yield From Raw Shale Oil
Sample Description Raw Oil HT OilRL09-345 RL10-17
Hydrogen, %wt 12.28 12.56Carbon, %wt 85.62 85.57
Nitrogen, %wt 1.49 1.41Sulfur, %wt 0.224 0.077
TAN, mg KOH/g 0.6 0.1Bromine #, g/100g 32 6.4
API @60F 33.0 33.3Specific Gravity @60F 0.8601 0.8586
Raw Shale Oil and Hydrostabilized Oil
Kinetic model
gas
Kerogen oil
coke
Secondary reactions are not relevant because the residence time of liquid and gaseous products formed is very short in relationship to overall reaction time.
Arrhenius parameters vary with progress of reaction; i.e. kerogen itself is a range of types, and different reactions dominate at different temperatures and times.
Regression procedure
• Input data – Temperature, time, mass yields of oil and gas, and an estimate of original kerogen content
• Mathematical formulation requires 6 parameters to describe the pre-exponential function and activation energy for each of the three paths.
• Regress a best fit to laboratory and field pilot plant data.
ACTIVATION ENERGY vs. TIME FOR THE 222 DAY CASE
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3000 3500 4000 4500 5000 5500
tr (hr)
Ea (K
cal/m
ole)
GASOILCOKE
TEMPERATURE vs. TIME
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tr (hr)
T (OF)222 day95 day 7 day
lab field pilot commercial
COMPARE KINETICS FOR 7 DAY, 95 DAY AND 222 DAY RUNSCUMULATIVE GAS PRODUCTION
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95 day
7 day
Z-BaSIC™ • Acronym for the Z-Based Structural Index
Correlation Method • Classify all compounds by z-series according to the
empirical formula CnH2n+zNuSvOw
• Method for – Identifying components of about 70 homologous
series in a mixture – Estimating the properties of those components – Quantifying the concentrations of those
components • Results in a closed mass balance at the molecular
and elemental level.
Identification of ‘z’ classes by molecular ions and GC retention time
2 8 . 0 0 3 0 . 0 0 3 2 . 0 0 3 4 . 0 0 3 6 . 0 0 3 8 . 0 0 4 0 . 0 0 4 2 . 0 0 4 4 . 0 0 4 6 . 0 0 4 8 . 0 0 5 0 . 0 0 5 2 . 0 00
1 0 0 02 0 0 03 0 0 04 0 0 05 0 0 0
T i m e - - >
A b u n d a n c e
I o n 2 0 4 . 0 0 ( 2 0 3 . 7 0 t o 2 0 4 . 7 0 ) : 0 0 3 9 0 1 . D
2 8 . 0 0 3 0 . 0 0 3 2 . 0 0 3 4 . 0 0 3 6 . 0 0 3 8 . 0 0 4 0 . 0 0 4 2 . 0 0 4 4 . 0 0 4 6 . 0 0 4 8 . 0 0 5 0 . 0 0 5 2 . 0 00
1 0 0 02 0 0 03 0 0 04 0 0 0
T i m e - - >
A b u n d a n c e
I o n 2 1 8 . 0 0 ( 2 1 7 . 7 0 t o 2 1 8 . 7 0 ) : 0 0 3 9 0 1 . D
2 8 . 0 0 3 0 . 0 0 3 2 . 0 0 3 4 . 0 0 3 6 . 0 0 3 8 . 0 0 4 0 . 0 0 4 2 . 0 0 4 4 . 0 0 4 6 . 0 0 4 8 . 0 0 5 0 . 0 0 5 2 . 0 001 0 0 02 0 0 03 0 0 0
T i m e - - >
A b u n d a n c e
I o n 2 3 2 . 0 0 ( 2 3 1 . 7 0 t o 2 3 2 . 7 0 ) : 0 0 3 9 0 1 . D
alkylbenzenes
alkylbenzothiophenes dihydropyrenes
phenylnaphthalenes
Z-BaSIC™ Information Logic
Preparation of original 'cp' files 'cp' file adjuster Z-BaSIC Applications
Physical Crude Oils and Intermediate
Process Streams
Laboratory and on-line monitored property data Composition and
Property Reports
Z-Assays(reconciled)
Model, Simulator and Optimizer Input files
First-Principal Simulators
Library Assays
LP Input files
HTSD, light gas analysis
Density
Elemental analysis -C, H, S, N, O & metals
GC-MSanalysis
Optional - NMR, viscosity, RVP, MW, etc.
Density
0.50.60.70.80.91
1.11.21.31.41.5
0 10 20 30 40 50Carbon number
g/cc
Hydrocarbon types EcoShale 32 wt%n-paraffins 12.623i-paraffins 13.991monolefins 1.906mononaphthenes 5.12diolefins 0.355cylcomonolefins 0.356dinaphthenes 7.671triolefins 0.078cyclodiolefins 0.546dicyclomonolefins 0.305trinaphthenes 7.282tetranaphthenes 1.927pentanaphthenes 1.266hexanaphthenes 0.081heptanaphthenes 0.41monoaromatics 2.068vinyl benzenes 0.469naphthenomonoaromatics 0.286phenyldienes 0.81dinapthenomonoaromatics,indenes 0.079trinaphthenomonoaromatics 0.823tetranapthenomonoaromatics 0.018diaromatics 1.828acenaphthene/naphthenodiaromatics 0.883dinaphthenodiaromatics 0.01acenaphthalenes/fluorenes 0.22triaromatics 0.33naphthenotriaromatics/dihydropyrenes 0.009phenylnaphthalenes 0.159tetraaromatics (peri-condensed) 0.006tetraaromatics (cata-condensed) 0.029naphthenoflourenes 0.001pentaaromatics (peri-condensed) 0.033 sub total 61.978
Heteroatom types EcoShale 32 wt%naphthenosulfides/thiols 0.646dinaphthenosulfides/thiols 0.649thiophenes 0.159trinaphthenosulfides/thiols 0.135thiophenol 0.052tetrahydrobenzothiophene 0.081tetranaphthenosulfides/thiols 0benzothiophenes 0.091benzodithiophenes 0.005dibenzothiophenes 0epithiophenanthrenes 0.002benzodibenzothiophenes 0.001pyrroles 2.397indoles 6.112carbazoles 0.0024-ring pyrrolics* 0.076pyridines 13.629quinolines 2.439phenanthridines 0.0654-ring pyridinics* 1.573phenols 4.758hydroxy tetralins 0.427naphthols 0.933dibenzofuran 0resorcinols 1.752dihydroxy tetralins 0.529 subtotal 36.513
Summary
• Have demonstrated the accuracy of the heat transfer simulation
• Have identified a fundamentally meaningful reaction scheme and kinetic treatment
• Have developed the means to interpret retorting results at the molecular level
• Now need to complete the verification through additional laboratory work and field experience.
• Apply this approach to oil shale in other parts of the world.
Thank you for your attention [email protected]
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