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

0

100

200

300

400

500

600

700

800

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

0

200

400

600

800

1000

1200

1400

0 20 40 60 80 100 120

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

20

25

30

35

40

45

50

55

60

65

3000 3500 4000 4500 5000 5500

tr (hr)

Ea (K

cal/m

ole)

GASOILCOKE

TEMPERATURE vs. TIME

0

100

200

300

400

500

600

700

800

0 1000 2000 3000 4000 5000

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

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

500 550 600 650 700 750T (OF)

G/K0

222 day

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 Jim@jwba.com