Shale oil composition and production kinetics
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1 Shale oil composition and production kinetics JWBA, Inc. Oil Shale Symposium Colorado School of Mines October 18-20, 2010 James W. Bunger, Ph.D. Christopher P. Russell, Ph.D. Donald E. Cogswell, M. S Red Leaf Resources, Inc. James W. Patten, Ph.D.
2 Topics Temperature time conditions Kinetic treatment Product yields Molecular compositions
3
4 Thru Feb 10 Time-temperature history Simulator (solid line) 7 days T avg - deg F Actual production (yellow data points) burner failure start N2 inerting losses to surroundings equal to input days from start
5 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.
6 Property - units Measured input data for Z-BaSIC file construction EcoShale 32 Utah Unocal 23 Colorado Estonia Kukersite 8 Carbon wt% Hydrogen wt% Nitrogen wt% Basic Nitrogen wt% NA Sulfur wt% Oxygen wt% ºC g/cc API gravity - degrees Additional property data on whole oils - Z-BaSIC output data UOP K factor Average MW - Dalton Conradson Carbon wt % Non-detect D-2887 distillation data 10% point ºF % point ºF % point ºF Kinematic ºC cst Kinematic 50.0 ºC - cst 3.04 NA NA Dynamic ºC - cp Dynamic 50.0 ºC -cp ND = non-detect NA= not analyzed
7 1400 Diesel Yield From Raw Shale Oil Boiling range distribution for Ecoshale 32 and WTI T - degrees Fahrenheit EcoShale 32 API 70% diesel range WTI 42 API 47% diesel range C21 0 C Wt percent over 10!
8 Raw Shale Oil and Hydrostabilized Oil Sample Description Raw Oil HT Oil RL RL10-17 Hydrogen, %wt Carbon, %wt Nitrogen, %wt Sulfur, %wt TAN, mg KOH/g Bromine #, g/100g Specific
9 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.
10 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.
11 65 ACTIVATION ENERGY vs. TIME FOR THE 222 DAY CASE Ea (Kcal/mole) GAS OIL COKE tr (hr)
12 TEMPERATURE vs. TIME lab field pilot commercial T ( O F) day 95 day 7 day tr (hr)
13 G/K 0 COMPARE KINETICS FOR 7 DAY, 95 DAY AND 222 DAY RUNS CUMULATIVE GAS PRODUCTION day 95 day 7 day T ( O F)
14 Z-BaSIC Acronym for the Z-Based Structural Index Correlation Method Classify all compounds by z-series according to the empirical formula C n H 2n+z N u S v O w 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.
15 Identification of z classes by molecular ions and GC retention time A b u n d a n c e Io n ( to ): D T i m e - - > A b u n d a n c e alkylbenzothiophenes dihydropyrenes alkylbenzenes phenylnaphthalenes Io n ( to ): D T i m e - - > A b u n d a n c e Io n ( to ): D T i m e - - >
16 Physical Crude Oils and Intermediate Process Streams Z-BaSIC Information Logic Laboratory and on-line monitored property data Z-Assays (reconciled) Composition and Property Reports Preparation of original 'cp' files 'cp' file adjuster Z-BaSIC Applications LP Input files GC-MS analysis Library Assays Model, Simulator and Optimizer Input files First-Principal Simulators Elemental analysis - C, H, S, N, O & metals Density HTSD, light gas analysis Optional - NMR, viscosity, RVP, MW, etc.
17 g/cc Density Carbon number
18 Hydrocarbon types EcoShale 32 wt% n-paraffins i-paraffins monolefins mononaphthenes 5.12 diolefins cylcomonolefins dinaphthenes triolefins cyclodiolefins dicyclomonolefins trinaphthenes tetranaphthenes pentanaphthenes hexanaphthenes heptanaphthenes 0.41 monoaromatics vinyl benzenes naphthenomonoaromatics phenyldienes 0.81 dinapthenomonoaromatics,indenes trinaphthenomonoaromatics tetranapthenomonoaromatics diaromatics acenaphthene/naphthenodiaromatics dinaphthenodiaromatics 0.01 acenaphthalenes/fluorenes 0.22 triaromatics 0.33 naphthenotriaromatics/dihydropyrenes phenylnaphthalenes tetraaromatics (peri-condensed) tetraaromatics (cata-condensed) naphthenoflourenes pentaaromatics (peri-condensed) sub total
19 Heteroatom types EcoShale 32 wt% naphthenosulfides/thiols dinaphthenosulfides/thiols thiophenes trinaphthenosulfides/thiols thiophenol tetrahydrobenzothiophene tetranaphthenosulfides/thiols 0 benzothiophenes benzodithiophenes dibenzothiophenes 0 epithiophenanthrenes benzodibenzothiophenes pyrroles indoles carbazoles ring pyrrolics* pyridines quinolines phenanthridines ring pyridinics* phenols hydroxy tetralins naphthols dibenzofuran 0 resorcinols dihydroxy tetralins subtotal
20 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.
21 Thank you for your attention
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