[PPT] - Shale oil composition and production kinetics JWBA, Inc. James W. PowerPoint Presentation

SLIDE 1

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.

SLIDE 2

Topics

Temperature – time conditions
Kinetic treatment
Product yields
Molecular compositions

SLIDE 3

SLIDE 4

100 200 300 400 500 600 700 800 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 T avg - deg 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 surroundings equal to input

SLIDE 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.

SLIDE 6

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

ils - 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

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10

Boiling range distribution for Ecoshale 32 and WTI 42

200 400 600 800 1000 1200 1400 20 40 60 80 100 120 Wt percent over T - degrees Fahrenheit C8 C21

EcoShale 32 API 70% diesel range

WTI 42 API 47% diesel range

Diesel Yield From Raw Shale Oil

SLIDE 8

Sample Description Raw Oil HT Oil RL09-345 RL10-17 Hydrogen, %wt 12.28 12.56 Carbon, %wt 85.62 85.57 Nitrogen, %wt 1.49 1.41 Sulfur, %wt 0.224 0.077 TAN, mg KOH/g 0.6 0.1 Bromine #, g/100g 32 6.4 API @60F 33.0 33.3 Specific Gravity @60F 0.8601 0.8586

Raw Shale Oil and Hydrostabilized Oil

SLIDE 9

Kinetic model

gas Kerogen

il

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.

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Regression procedure

Input data – Temperature, time, mass yields of
il 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.

SLIDE 11

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 (Kcal/mole) GAS OIL COKE

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TEMPERATURE vs. TIME 100 200 300 400 500 600 700 800 1000 2000 3000 4000 5000 tr (hr) T (

OF)

222 day 95 day 7 day

lab field pilot commercial

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COMPARE KINETICS FOR 7 DAY, 95 DAY AND 222 DAY RUNS CUMULATIVE GAS PRODUCTION 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 500 550 600 650 700 750 T (

OF)

G/K0 222 day 95 day 7 day

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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.

SLIDE 15

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 0 1 0 0 0 2 0 0 0 3 0 0 0 4 0 0 0 5 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 0 1 0 0 0 2 0 0 0 3 0 0 0 4 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 0 1 0 0 0 2 0 0 0 3 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

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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-MS analysis Optional - NMR, viscosity, RVP, MW, etc.

SLIDE 17

Density

0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5

10 20 30 40 50 Carbon number g/cc

SLIDE 18

Hydrocarbon types EcoShale 32

wt%

n-paraffins

12.623

i-paraffins

13.991

monolefins

1.906

mononaphthenes

5.12

diolefins

0.355

cylcomonolefins

0.356

dinaphthenes

7.671

triolefins

0.078

cyclodiolefins

0.546

dicyclomonolefins

0.305

trinaphthenes

7.282

tetranaphthenes

1.927

pentanaphthenes

1.266

hexanaphthenes

0.081

heptanaphthenes

0.41

monoaromatics

2.068

vinyl benzenes

0.469

naphthenomonoaromatics

0.286

phenyldienes

0.81

dinapthenomonoaromatics,indenes

0.079

trinaphthenomonoaromatics

0.823

tetranapthenomonoaromatics

0.018

diaromatics

1.828

acenaphthene/naphthenodiaromatics

0.883

dinaphthenodiaromatics

0.01

acenaphthalenes/fluorenes

0.22

triaromatics

0.33

naphthenotriaromatics/dihydropyrenes

0.009

phenylnaphthalenes

0.159

tetraaromatics (peri-condensed)

0.006

tetraaromatics (cata-condensed)

0.029

naphthenoflourenes

0.001

pentaaromatics (peri-condensed)

0.033

sub total

61.978

SLIDE 19

Heteroatom types EcoShale 32

wt%

naphthenosulfides/thiols

0.646

dinaphthenosulfides/thiols

0.649

thiophenes

0.159

trinaphthenosulfides/thiols

0.135

thiophenol

0.052

tetrahydrobenzothiophene

0.081

tetranaphthenosulfides/thiols benzothiophenes

0.091

benzodithiophenes

0.005

dibenzothiophenes epithiophenanthrenes

0.002

benzodibenzothiophenes

0.001

pyrroles

2.397

indoles

6.112

carbazoles

0.002

4-ring pyrrolics*

0.076

pyridines

13.629

quinolines

2.439

phenanthridines

0.065

4-ring pyridinics*

1.573

phenols

4.758

hydroxy tetralins

0.427

naphthols

0.933

dibenzofuran resorcinols

1.752

dihydroxy tetralins

0.529

subtotal

36.513

SLIDE 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.

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Shale oil composition and production kinetics JWBA, Inc. James W. - - PowerPoint PPT Presentation