(H. C. Stauffer (Eds.) ) Oil Shale, Tar Sands, and PDF

Publication Date: September 3, 1981 | doi: 10.1021/bk-1981-0163.
fw001
Oil Shale, Tar Sands, and

Related Materials
In Oil Shale, Tar Sands, and Related Materials; Stauffer, H.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
Publication Date: September 3, 1981 | doi: 10.1021/bk-1981-0163.fw001

Oil Shale, Tar Sands, and
Related Materials
H . C . S t a u f f e r , EDITOR
Gulf Research & Development Company

Based on a symposium
sponsored by the
Division of Fuel Chemistry
at the Second Chemical Congress
of the North American Continent,
Las Vegas, Nevada
August 25-29, 1980.
ACS SYMPOSIUM S E R I E S 163
AMERICAN CHEMICAL SOCIETY

W A S H I N G T O N , D. C. 1981

Library of CongressCIPData
Oil shale, tar sands, and related materials.
(ACS symposium series, ISSN 0097-6156; 163)
Includes bibliographies and index.
1. Oil shales—Congresses. 2. Oil sands—Congresses.
I. Stauffer, H. C., 1922- . II. American Chemi-
cal Society. Division of Fuel Chemistry. III. Chemical
Congress of the North American Continent (2nd:
1980; Las Vegas, Nev.) IV. Series.
TN858.A1038 665'.4 81-10948
ISBN 0-8412-0640-6 AACR2 ACSMC8 163 1-395
1981
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PREFACE
omestic oil shale and tar sand deposits constitute a tremendous re-
D source. The proven, recoverable oil shale reserves alone far exceed
those remaining for petroleum. In light of this fact, it is not surprising
that there are many people having trouble comprehending our vulnerable
energy position.
Attempts to develop a commercial oil shale industry historically have
been on-again, off-again efforts. In almost yearly cyclical fashion, one has
Publication Date: September 3, 1981 | doi: 10.1021/bk-1981-0163.pr001
heard or read at least one paper enthusiastically suggesting the general

theme, " A n Oil Shale Industry—Just Around The Corner." Until now,
however, the corner has never been turned and the development pace of
this sorely needed resource has been low key at best. All of our domestic
heavy oil production and tar sands development endeavors have been in
much the same category.
The ability to turn the corner always has been stalled by unfavorable
economics. Some combination of factors arises which continually delays
the development of these alternative energy resources because of their
noncompetitive position compared with the price of foreign oil. In reality,
this has obscured the real issue—the fragile nature of our domestic energy
structure which is so dependent on the ready availability of imported crude.
Hope springs eternal, however, and recent developments have indi-
cated that the corner may indeed have been turned at last. Although the
D O E oil shale research, development, and demonstration program has been
trying to foster a technically and environmentally sound industry capable
of meeting the President's goal of 400,000 bbl/d by 1990, the recent sign
ing of Senate Bill S.932 should provide a significant and needed impetus.
This bill, The Energy Security Act, provides for a United States Synthetic
Fuels Corporation which has the mission of encouraging the production of
500,000 bbl/d from alternative sources by 1987 and 2,000,000 bbl/d by
1992. Even more recently, several major developers have announced
definitive plans for tract development. On-site activity has commenced to
achieve a production goal of 50,000 bbl/d before 1990.
These are most worthy goals, but past procrastination will make them
difficult to attain. It should not be surprising that in situ retorting is still
in its early development stage; that a single, commercial surface retort
module has yet to be constructed and successfully demonstrated; or that a
full slate of products refined from syncrude has still to be proven acceptably
interchangeable with those derived from petroleum.
ix

With respect to recent events the timing of this symposium was only
coincidental. Its content, however, is not. The participants have recognized
the diverse problems, and many of them are addressed in this volume. The
novel concepts of oil shale fracturing and retorting as well as tar sands
recovery processes need to be evaluated. Much needed input has been
provided on rubbling and retorting kinetics and mechanisms, which still
are poorly understood. Our tendency to look for simple solutions to com-
plex problems is apparent in the discussion of "simple" hydrogenation of
shale oil to products of questionable and perplexing stability characteristics.
In view of our long-term domestic energy deficit, the stimulating discussion
of the potential for a very large-scale oil shale operation merits serious
consideration.
Nature's petroleum supply is constrained now by what remains in the
Publication Date: September 3, 1981 | doi: 10.1021/bk-1981-0163.pr001
ground; development of our oil shale and tar sands resources appear only
to be constrained by our own actions.
The credit for the content of this symposium belongs to the partici-
pants and their sponsors. I sincerely appreciate their contributions and
wish to acknowledge P. C . Scott and C. W. Matthews for their help in
its organization.
H . C. S T A U F F E R
Gulf Research & Development Company

P.O. Drawer 2038
Pittsburgh, P A 15230
April 10, 1981

1
The Department of Energy's Oil Shale R, D, & D
Program: An Overview
ARTHUR M. HARTSTEIN and BRIAN M. HARNEY
Office of Oil Shale, Department of Energy, Washington, D.C. 20545
Publication Date: September 3, 1981 | doi: 10.1021/bk-1981-0163.ch001
The largest untapped fossil fuel resource in the United

States is the o i l bearing shales in the western part of the
country and the black shales in the east. The o i l shale
resource concentrated in three western states is estimated
to be equivalent to more than two trillion barrels of crude
o i l . An additional two trillion barrels of oil exists in the
lean deposits of the Eastern U.S.
Since the earliest commercial interest more than 100 years
ago, the history of o i l shale has been one of ups-and-downs.
In almost cyclical fashion, the shale industry has appeared to
be on the verge of expanding rapidly, economics have appeared
potentially viable, and the problems have seemed minimal. But
then, a combination of factors, such as jumps in construction
costs or the discovery of new conventional oil resources, have
led to delays and in some cases, decisions to drop shale oil
development.
Recent events, however, have reversed this trend. The ever-
rising price of imported petroleum, the continuing volatile
situation in the middle east and the passage by the Congress of
a variety of significant financial incentive programs for synthe-
tic fuels has stimulated a new interest in moving previously
dormant o i l shale projects ahead.
The Department of Energy (DOE) has established a research,
development, and demonstration (R,D&D) program for encouraging
the development of the country's o i l shale resource to help in
the mitigation of the present and future energy demands. The
aim of the Oil Shale R,D&D Program is to stimulate the commer-
cial production of shale o i l by eliminating technical and envir-
onmental barriers. This paper provides an overview of the DOE
Oil Shale R,D&D Program, addressing its essential elements. It
should be noted that budget constraints do not permit a l l
portions of the program plan to be supported as yet. Moreover,
in many cases, the program areas are addressed jointly with
industry. Oil shale program funding for the plan is $31.3
million in Fiscal Year 1981.
This chapter not subject to U.S. copyright.

Published 1981 American Chemical Society

2 OIL SHALE, T A R SANDS, AND RELATED MATERIALS
Program Goal and Objectives
The Department o f Energy's R,D&D o i l shale goal i s t o permit

the e n t i r e o i l shale resource, both east and west, t o c o n t r i b u t e
to domestic energy proportionate to the resource and with a r e -
c o g n i t i o n o f the unique environmental character o f the o i l shale
areas. In concert with t h i s g o a l , the o b j e c t i v e s o f the R,D&D
program are:
o To overcome t e c h n o l o g i c a l b a r r i e r s to o i l shale commer-

cialization
o To f o s t e r development o f innovative processes for a l l

shales that reduce environmental impact
o To obtain accurate environmental data and demonstrate

or develop adequate environmental c o n t r o l systems
The a n a l y s i s o f commercialization i n c e n t i v e s and m i t i g a t i o n

of i n s t i t u t i o n a l b a r r i e r s i s the r e s p o n s i b i l i t y o f the A s s i s t a n t
Secretary for Resource A p p l i c a t i o n s . R,D&D a c t i v i t i e s are the
r e s p o n s i b i l i t y o f the A s s i s t a n t Secretary for F o s s i l Energy,
although the lead f o r environmental planning r e s t s with the
A s s i s t a n t Secretary for Environment. The R,D&D program,
however, i n t e g r a t e s the a c t i v i t i e s under the A s s i s t a n t Secretary
for F o s s i l Energy and the A s s i s t a n t Secretary for Environment.
Program Strategy
In essence, the DOE program goal i s t o develop the techno-

logy necessary for the production o f o i l shale on a commercial
basis and i n an environmentally acceptable manner. The DOE
strategy to accomplish t h i s end i s comprised o f two major a c t i -
v i t y elements:
o Research and Development
o Development and Demonstration Support
Through the existence o f these p a r a l l e l a c t i v i t i e s , the

DOE O i l Shale R,D&D Program focuses near term research and de-
velopment (R&D) on supporting i n d u s t r i a l development while main-
t a i n i n g an adequate l e v e l o f more advanced R&D attuned to future
needs. The technology developments that w i l l r e s u l t by achieving
the program's o b j e c t i v e s w i l l be made a v a i l a b l e to the o i l shale
i n d u s t r i a l community. I n d u s t r i a l p a r t i c i p a t i o n i n DOE sponsored
demonstrations i s encouraged as means o f maintaining the tech-
n o l o g i c a l alignment o f the R,D&D Program with the needs o f i n -
dustry. These demonstration a c t i v i t i e s involve the DOE Program

1. HARTSTEIN A N D HARNEY DOE's Oil Shale R, D, & D Program 3
i n the i n d u s t r i a l d e c i s i o n process and f a c i l i t a t e o i l shale

i n d u s t r y growth. Information and experience gained through the
c o n s t r u c t i o n and o p e r a t i o n o f any f a c i l i t i e s r e s u l t i n g from
these i n d u s t r y supportive a c t i v i t i e s w i l l be used d e f i n i n g future
R&D requirements which may be s a t i s f i e d d i r e c t l y by the p r i v a t e
sector through the program. The program i s designed i n concert
with and i n support o f i n c r e a s i n g i n d u s t r y a c t i v i t y .
The Program's R&D a c t i v i t y elements are s t r u c t u r e d to
p a r a l l e l and complement a c t i v i t i e s that i n d u s t r i a l developers
would need to perform when e s t a b l i s h i n g a commercial o i l
shale o p e r a t i o n . The i n i t i a l a c t i v i t i e s o f a developer
include tasks to c h a r a c t e r i z e the resource under c o n s i d e r -
a t i o n and s i t e planning f o r resource development. Following
t h i s , the developer needs to consider the p o t e n t i a l p h y s i c a l
environment and socioeconomic impacts before committing to a

proposed p r o j e c t . O i l shale resource development and e x t r a c -
t i o n e n t a i l s i t e p r e p a r a t i o n , mining (except f o r true i n s i t u
technologies) , and r u b b l i n g the i n s i t u r e t o r t i n preparation
for i n place combustion or t r a n s p o r t i n g the mined o i l shale to
a surface r e t o r t . R e t o r t i n g would then be undertaken, a f t e r
which the shale o i l would be upgraded and r e f i n e d . At each
point i n t h i s sequence, the o i l shale program w i l l develop
enhanced technology to e s t a b l i s h a p o t e n t i a l developer's
effectiveness .
Key T e c h n i c a l and Environmental Needs i n R,D&D
T e c h n i c a l . The O i l Shale R,D&D Program i s d i r e c t e d toward

developing a greater understanding o f the o i l shale resource and
p e r f e c t i n g an e f f e c t i v e means f o r the recovery o f shale o i l .
Program a c t i v i t i e s are d i r e c t e d toward the s o l u t i o n o f key t e c h -
n i c a l and environmental needs r e p r e s e n t i n g s i g n i f i c a n t b a r r i e r s
to commercial o i l shale development. Based on a review o f t e c h -
nology r e q u i r e d f o r o i l shale development, the f o l l o w i n g Key
T e c h n i c a l Needs have been i d e n t i f i e d as those that should
r e c e i v e the highest p r i o r i t y i n the R,D&D Program:
o E f f i c i e n t O i l Shale Rock Breakage and Retort Bed Pre-

p a r a t i o n Techniques,
o Development o f Retort Diagnostics and Instrumentation,
o Development o f Retort Control Procedures,
o Systems Engineering Methods f o r T o t a l O i l Shale Process

Development,
o E f f i c i e n t and E f f e c t i v e O i l Shale Mining Systems,

o Advanced Shaft Sinking Technology,
o Chemical K i n e t i c s o f the T o t a l P y r o l y s i s Process,
o Understanding Retorting Mechanisms and Developing a

Prediction
o Development o f A l t e r n a t i v e R e t o r t i n g Procedures.
Rock Breakage and Retort Bed P r e p a r a t i o n . Efficient

recovery o f o i l from shale depends c r i t i c a l l y upon having a
bed o f o i l shale rubble that i s r e l a t i v e l y uniform, both i n
p a r t i c l e s i z e and v o i d f r a c t i o n . Mining and r u b b l i n g methods
must be developed to assure optimal u n i f o r m i t y . Otherwise
sweep e f f i c i e n c y w i l l be poor, and s i g n i f i c a n t amounts o f o i l

shale rubble w i l l not be r e t o r t e d .
It i s expected that the R,D&D e f f o r t w i l l r e s u l t i n the
development o f technology f o r breaking o i l shale f o r mining
and preparing rubble beds such that e f f i c i e n t and productive
shale e x t r a c t i o n and modified i n s i t u r e t o r t i n g can be accom-
p l i s h e d . Retorts w i l l be designed and constructed which meet
the processing requirements f o r p a r t i c l e s i z e d i s t r i b u t i o n ,
uniform p e r m e a b i l i t y , uniform void d i s t r i b u t i o n , and bounding
of the f r a c t u r e d r e g i o n .
Retort Diagnosis and Instrumentation. The development o f

c o n t r o l instrumentation and methods f o r i n s i t u r e t o r t i n g i s
important f o r determining r e t o r t performance and y i e l d e f f i -
c i e n c y . The e f f o r t o f the RD&D program w i l l r e s u l t i n the
design o f thermal sensors, gas sampling devices, pressure
probes, remote sensing d e v i c e s , s t r a i n and displacement
gauges, and h e a l t h and s a f e t y monitoring equipment. This
equipment w i l l be designed and then tested and modified
through use i n s e v e r a l f i e l d t e s t s .
Retort C o n t r o l Procedures. The development o f r e t o r t con-

t r o l and operating procedures i s c r u c i a l to the success o f both
i n s i t u and modified i n s i t u r e t o r t i n g o f o i l s h a l e . The R,D&D
e f f o r t w i l l e s t a b l i s h a set o f b a s e l i n e operating plans from
data c o l l e c t e d from l a b o r a t o r y experiments, f i e l d t e s t s and the
outputs o f p r e d i c t i v e models. From the data c o l l e c t e d , an
e v a l u a t i o n w i l l be made on the e f f e c t s o f i n t e r m i t t e n t a i r
flows, l i q u i d water a d d i t i o n s , and other c o n t r o l parameters.
The r e s u l t o f t h i s e f f o r t w i l l be a r e t o r t operating plan
that maximizes r e t o r t i n g rate and y i e l d while c o n t r o l l i n g
temperature and burn front symmetry.
Systems Engineering. A systematic procedure f o r resource

1. HARTSTEIN A N D HARNEY DOE's OH Shale R, D, & D Program 5
i d e n t i f i c a t i o n and c h a r a c t e r i z a t i o n and for determination o f

appropriate recovery processes i s needed to assure e f f i c i e n t
and e f f e c t i v e use o f a l l domestic o i l shale r e s o u r c e s . The
need r e l a t e d o b j e c t i v e s o f the R,D&D program are: (1) to
develop and u t i l i z e methods f o r the planning o f o i l shale
development by matching o i l shale resources with appropriate
recovery processes; (2) to develop planning t o o l s (e.g., equip-
ment s e l e c t i o n c r i t e r i a , production models, economic models)
which w i l l a i d i n the design and a n a l y s i s o f e f f i c i e n t shale
o i l production f a c i l i t i e s ; and (3) t o determine the o v e r a l l
economics f o r the recovery o f energy products from o i l shale
by the a l t e r n a t i v e processes .
O i l Shale Mining Systems. Equipment and methods now used

for c o a l and hard rock mining are w e l l developed but are not
always a p p l i c a b l e to the demands o f o i l shale mining. Research
and development i s needed t o meet the p a r t i c u l a r requirements
of the o i l shale i n d u s t r y . The o b j e c t i v e o f the R,D&D program
i s t o develop technology and equipment f o r high volume, cost
e f f e c t i v e , underground and surface mining methods f o r e x t r a c t i n g
o i l shale f o r subsequent surface and modified i n s i t u p r o c e s s i n g .
Shaft Sinking Technology. The development o f shafe s i n k i n g

systems i s c r u c i a l f o r the l a r g e s c a l e commercial u t i l i z a t i o n
of o i l s h a l e . The R,D&D e f f o r t w i l l c a r e f u l l y examine the
current state o f the a r t i n s h a f t / s l o p e development. A compre-
hensive research and development plan w i l l be e s t a b l i s h e d that
attacks a l l the major d e f i c i e n c i e s i n the current s t a t e o f the
art f o r accessing o i l shale r e s o u r c e s . Access development system
concepts w i l l be defined a f t e r a s e r i e s o f tasks which examine
c u t t i n g and d r i l l i n g methods, water/ground c o n t r o l , and l a r g e
s c a l e d r i l l i n g . The expected r e s u l t o f t h i s e f f o r t w i l l be the
development o f techniques f o r e f f i c i e n t , s a f e , and environment-
a l l y acceptable shaft s i n k i n g .
Chemical K i n e t i c s . Several models have been developed

which simulate the p h y s i c a l p r o p e r t i e s o f o i l shale r e t o r t i n g
(e.g., shale composition, r e t o r t i n g r a t e s , p a r t i c l e s i z e s ,
porosity d i s t r i b u t i o n , e t c . ) . For the models to a c c u r a t e l y
simulate r e t o r t i n g , they should i n c l u d e the d e t a i l s o f the
major chemical r e a c t i o n s i n the system. The R,D&D program w i l l
develop the b a s i c data on chemical k i n e t i c s needed to model the
complex r e a c t i o n s taking place i n r e t o r t i n g . Among these
r e a c t i o n s are mineral decomposition, e s p e c i a l l y that o f
carbonates, which are l a r g e consumers o f energy; r e a c t i o n s
char with steam and carbonate to produce v a l u a b l e CO and
hydrogen; degradation ( l o s s ) r e a c t i o n s o f o i l ; gas phase
r e a c t i o n s producing hydrogen and CO2; gaseous s u l f u r e v o l u -

6 OIL S H A L E , T A R SANDS, AND RELATED MATERIALS
t i o n ; e t c . More work i s needed on gas phase r e a c t i o n s ,

e s p e c i a l l y on water gas and water gas s h i f t r e a c t i o n s , o i l
cracking stoichiometry o f hydrocarbon combustion, and s u l -
fur r e a c t i o n s i n s h a l e .
R e t o r t i n g Mechanisms. R e t o r t i n g i s only c r u d e l y under-

stood i n lab and f i e l d r e t o r t s . Important o p e r a t i o n a l pro-
blems i n c l u d e c o n t r o l o f burn f r o n t , s t a r t u p and sweep
e f f i c i e n c y , e f f e c t o f p a r t i c l e s i z e d i s t r i b u t i o n , i n l e t gas
composition, e s p e c i a l l y steam and a i r mixtures, bed i r r e g u -
l a r i t i e s , flow r a t e , p e r m e a b i l i t y changes during r e t o r t i n g ,
and temperature c o n t r o l . Program research w i l l address key
questions i n the area o f r e t o r t i n g mechanisms. A knowledge
of the mechanisms t a k i n g place during r e t o r t i n g i s r e q u i r e d
to i n t e r p r e t r e s u l t s o f experiments i n p i l o t and f i e l d r e t o r t s
to develop p r e d i c t i v e models, and f i n a l l y t o suggest process
m o d i f i c a t i o n s i n order to optimize r e t o r t performance,
e s p e c i a l l y o i l y i e l d s , and production r a t e s . The development
of r e t o r t i n g models w i l l a l s o be pursued as a means o f under-
standing and p r e d i c t i n g r e t o r t behavior.
A l t e r n a t i v e R e t o r t i n g Procedures. O i l shale r e t o r t i n g i s
approaching commercially v i a b l e l e v e l s o f development. How-
ever, the technology i s not s u f f i c i e n t l y advanced to assure
that o p t i m a l l y e f f i c i e n t and cost e f f e c t i v e r e t o r t i n g methods
are employed. The R,D&D program w i l l examine a l t e r n a t i v e r e t o r t -
ing processes with the o b j e c t i v e o f improving e x t r a c t i o n e f f i -
c i e n c y and economics. Studies w i l l i n c l u d e : (1) the use o f
oxygen ( i n s t e a d o f a i r ) plus steam to o b t a i n high BTU o u t l e t gas
and reduce e x i t gas handling and cleanup; (2) the s u b s t i t u t i o n
of water mist f o r steam to improve heat balance; (3) determining
r e t o r t i n g c o n d i t i o n s to produce v a r i o u s optimum product mixes,
e.g., maximum naphtha, minimum r e s i d u a l s , e t c . ; and (4) d e t e r -
mining r e t o r t i n g c o n d i t i o n s to produce minimum environmental
e f f e c t s (e.g., lowest s u l f u r i n o u t l e t gas, l e a s t s o l u b l e spent
shale, e t c . ) ; (5) use o f f l u i d beds to increase throughput,
improve y i e l d and lead to more favorable economics.
Environmental R&D Needs. The environmental research i n

1
the R,D&D Program represents a s i g n i f i c a n t p o r t i o n o f the DOE s
Environmental Development Plan. The o v e r a l l o b j e c t i v e o f the
Program's Environmental A c t i v i t y i s t o develop s o l u t i o n s t o
environmental problems a s s o c i a t e d with the process technologies
involved i n o i l shale production. To achieve t h i s o b j e c t i v e , a
s e r i e s of Key Environmental Needs have a l s o been e s t a b l i s h e d :
o Development o f Environmentally Acceptable Retort

Abandonment Strategy,

1. HARTSTEIN A N D HARNEY DOE's Oil Shale R, D, & D Program 7
o Guidelines to Ensure Health and Safety o f Workers

and General P u b l i c ,
o Development of S o l i d Waste Management Systems,
o Development of Water Treatment Systems,
o Development of an Emission C o n t r o l Strategy,
o M i t i g a t i o n of E c o l o g i c a l Impacts,
o M i t i g a t i o n of S o c i a l and Economic Impacts,

o Development of Compliance Plans, and
o Development of Subsidence Control Procedures.
Development of Environmentally Acceptable Retort

Abandonment Strategy. The spent shale remaining i n underground
r e t o r t s a f t e r product recovery contains s a l t s and carbonaceous
residues that can be leached by groundwater and thereby con-
taminate a q u i f e r s . In a d d i t i o n , some caving i n from the weight
of the overburden may occur r e s u l t i n g i n subsidence at the sur-
face .
The research r e l a t e d to t h i s need w i l l determine (1) the
p o t e n t i a l f o r groundwater i n t r u s i o n , what m a t e r i a l s are l i k e l y
to be d i s s o l v e d i n groundwater, the p e r m e a b i l i t y of the geologic
media to the s o l u b l e components, the t o x i c p r o p e r t i e s o f these
components, and the p e r s i s t e n c e of any t o x i c l e a c h i n g and sub-
sidence. The more general problem o f subsidence i n underground
mines, the s a f e t y and e c o l o g i c a l aspects, are d e a l t with i n a
separate area.
Guidelines to Ensure Health and Safety of Workers and

General P u b l i c . Operations o f an o i l shale i n d u s t r y w i l l i n t r o -
duce a new set o f i n d u s t r i a l working c o n d i t i o n s and p o s s i b l e
p u b l i c h e a l t h r i s k s as a r e s u l t of plant operations or product
distribution. The research d i r e c t e d toward t h i s need w i l l
examine the p o t e n t i a l h e a l t h and s a f e t y r i s k s to workers and
the general p u b l i c . A l l aspects o f the f u e l c y c l e w i l l be
examined from the mine and r e t o r t to the r e f i n e r y and end use of
the shale o i l products. P r o t e c t i v e measures, whether they be
through c o n t r o l s , process m o d i f i c a t i o n s , or i s o l a t i o n o f high
r i s k areas, w i l l be evaluated and e f f e c t i v e measures w i l l be
applied.
Development of S o l i d Waste Management Systems. Surface

processes produce extremely high volumes o f s o l i d waste i n

8 OIL SHALE, TAR SANDS, AND RELATED MATERIALS
the form of spent s h a l e . This research w i l l evaluate methods

of compacting and s t a b l i z i n g spent shale and other s o l i d wastes
such as sludges and spent c a t a l y s t s . The research w i l l lead to
the e v a l u a t i o n o f a l t e r n a t i v e s for s t a b l i z i n g and achieving
s e l f - s u s t a i n i n g ecosystems on the s o l i d waste p i l e s with minimum
p o t e n t i a l for water and wind e r o s i o n o f t o x i c m a t e r i a l s .
Development of Water Treatment Systems. In s i t u processes

produce approximately one b a r r e l o f r e t o r t water contaminated
with carbonaceous residues f o r each b a r r e l o f shale o i l recover-
ed. Surface processes also produce r e t o r t water but i n lower
q u a n t i t i e s . Although current plans do not c a l l f o r discharge
of wastewater, i t much be cleaned for reuse i n the process and
other uses, such as dust c o n t r o l and s o l i d waste management.
An o b j e c t i v e o f t h i s research i s to i d e n t i f y components i n the

wastewater that present e i t h e r a h e a l t h or environmental hazard
with respect to the intended use o f the water and to develop
systems to remove these components. Another o b j e c t i v e i s to
determine the consumptive water requirements o f d i f f e r e n t o i l
shale processes.
Development of an Emissions C o n t r o l Strategy. There are

two major components to the emissions c o n t r o l need. One i s
d i r e c t e d toward determination o f the emission c o n t r o l r e q u i r e -
ments based on the projected emission r a t e s and composition o f
the emission streams. In the case o f c r i t e r i a or regulated
p o l l u t a n t s , systems must be engineered to maintain ambient a i r
q u a l i t y w i t h i n the r e g i o n . In a d d i t i o n , m o d i f i c a t i o n o f a v a i l -
able technology and development o f new systems may be r e q u i r e d
i f r i s k a n a l y s i s i n d i c a t e s that unique substances i n the emission
stream r e q u i r e d removal.
The other component i s d i r e c t e d toward e s t i m a t i o n o f the
c a p a c i t y o f the r e g i o n to accept i n d u s t r i a l development—the
r e g i o n a l c a r r y i n g c a p a c i t y — b a s e d on the m e t e o r o l o g i c a l charac-
t e r i s t i c s o f the r e g i o n . More s p e c i f i c needs are (1) more
accurate atmospheric models to p r e d i c t the t r a n s p o r t and d i s -
p e r s i o n o f atmospheric p o l l u t a n t s , (2) determining r a t e s at which
p o l l u t a n t s are removed from the atmosphere, and (3) q u a n t i t a t i v e
information on the e f f e c t s o f a i r p o l l u t a n t s on c r i t i c a l atmos-
pheric processes r e l a t e d to u n d e s i r a b l e e f f e c t s , e.g., p r e c i p i -
t a t i o n q u a l i t y , decreased v i s i b i l i t y , and l o c a l c l i m a t e m o d i f i -
cation .
The research tasks that compose t h i s segment o f the plan
lead to the development o f workable emission c o n t r o l s and
estimates o f e f f e c t s o f i n d u s t r i a l i z a t i o n on r e g i o n a l a i r
quality.

1. HARTSTEIN A N D HARNEY DOEs Oil Shale R, D, & D Program 9
M i t i g a t i o n o f E c o l o g i c a l Impacts. O i l shale operations

w i l l cause much d i s r u p t i o n o f the surface environment through
normal c o n s t r u c t i o n and operation a c t i v i t i e s — l a r g e amounts o f
s o l i d waste s t o c k p i l e s on the s u r f a c e , water treatment opera-
t i o n s , steam generation, mining, m a t e r i a l handling, e t c . The
o b j e c t i v e s o f the e c o l o g i c a l research, i n a d d i t i o n to that
which i s an i n t e g r a l part o f other a c t i v i t i e s such as the s o l i d
waste management system, w i l l be t o (1) evaluate o v e r a l l e f f e c t s
of the operation on the e c o l o g i c a l communities ( p l a n t s , w i l d -
l i f e , f i s h ) and (2) develop e c o l o g i c a l t e s t procedures that w i l l
be used by other parts o f the program t o evaluate systems per-
formance with respect t o e c o l o g i c a l c r i t e r i a . This work w i l l
be geared to the environmental impact approach described above.
M i t i g a t i o n o f S o c i a l and Community Economic Impacts. The

s o c i a l and community economic aspects o f t e c h n o l o g i c a l develop-
ments are among the most d i f f i c u l t t o deal with. To a l a r g e
extent, t h i s i s due to the f a c t that s o l u t i o n s i n v o l v e i n s t i t u -
t i o n a l arrangements and l e g i s l a t i v e i n i t i a t i v e s beyond the scope
of most R&D operations. The problems do not lead themselves
to c o n t r o l l e d experiments that can be c a r r i e d out i n the f i e l d
or l a b o r a t o r y . I n s t a l l a t i o n o f m i t i g a t i n g measures such as
front-end f i n a n c i a l support t o communities for planning and
1
development w i l l be d e a l t with i n DOE s i n d u s t r i a l i z a t i o n p l a n t .
This part o f the R,D&D plan w i l l focus on the s o c i a l and economic
issues for which s o l u t i o n s are not known and which t h e r e f o r e
require additional research.
Methods for C o n t r o l l i n g or Preventing Subsidence. Under-

ground mines are always s u s c e p t i b l e to subsidence, which pre-
sents a concern for s a f e t y and environmental disturbance,
i n c l u d i n g a q u i f e r d i s r u p t i o n and changes i n the surface land
form. Some o f the r e t o r t abandonment c o n t r o l measures w i l l
a l s o act to prevent subsidence. The R&D conducted to s a t i s f y
t h i s need w i l l focus on general underground mining whether r e -
l a t e d to underground processes or surface r e t o r t i n g processes.
It w i l l be c l o s e l y t i e d to the mining tasks and include
analyses o f s a f e t y , h y d r o l o g i c a l d i s r u p t i o n , and changes i n
surface f e a t u r e s . The research w i l l focus p r i m a r i l y on pre-
v e n t i o n or planned, c o n t r o l l e d subsidence.
Development o f Compliance Plans. The R,D&D tasks, f o r

environmental as w e l l as the other three a c t i v i t i e s included i n
the Management Plan are c a r r i e d out i n conjunction with, o r as
part o f , major f i e l d p r o j e c t s . These p r o j e c t s , which involves
engineering and c o n s t r u c t i o n a c t i v i t i e s , must comply with
F e d e r a l , s t a t e , and l o c a l standards, and i n p a r t i c u l a r , with
p r o v i s i o n s o f the National Environmental P o l i c y Act (NEPA).

DOE prepares Environmental Assessments, and Environmental

Impact Statements when a p p r o p r i a t e , f o r those major f i e l d pro-
j e c t s . A i r , water, and other environmental monitoring, as r e -
quired t o demonstrate compliance with NEPA and a p p l i c a b l e permits,
i s conducted as part o f t h i s need; that data i s made a v a i l a b l e
to other tasks f o r v a r i o u s analyses and d e c i s i o n s .
Process S p e c i f i c R,D&D
In a d d i t i o n , t o s a t i s f y i n g key needs which p r e s e n t l y impede

o i l shale commercialization the O i l Shale R,D&D Program w i l l
simultaneously address the f o l l o w i n g processes.
Surface Processing. The DOE i s pursuing a s u r f a c e module

demonstration program as described i n P.L. 95-238. This pro-

gram w i l l r e s u l t i n both design and business proposals f o r the
c o n s t r u c t i o n o f a surface r e t o r t module. A d e c i s i o n to proceed
with c o n s t r u c t i o n o f designed modules on a cost shared b a s i s
i s being held i n abeyance pending i n d u s t r i a l a c t i o n s and the
a v a i l a b i l i t y o f other f i n a n c i a l i n c e n t i v e programs such as those
to be provided by the newly formed Synthetic Fuels Corporation.
Other research and development supporting surface r e t o r t i n g i s
mainly focused on mining and environmental e f f e c t s with long
term R&D d i r e c t e d to improving surface r e t o r t i n g processes.
In S i t u P r o c e s s i n g . The current near term emphasis o f the

Program's research a c t i v i t i e s i s on developing and expanding i n
s i t u r e t o r t i n g process technology, with p a r t i c u l a r emphasis on
modified i n s i t u methods. This programmatic d i r e c t i o n i s based
on the f a c t that i n s i t u o i l shale technology has not advanced
to the point where i t has been proven t o be t e c h n i c a l l y or
economically f e a s i b l e . Engineering analyses i n d i c a t e that i n
s i t u processes have the p o t e n t i a l t o be more cost e f f e c t i v e and
l e s s d i s r u p t i v e to the environment than surface r e t o r t i n g .
Therefore, the program i s focused on developing the necessary
t e c h n i c a l and environmental information from which an economic
and environmentally acceptable i n s i t u technology can be
engineered.
In a d d i t i o n to t h i s technology base program, the DOE i s
also sponsoring s e v e r a l major i n s i t u o i l shale f i e l d demon-
s t r a t i o n t e s t s . The f i e l d demonstration t e s t program and the
technology based R&D programs are i n t e g r a l l y r e l a t e d , i n that
f i e l d demonstration s i t e s are o f t e n used as s i t e s f o r R,D&D pro-
gram e f f o r t s and information gained from the f i e l d t e s t s i s used
to guide the o v e r a l l R,D&D program. Each o f these p r o j e c t s has
been evaluated to determine the program technology requirements
that can be met by ongoing i n d u s t r y c o n t r a c t and the other t e c h -

1. HARTSTEIN A N D HARNEY DOEs Oil Shale R, D, & D Program 11
nology requirements that can be achieved through m o d i f i c a t i o n

of the ongoing e f f o r t . In a d d i t i o n t o p r o v i d i n g v a l u a b l e tech-
nology base i n f o r m a t i o n , i t i s a n t i c i p a t e d that one or more o f
these p r o j e c t s could provide t e c h n i c a l evidence o f process f e a -
sibility. Use o f e x i s t i n g p r o j e c t s t o accomplish planned tasks
w i l l be maximized to reduce t o t a l program c o s t s .
Novel Processing Techniques. In a d d i t i o n to the develop-

ment o f more advanced aboveground and i n s i t u methods, research
i s being conducted i n t o new and novel technologies f o r e x t r a c t i o n
and processing o f o i l shale products. Although not c u r r e n t l y
competitive f o r near term commercial development, these e f f o r t s
are i n d i c a t o r s o f l i k e l y second generation advances i n o i l shale
technology.
The novel technologies being developed are i n two general

categories.
o Radio Frequency Heating
o Hydrogen Retorting
Program Operating Plans
The O i l Shale R,D&D Program i s defined i n a d r a f t document

which include two main s e c t i o n s : a Management and S t r a t e g i c Plan
which d e s c r i b e s the R,D&D program management s t r u c t u r e and the
long term s t r a t e g i c aspects o f the Department o f Energy's program
for achieving i t s technology o b j e c t i v e s , and an Implementation
Plan which d e t a i l s o i l shale R,D&D a c t i v i t i e s over the next
s e v e r a l years t o the s u b a c t i v i t y task l e v e l . In c o n t r a s t t o the
Implementation Plan, the Management and S t r a t e g i c Plan d e s c r i b e s
the Program's o b j e c t i v e s as they w i l l be a t t a i n e d by s a t i s f y i n g
a s e r i e s o f t e c h n o l o g i c a l needs, each o f which may r e q u i r e the
s u c c e s s f u l performance o f one or more sets o f tasks sometime i n
the f u t u r e . Described are o i l shale R,D&D a c t i v i t i e s f o r a
multiyear period i n terms o f needs, with emphasis placed upon
s o l v i n g key t e c h n i c a l and environmental needs i n h i b i t i n g o i l
shale commercialization and developing an a c t i v i t y b a s e l i n e f o r
each o f s e v e r a l candidate technologies to e s t a b l i s h program
d i r e c t i o n , resource requirements, and expected accomplishment.
Both plans serve as a b a s i s f o r developing and j u s t i f y i n g future
budget requests over t h e i r r e s p e c t i v e p e r i o d s .
S t r a t e g i c Plan. The p o l i c y , management, o r g a n i z a t i o n , and

long term aspects o f the O i l Shale R,D&D Program, as d i r e c t e d
toward s a t i s f y i n g i t s goal and o b j e c t i v e s , are described i n the
Management and S t r a t e g i c Plan. The d i s c u s s i o n i s i n three parts
addressing planned program e f f o r t s concerned w i t h :

o Key T e c h n i c a l Need R,D&D
o Key Environmental Need R,D&D
o Process S p e c i f i c R,D&D
These e f f o r t s are defined at the fundamental needs l e v e l ,

each R,D&D o b j e c t i v e (a key need being one such o b j e c t i v e ) r e -
q u i r i n g the f u l f i l l m e n t o f one o r more o f these fundamental
needs before i t i s obtained. This i s i n c o n t r a s t to the manner
in which the Implementation Plan i s d e f i n e d , wherein needs are
s p e c i f i e d i n terms o f the d e t a i l e d tasks r e q u i r e d t o s a t i s f y
them. S t r a t e g i c plans are o u t l i n e d i n a plane higher than that
used i n the Implementation Plan. Another d i s t i n c t i o n between
the two i s i n t h e i r planning time h o r i z o n . S t r a t e g i c plans are

defined over a long term p e r i o d , g e n e r a l l y about ten years,
whereas the Implementation Plan concentrates on the near term
period not exceeding f i v e years. To show c o n t i n u i t y between the
two plans, the time span addressed i n the Implementation Plan i s
a l s o defined with the s t r a t e g i c plans and need i d e n t i f i e r s u n i -
quely assigned i n the Implementation Plan are referenced i n
the S t r a t e g i c plans .
Implementation Plan. Short term plans are defined i n the

Implementation Plan i n terms o f the a c t i v i t i e s and tasks t o be
performed. Outlined w i t h i n the Plan are the research tasks that
w i l l be performed during the next f i v e year period t o enhance
and encourage commercial o i l shale development. The R,D&D tasks
are described with respect t o major a c t i v i t y areas (resource
c h a r a c t e r i z a t i o n , environment, development and e x t r a c t i o n , and
processing and i n s t r u m e n t a t i o n ) . Component s u b a c t i v i t i e s w i t h i n
each o f these a c t i v i t i e s provides a framework f o r o r g a n i z i n g
tasks around s p e c i f i e d technology areas. For each program task
the performance periods are s p e c i f i e d i n c o n j u n c t i o n with task
d e l i v e r a b l e s and p a r t i c i p a t i n g o r g a n i z a t i o n s . The Plan, con-
ceived as a working document which i s annually updated, thus
serves as a b a s i s f o r implementing the R,D&D Program by the
various research and i n d u s t r y p a r t i c i p a n t s .
RECEIVED March 19, 1981.

2
Computer Simulation of Explosive Fracture of
Oil Shale
THOMAS F. ADAMS
G-6, Mail Stop 665, Los Alamos National Scientific Laboratory,
P.O. Box 1663, Los Alamos, NM 87545
A necessary first step in the recovery of o i l from o i l shale

is the reduction of the rock to rubble. In mining operations,
the o i l shale is blasted loose and hauled to the surface for
further crushing or direct processing. In in situ methods,
the o i l shale must be rubbled in place, with l i t t l e or no direct
access to the resource bed. The efficiency and economic
viability of shale o i l recovery, therefore, depend directly on
blasting technology. The optimization of existing blasting
methods and, especially for in situ applications, the develop-
ment of new methods beyond the current state of the art will be
needed to use our o i l shale resources effectively.
Advances in blasting technology could perhaps be made by
trial and error, but experiments on the required scale are
costly. An alternative approach would be to develop analytical
and computational methods to simulate blasting in rock, and to
use the computer to aid in the design of new methods and the
planning and analysis of critical experiments. The computer
would not in itself specify blast patterns or delays, but would
allow the basic phenomenology of blasting to be studied.
Computer codes would become tools to study the effect of
changing design parameters such as the depth of burial or
explosive type on the results of blasting. New ideas could be
explored at modest cost before going to the field for large-
scale tests.
Computer Simulation
Computer simulation of explosive fracture of rock can be

carried out with finite difference stress wave propagation
codes, such as the YAQUI code (J_). YAQUI integrates in time the
coupled partial differential equations for the conservation of
mass, momentum, and energy. For a compressible fluid, these
equations are
^ + V • (Pu) = 0 , (1)
0097-615 6/ 81 /0163-0013$05.00/0
© 1981 American Chemical Society

3u +
+ (u V)u + _ V p = 0 (2)
3t
and
9t 2
2
_ L (I + \ u ) + (u - v ) (I + ^ u ) +
2 p
2
\ v- (pu) = 0 . (3)
Here, it i s the v e l o c i t y , p i s the mass d e n s i t y , p i s the

pressure, and I i s the s p e c i f i c i n t e r n a l energy. Viscous terms,
not shown here, a l s o enter the equations.
Rock i s a m a t e r i a l with strength. Therefore, i n the s o l i d
dynamics v e r s i o n o f YAQUI, the pressure terms i n the momentum
and energy equations are replaced with analogous terms i n v o l v i n g
the s t r e s s tensor. YAQUI i s a two-dimensional code, so i t can

t r e a t problems i n plane s t r a i n or c y l i n d r i c a l symmetry. T h i s i s
s u f f i c i e n t f o r many b l a s t i n g a p p l i c a t i o n s , such as a c y l i n d r i c a l
charge i n a borehole d r i l l e d i n p e r p e n d i c u l a r to the rock face.
YAQUI i s an "ALE" ( A r b i t r a r y Lagrangian-Eulerian) code ( 2 ) ,
although f o r these applications the Lagrangian option i s
g e n e r a l l y used.
Numerical methods to s o l v e f l u i d flow and s t r e s s wave
propagation problems have been developed over the years a t Los
Alamos. Given these methods and l a r g e modern computers, the
d i f f i c u l t y i n s o l v i n g these equations l i e s i n s p e c i f y i n g the
initial and boundary c o n d i t i o n s and i n the model used t o
describe the m a t e r i a l response. In p r a c t i c e , this means
s i m u l a t i n g n u m e r i c a l l y the detonation o f the high e x p l o s i v e and
the subsequent behavior o f the r e a c t i o n products, and developing
a constitutive relation. In f l u i d problems, the analog o f the
c o n s t i t u t i v e r e l a t i o n i s the equation o f s t a t e , which gives the
pressure as a f u n c t i o n o f the d e n s i t y and i n t e r n a l energy. The
s p e c i f i c a t i o n o f the equation o f s t a t e c l o s e s the s e t o f
equations (1-3) and makes a numerical s o l u t i o n p o s s i b l e . The
c o n s t i t u t i v e r e l a t i o n f o r rock serves the same r o l e , except that
i t i n v o l v e s the s t r e s s and s t r a i n tensors. I t must be w r i t t e n
i n incremental form, s i n c e the current s t a t e o f a s o l i d depends
on i t s l o a d i n g h i s t o r y . The d e s c r i p t i o n o f rock f r a c t u r e and
fragmentation i s an i n t e g r a l p a r t o f the c o n s t i t u t i v e r e l a t i o n .
E x p l o s i v e Behavior. The behavior o f the e x p l o s i v e must be

a c c u r a t e l y described, s i n c e the e x p l o s i v e i s the source o f
energy i n b l a s t i n g . Numerical methods f o r modeling e x p l o s i v e s
and the p r o p e r t i e s o f many common e x p l o s i v e s have been d i s c u s s e d
i n a book by Mader (3.). An i d e a l detonation i s one i n which the
chemical energy o f the e x p l o s i v e i s r e l e a s e d n e a r l y i n s t a n t a -
neously a t the detonation f r o n t . Many m i l i t a r y e x p l o s i v e s are
i d e a l i n t h i s sense, while commercial e x p l o s i v e s , such as ANFO,
are n o n - i d e a l . In non-ideal e x p l o s i v e s , the chemical energy i s
released over some d i s t a n c e behind the detonation f r o n t . The
behavior o f such e x p l o s i v e s , i n c l u d i n g the detonation v e l o c i t y ,

2. ADAMS Computer Simulation of Explosive Fracture 15
Chapman-Jouguet (C-J) pressure, and the d e t o n a b i l i t y , can depend

s t r o n g l y on the charge diameter, confinement, and method o f
initiation. I t i s , therefore, important that commercial
e x p l o s i v e s be t e s t e d under circumstances as c l o s e as p o s s i b l e to
those where they w i l l be used i n the f i e l d .
The behavior o f ANFO i n 0.1- and 0.2-m-diameter c y l i n d e r s
has been studied i n f i e l d t e s t s 5). Most o f the data were
obtained i n high-speed photography o f detonations o f e x p l o s i v e -
f i l l e d p l a s t i c or c l a y pipes immersed i n water. The detonation
v e l o c i t y can be determined q u i t e a c c u r a t e l y and i n the water
tank t e s t s , the propagation o f the shock i n the water and the
motion o f the i n t e r f a c e between the water and the pipe can be
followed. An equation o f s t a t e f o r the e x p l o s i v e r e a c t i o n
products i s then c a l c u l a t e d with a chemistry code. The equation
o f s t a t e i s used i n a two-dimensional s t r e s s wave code to

simulate the water tank t e s t . The equation o f s t a t e i s modified
i n f u r t h e r chemistry c a l c u l a t i o n s by v a r y i n g the degree o f
combustion a t the detonation f r o n t u n t i l the s i m u l a t i o n c l o s e l y
reproduces the a c t u a l t e s t . The data obtained f o r ANFO a r e
summarized i n Table I . S e v e r a l commercial e x p l o s i v e s besides
ANFO have a l s o been c h a r a c t e r i z e d i n t h i s way.
Table I
Behavior o f ANFO i n Various Diameters (4)
Diameter Detonation V e l o c i t y C-J Pressure

0.1 m 3500 m/s 2.4 GPa
0.2 4100 3.6
i n f i n i t e (ideal) 5400 7.3
Constitutive Relations
Geologic m a t e r i a l s l i k e o i l shale are commonly t r e a t e d as

elastic/plastic solids. F r a c t u r e under i n t e n s e l o a d i n g i s then
modeled as an extension o f p l a s t i c i t y or i s t r e a t e d with a
separate f r a c t u r e model. In a p p l i c a t i o n s l i k e rock b l a s t i n g ,
the l a t t e r approach i s p r e f e r a b l e , s i n c e f r a c t u r e o f rock i s
q u a l i t a t i v e l y d i f f e r e n t from p l a s t i c flow. Even so, continuum
damage models have been used to model b l a s t i n g f o r engineering
applications. Some c a l c u l a t i o n s with such a model w i l l be
presented below.
Fracture Model. A powerful fracture model based on
S t a t i s t i c a l Crack Mechanics (SCM) i s being developed a t Los
Alamos (6^. I n t h i s model, the rock i s t r e a t e d as an e l a s t i c
m a t e r i a l c o n t a i n i n g a d i s t r i b u t i o n o f penny-shaped flaws and
cracks o f v a r i o u s s i z e s and o r i e n t a t i o n s . P l a s t i c i t y near crack
t i p s i s taken i n t o account through i t s e f f e c t on the f r a c t u r e
toughness.

The SCM model makes use o f two r e s u l t s from fracture

mechanics: the c o n d i t i o n f o r s t a b i l i t y against crack growth f o r
an a r b i t r a r y s t a t e o f s t r e s s , and the r e d u c t i o n i n the e f f e c t i v e
e l a s t i c moduli o f a body c o n t a i n i n g a penny-shaped crack. The
f i r s t r e s u l t i s a g e n e r a l i z e d G r i f f i t h c r i t e r i o n , which can be
used to say which cracks i n the s t a t i s t i c a l d i s t r i b u t i o n w i l l
grow given the a p p l i e d s t r e s s e s . The second r e s u l t allows the
weakening o f the rock as i t i s f r a c t u r e d to be modeled.
The use o f the g e n e r a l i z e d G r i f f i t h c r i t e r i o n not only
allows cracks to extend under t e n s i l e l o a d i n g , but a l s o allows
cracks to extend i n shear, even under moderate normal com-
pression. T h i s means that closed shear cracks can extend under
i n t e n s e l o a d i n g (as near an e x p l o s i v e charge), causing the
m a t e r i a l to be much weaker under subsequent t e n s i l e l o a d i n g .
The r e d u c t i o n i n the e l a s t i c moduli i s a l s o important i n that i t

leads to the c o r r e c t d i r e c t i o n a l response as the rock i s
fractured. Thus, phenomena such as s p a l l are modeled i n a
r e a l i s t i c fashion.
The SCM theory i s being implemented and t e s t e d i n s t r e s s
wave codes a t t h i s time. E a r l y r e s u l t s are encouraging, and
t h i s approach holds great promise f o r the f u t u r e .
Damage Model. I t i s possible to extend the usual
elastic/plastic theory for solids to include fracture
11
phenomenologically i n terms o f a "damage parameter. T h i s has
been done by v a r i o u s i n v e s t i g a t o r s (7, .8), i n c l u d i n g Johnson (5)
with h i s Continuum Damage Model (CDM). In the CDM, the damage
parameter v a r i e s from zero to one as the rock goes from f u l l y
i n t a c t to h e a v i l y broken. The c o n s t i t u t i v e r e l a t i o n i n the CDM
i s a standard e l a s t i c / p l a s t i c model, except that the f a i l u r e
s u r f a c e i s a f u n c t i o n o f the damage parameter. The damage
parameter can be i n t e r p r e t e d as a measure o f the l o s s o f shear
strength a t zero c o n f i n i n g pressure. The l e v e l o f damage i n a
computational c e l l i n c r e a s e s during p l a s t i c flow.
The CDM has two a d d i t i o n a l f e a t u r e s that allow i t to
represent f r a c t u r e i n rocks. F i r s t , there i s a b r i t t l e / d u c t i l e
t r a n s i t i o n pressure. Above t h i s pressure, the rock behaves as
an elastic/plastic ductile solid, the f a i l u r e surface i s
independent o f the l e v e l o f damage, and the damage i s not
allowed to i n c r e a s e , even i f the f a i l u r e surface i s exceeded.
Second, the CDM allows f o r non-vanishing p l a s t i c volume s t r a i n
to approximate the d i l a t a n c y observed i n certain laboratory
experiments on o i l s h a l e .
The CDM has the disadvantage o f being built around
p l a s t i c i t y , which i s i n h e r e n t l y d i f f e r e n t from f r a c t u r e . In
a d d i t i o n , as a s c a l a r model ( f r a c t u r e described by a s i n g l e
damage parameter), i t cannot represent the tensor response o f
rock as a c c u r a t e l y as the SCM model. Nevertheless, i t does have
appropriate phenomenological features and, p r o p e r l y c a l i b r a t e d ,
should allow u s e f u l engineering c a l c u l a t i o n s .

Material Constants. Elastic wave v e l o c i t i e s have been

obtained f o r o i l shale by u l t r a s o n i c methods f o r v a r i o u s modes
o f propagation. E l a s t i c constants can be i n f e r r e d from these
data i f the o i l shale i s assumed to be a t r a n s v e r s e l y i s o t r o p i c
s o l i d ( 9 . ) . T h i s i s a reasonable approximation c o n s i d e r i n g the
bedded nature o f the rock. Many of the p r o p e r t i e s of o i l shale
depend on the grade (kerogen content), which i n turn i s
c o r r e l a t e d with the d e n s i t y ( 1 0 ) . The high pressure behavior o f
o i l shale under shock l o a d i n g has been s t u d i e d i n gas-gun impact
experiments ( 1 1 ) .
Data on the strength o f o i l shale are more d i f f i c u l t to
obtain, especially data f o r the intermediate strain rates
(10-103/s) relevant to blasting. Extensive quasi-static
t r i a x i a l t e s t i n g data are a v a i l a b l e f o r o i l shale of two grades
at a range o f c o n f i n i n g pressures (Jj?). These data were

averaged over sample o r i e n t a t i o n to g i v e mean y i e l d strengths.
I t has been shown that y i e l d strength varies significantly
depending on the o r i e n t a t i o n with respect to the bedding planes
( 1 3 ) , at least i n q u a s i - s t a t i c tests.
The triaxial testing data and other data (e.g., from
three-point bending t e s t s ) can a l s o be i n t e r p r e t e d i n terms of
the f r a c t u r e toughness o f o i l s h a l e . Rather than r e f e r r i n g to a
p l a s t i c y i e l d s t r e n g t h , the f r a c t u r e toughness serves as an
input constant f o r the SCM f r a c t u r e model. Other input data
needed f o r the SCM model include the mean crack (or flaw) s i z e
and d e n s i t y as a f u n c t i o n o f o r i e n t a t i o n throughout the sample.
These data could be obtained d i r e c t l y by examination of samples
or i n d i r e c t l y i n simple l a b o r a t o r y t e s t s .
Regardless of the m a t e r i a l model being used, data at i n t e r -
mediate s t r a i n r a t e s under c o n t r o l l e d l a b o r a t o r y c o n d i t i o n s are
needed. Such data should be obtainable soon with the new l a r g e
diameter gas gun and Split-Hopkinson Bar facilities being
e s t a b l i s h e d at Los Alamos.
Comparison between C a l c u l a t i o n s and F i e l d Experiments
Any complex code, such as YAQUI, must be c a l i b r a t e d and

v e r i f i e d by comparing c a l c u l a t i o n s with the r e s u l t s of r e a l i s t i c
f i e l d experiments. A s e r i e s of e x p l o s i v e f i e l d t e s t s u s i n g ANFO
i n o i l shale has been conducted i n the Colony Mine near R i f l e ,
Colorado. These experiments were performed under DOE auspices
with the cooperation o f A t l a n t i c R i c h f i e l d , TOSCO, and the
Colony Development Corporation. They were conducted for
comparison with code calculations and to o b t a i n e m p i r i c a l
i n f o r m a t i o n about b l a s t i n g i n o i l s h a l e .
Field Experiments. Fifteen i n t e r m e d i a t e - s i z e experiments
were conducted with amounts of ANFO ranging from 5 kg to over
1 0 0 kg. Three of the ,experiments were h e a v i l y equipped with
s t r e s s and v e l o c i t y gauges i n separate instrumentation boreholes
and d i a g n o s t i c cables i n s i d e the e x p l o s i v e boreholes (to g i v e

18 OIL SHALE, T A R SANDS, A N D R E L A T E D MATERIALS
r e a l - t i m e data on the detonation). The other experiments had

v a r y i n g l e v e l s o f i n s t r u m e n t a t i o n . E x t e n s i v e p r e - and post-shot
g e o l o g i c mapping were conducted a t each experiment s i t e . Pre-
and post-shot core samples were taken i n the v i c i n i t y o f some o f
the experiments. Where r u b b l i n g extended to the s u r f a c e , c r a t e r
p r o f i l e s were measured and data concerning the rubble were taken.
A complete a n a l y s i s and c o r r e l a t i o n o f the data i s i n
progress and w i l l be published elsewhere. The a n a l y s i s i s being
done p a r t l y i n the framework o f s c a l i n g r e l a t i o n s , where v a r i o u s
experiments are compared a f t e r removing f i r s t order e f f e c t s due
to d i f f e r e n t charge s i z e or depth o f b u r i a l . This aids i n
q u a n t i f y i n g e f f e c t s , such as the i n f l u e n c e o f s i t e - s p e c i f i c
geology (e.g., j o i n t and f a u l t s t r u c t u r e s ) , on c r a t e r s i z e and
shape.
In the remainder o f t h i s r e p o r t , we compare three YAQUI

calculations with the r e s u l t s o f the corresponding field
experiments. The c a l c u l a t i o n s and experiments to be discussed
a l l i n v o l v e d s i n g l e c y l i n d r i c a l charges o f 0.15-m-diameter ANFO
emplaced i n boreholes d r i l l e d s t r a i g h t i n t o the mine f l o o r . The
charge lengths and depths o f b u r i a l are given i n Table I I . The
detonator was placed a t the bottom o f the charge i n each case.
Table I I
Data f o r Three O i l Shale B l a s t i n g Experiments
Depth o f B u r i a l
Designation Charge Length Charge Bottom Charge Top
79-7 0.99 m 4.57 m 3.58 m
79-8 0.99 3.30 2.31
79-10 1.73 3.30 1.57
These three experiments form an i n t e r e s t i n g subset o f the

larger series. Experiment 79-7 was buried deeply enough that i t
was f u l l y contained, with no c r a t e r formation or even s u r f a c e
flaw a c t i v a t i o n . Post-shot d r i l l i n g d i d r e v e a l a rubbled region
around the charge. In experiment 79-8, the same s i z e charge was
used, buried 1.3 m c l o s e r to the s u r f a c e . An extensive shallow
c r a t e r was formed, s t a r t i n g about midway from the top o f the
charge to the mine f l o o r and extending outward. The c r a t e r was
asymmetric as a r e s u l t o f the i n f l u e n c e o f the l o c a l joint
structure. F i n a l l y , experiment 79-10 had the same charge bottom
depth as 79-8, but had more e x p l o s i v e . T h i s experiment produced
a roughly c o n i c a l crater s t a r t i n g near the center o f the
charge. T h i s c r a t e r was a f f e c t e d very l i t t l e by the j o i n t
structure.
YAQUI C a l c u l a t i o n s . The YAQUI code described above was used
to simulate experiments 79-7, 79-8, and 79-10. A continuum
damage model s i m i l a r to the one developed by Johnson (5.), using
Johnson's damage constants, was used with a rate-independent

elastic/plastic routine. I t i s instructive to f o l l o w the

sequence o f events that occurred i n experiment 79-8. Figures
1-4 show the l o c a t i o n o f the shock wave and the extent o f the
"damage" 0.2, 0.6, 1.0, and 2.0 ms, r e s p e c t i v e l y , a f t e r the
f i r i n g o f the detonator. At 0.2 ms (Figure 1), the detonation
f r o n t has moved more than halfway up the charge. The upward-
moving shock can be seen along with the region of intense damage
around the bottom o f the charge. By 0.6 ms (Figure 2 ) , the
detonation i s over and the shock wave i s propagating through the
o i l shale toward the f r e e s u r f a c e . Extensive r u b b l i n g has
occurred i n the v i c i n i t y o f the charge.
The shock wave i s approaching the f r e e surface a t 1.0 ms
(Figure 3 ) . Some a d d i t i o n a l damage has now occurred i n a region
bounded roughly by an i n v e r t e d 45° cone extending upward from
near the top o f the charge. T h i s i s the region where the

maximum shear l o a d i n g occurred during the f i r s t passage o f the
shock wave. The 45° angle i s r e l a t e d to the r a t i o o f the sound
speed i n o i l shale to the detonation v e l o c i t y i n ANFO. Had the
SCM model been used i n s t e a d o f the damage model, c l o s e d shear
cracks would have grown i n t h i s region as the shear wave passed.
A t e n s i l e r e l i e f wave propagates downward a f t e r the shock
reaches the f r e e s u r f a c e . T h i s causes a l a y e r of s p a l l damage
to occur near the surface above the charge. By 2.0 ms
(Figure 4 ) , the s p a l l l a y e r has formed and the f u l l extent o f
the computed damage can be seen. The c a l c u l a t i o n was c a r r i e d
out long enough to f o l l o w a l l the dynamic phases o f the b l a s t ,
but not long enough to f o l l o w the throwout of d e b r i s or the
formation o f the a c t u a l c r a t e r . The combination o f heavy damage
near the charge, the shear-damaged region, and the s p a l l l a y e r
presumably represent the c r a t e r that w i l l be formed. The
c a l c u l a t i o n does not, i n f a c t , show complete r u b b l i n g i n the
region above the charge. T h i s i s c o n s i s t e n t with the f a c t that
i n the f i e l d only a shallow c r a t e r , h e a v i l y i n f l u e n c e d by the
l o c a l geology, was formed.
F i g u r e 5 shows the extent o f damage c a l c u l a t e d a t 2.0 ms f o r
experiment 79-7. The regions o f damage around the charge and
shear damage above the charge are v i s i b l e , as i n the c a l c u l a t i o n
f o r experiment 79-8. However, n e i t h e r damaged region reaches
the s u r f a c e , and the t e n s i l e r e l i e f wave was too weak to produce
a s p a l l l a y e r . Thus, the c a l c u l a t i o n i s i n good agreement with
the observation i n the f i e l d that there was no surface damage,
although there was an extensive rubbled region around the charge.
F i g u r e 6 shows the c a l c u l a t e d damage d i s t r i b u t i o n a t 2.0 ms
f o r experiment 79-10. The r e l a t i v e l y shallow depth o f b u r i a l
f o r t h i s charge r e s u l t s i n intense damage. The three regions o f
damage seen i n e a r l i e r c a l c u l a t i o n s now merge to form a c r a t e r
much l i k e the one that was observed. The i n t e n s i t y o f rock
breakage shown i n the c a l c u l a t i o n makes i t easy to understand
why the j o i n t s t r u c t u r e had l i t t l e i n f l u e n c e on the c r a t e r i n
the f i e l d .

20 OIL SHALE, T A R SANDS, ANDRELATED MATERIALS
11
Figure 1. Damage distribution and mean stress contour plot at 0.2 ms in com-
puter simulation of Experiment 79-8. The mean stress contour level is lOMPa com-
pressive. The distribution and density of the dots show the extent of the damage. The
blank region inside the damaged area is the explosive, which lies on an axis of cylindrical
symmetry. The dimensions of the plot frame are 14 m X 9 m. The top boundary is the
mine floor. At this time, the detonation front is traveling upward through the explosive.
A shock wave is propagating upward and away from the charge, and damage is occurring
near the portion of the charge that has been detonated.
puter simulation of Experiment 79-8. The contour level and plot dimensions are the
same as in Figure 1. At this time, the detonation is complete. A shock wave is propa-
gating upward toward the free surface. Extensive damage has occurred around the
charge.

ADAMS Computer Simulation of Explosive Fracture
same as in Figure 1. At this time, the shock wave is approaching the free surface. Dam-
age has occurred above the charge in addition to the damage around the charge.
same as in Figure 1. At this time, a layer of spall damage can be seen near the free
surface. It developed as the tensile relief wave propagated downward following the
interaction of the explosively generated shock with the free surface. This figure shows
the final computed damage distribution.

OIL SHALE, T A R SANDS, ANDRELATED MATERIALS
same as in Figure 1. Note that the charge is buried more deeply here. This figure shows
the final computed damage distribution. No spall damage has occurred near the surface
because of the increased depth of burial.
same as in Figure 1. Note that the bottom of the charge is at the same depth as in
Experiment 79-8 (Figures 1-4), but the charge is larger and extends closer to the free
surface. The shallower effective depth of burial has resulted in the formation of a
crater-shaped damage region, much as was observed in the corresponding field experi-
ment.

Conclusion
The steps in assembling the computational tools needed to

simulate the explosive fracture of o i l shale have been
described. The resulting code, with its input data, was then
used to simulate three explosive field experiments. The results
of the calculations are in good agreement with what actually
occurred in the field. Further detailed comparisons are in
progress for these experiments and the others that have been
conducted. As this is done, improvements will be made in the
input data and in the code physics.
The development of computer codes as tools to predict rock
breakage makes a variety of interesting studies possible. The
properties of the explosive can be changed to see how the extent
of rubbling is affected. Studies of spacing and delays for

decked charges are also possible. Finally, the codes can be
applied in situations, such as confined-volume blasting, at the
frontiers of blasting technology. These areas are vital to the
effective utilization of our o i l shale resources, especially
with in situ techniques. Computer simulation will play a
central role in the development of new technology for energy and
mineral resource recovery.
Acknowledgment
This work was performed under the auspices of the U. S.

Department of Energy.
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Lagrangian-Eulerian Computer Program for Fluid Flow at All
Speeds," Los Alamos Scientific Laboratory report LA-5100,
March 1973.
2. Hirt, C. W.; Amsden, A. A.,; Cook, J. L. "An Arbitrary
Lagrangian-Eulerian Computing Method for A l l Flow Speeds,"
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3. Mader, C. L. "Numerical Modeling of Detonations";
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7. Butkovich, T. R. "Correlations between Measurements and

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presented at the 2nd International Conference on Numerical
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12. Johnson, J. N.; Simonson, E. R. "Analytical Failure
Surfaces for Oil Shale of Varying Kerogen Content," in
Timmerhaus, K. D.; Barber, M. S., Eds., "High Pressure
Science and Technology, Sixth AIRAPT Conference," Vol. 2;
Plenum: New York, 1979, pp. 444-454.
13. McLamore, R.; Gray, J. "The Mechanical Behavior of
Anistropic Sedimentary Rocks," J. Eng. Ind. 1967, 89, 62.
RECEIVED January 19, 1981.

3
Fracturing of Oil Shale by Treatment with Liquid
Sulfur Dioxide
D. F. BUROW and R. K. SHARMA
Department of Chemistry, University of Toledo, Toledo, OH 43606
Development of o i l shale deposits as sources of fuels,

lubricants, and chemical feedstocks is being considered as an
alternative to present reliance on conventional petroleum
reserves. Procedures, advantages, and disadvantages for mining/
surface processing and for in situ retorting have been widely
discussed (1, 2, 3). In the former approach, crushing of the
shale is essential for efficient o i l recovery. As a result of
tests with a variety of mechanical crushers (4), i t is apparent
that the effectiveness of mechanical crushing is limited by the
characteristics of the shale. A slab-forming tendency allows
large pieces to pass through many conventional crushers. The
resilience and slippery nature of the shale limits the effective-
ness of mechanical impact. Furthermore, shale abrasiveness and
a tendency for the shale to adhere to crusher surfaces causes
maintenance problems with crushers. In situ retorting is
enhanced by fracturing with explosive charges or expansion of
existing fractures with fluids such as water. Fracturing by
explosive charges is frequently limited to the vicinity of the
charge since the explosive shock is dissipated by shale
resilience. Efficient fracturing by aqueous fluids is limited
by a tendency for capillary adhesion of water in the fissures
and by available water supplies in arid regions where o i l shale
deposits often occur.
Employment of chemical comminution techniques for surface
processing of o i l shales could circumvent many of the limitations
to mechanical crushing as well as reduce or eliminate capital and
maintenance costs of crushers. For in situ processing, such
techniques could provide an alternative to explosive or hydro-
static fracturing. Our recent success in comminuting and desul-
furizing coal by treatment with liquid sulfur dioxide 05, 6),
suggested that similar treatments might be successfully applied
to o i l shale processing.
Liquid SO2 is a remarkably subtle and selective solvent with
moderate Lewis acid properties, a substantial resistance to
oxidation and reduction when pure, and a propensity to support a
0097-615 6/81/0163-0025 $05.00/0


v a r i e t y o f i o n i c , f r e e r a d i c a l , and molecular r e a c t i o n s (7) .

P h y s i c a l p r o p e r t i e s of l i q u i d SO2 which can be e x p l o i t e d advanta-
geously i n c l u d e : a -10° bp, moderate vapor pressure a t room
temperature, high d e n s i t y , low v i s c o s i t y , and low surface t e n s i o n .
Since SO2 has a b o i l i n g p o i n t of -10°C, i t i s e a s i l y l i q u i f i e d
and/or removed a f t e r r e a c t i o n ; i t can be e a s i l y manipulated
without the need f o r e x o t i c c o n s t r u c t i o n m a t e r i a l s . Furthermore,
i t i s an inexpensive m a t e r i a l which i s r e a d i l y a v a i l a b l e i n l a r g e
q u a n t i t i e s from smelting and f o s s i l f u e l combustion; i f not
u t i l i z e d , i t must be disposed o f i n some s t a b i l i z e d form a t con-
s i d e r a b l e expense. Thus, the d i r e c t use of s u l f u r d i o x i d e could
provide an a l t e r n a t i v e means o f cost recovery f o r p o l l u t i o n
abatement technology.
Here we wish t o r e p o r t the r e s u l t s o f p r e l i m i n a r y e x p e r i -
ments i n which o i l shales are t r e a t e d with l i q u i d s u l f u r d i o x i d e

to e f f e c t f r a c t u r i n g ; observations made during these experiments
suggest that l i q u i d SO2 may a l s o be of u t i l i t y i n other phases
of o i l shale p r o c e s s i n g . We a r e , p r e s e n t l y , unaware of any
previous r e p o r t s o f such experiments.
Experimental
S u l f u r d i o x i d e was d r i e d and manipulated as described e l s e -

where ( 7 ) . A 1 - l i t e r s t a i n l e s s s t e e l autoclave (Parr Model 4641)
was u t i l i z e d f o r p r o c e s s i n g a t pressures i n excess o f c a . 3 atm.
In experiments u t i l i z i n g l a r g e r shale pieces (6-8 cm), clamped
shale samples, or s u p e r c r i t i c a l c o n d i t i o n s , samples were placed
d i r e c t l y i n the autoclave. For s u b - c r i t i c a l experiments using
small shale p i e c e s , samples were sealed i n f r i t t e d g l a s s tubes
with l i q u i d SO2 ( c a . 2:1 or l e s s S02/shale by weight) to
f a c i l i t a t e recovery of e x t r a c t s . S u l f u r d i o x i d e was d i s t i l l e d
on to the shale a t -78°C; the system was then sealed and brought
up to p r o c e s s i n g temperature. Temperatures of 25, 70, and 170°C
were used; s u p e r c r i t i c a l c o n d i t i o n s f o r SO2 were achieved a t
the l a t t e r temperature.
Processing time was c a . 2 hours f o r elevated temperature
experiments; f o r room temperature experiments, the time ranged
from 2 t o 24 hours. No mechanical a g i t a t i o n was employed. Upon
c o o l i n g , the SO2, s h a l e , and e x t r a c t were recovered. The shales
were inspected immediately upon recovery and a t s e v e r a l i n t e r v a l s
thereafter. S u l f u r analyses and i n f r a r e d s p e c t r a o f the shales
were performed on o r i g i n a l , processed, and processed/heated
samples to determine r e s i d u a l SO2 content. I n f r a r e d s p e c t r a of
the e x t r a c t s were a l s o obtained. A l l i n f r a r e d s p e c t r a were
recorded on a P e r k i n Elmer Model 621 spectrophotometer; s o l i d
samples were examined as KBr p e l l e t s and shale e x t r a c t s were
examined as t h i n f i l m s (neat) between NaCl p l a t e s .
Shale samples were a l s o t r e a t e d with gaseous SO2, l i q u i d
CO2, l i q u i d NH3, water, and s e v e r a l organic l i q u i d s at 25°C f o r
2 days. Procedures e q u i v a l e n t t o those used with l i q u i d SO2 were

3. BUROW A N D SHARMA Fracturing of Oil Shale 27
employed f o r treatment with gaseous SO2, l i q u i d CO2, and l i q u i d

NH3. Treatment with other l i q u i d s c o n s i s t e d of immersion of
shale samples i n the l i q u i d contained i n covered beakers.
Samples of Antrim, Green R i v e r , and Moroccan o i l shales were
obtained from the Laramie Energy Technology Center. The composi-
t i o n of t y p i c a l samples of these three shales i s i l l u s t r a t e d i n
Table I.
Results and D i s c u s s i o n
Upon exposure of the shales to l i q u i d SO2, h i g h l y c o l o r e d

s o l u t i o n s develop due to formation of donor-acceptor complexes
between e x t r a c t e d o i l c o n s t i t u e n t s and the SO2. Green R i v e r
shale produces red-brown s o l u t i o n s , Moroccan shale forms orange
s o l u t i o n s , and Antrim shale forms yellow s o l u t i o n s ; i n each case,

these c o l o r s are more intense when higher p r o c e s s i n g temperatures
are used.
F r a c t u r i n g of Shales. L i q u i d SO2 causes extensive

f r a c t u r i n g i n each of the three shales examined i n t h i s p r e l i m i n -
ary study; Figure 1 i l l u s t r a t e s r e p r e s e n t a t i v e examples of t h i s
f r a c t u r i n g . T h i s f r a c t u r i n g occurs both along and across
l a m i n a t i o n s . With the l a r g e r lumps, laminations are f r e q u e n t l y
expanded to 1-2 cm; f r a c t u r e s across laminations are l e s s
pronounced but d i s t i n c t l y v i s i b l e . Green River shale e x h i b i t s
numerous small cracks whereas the other two shales e x h i b i t a
fewer number of l a r g e r cracks. With p r o c e s s i n g temperatures
below 25°C, the degree of f r a c t u r i n g i s g r e a t e s t i n Moroccan
and l e a s t i n Antrim shale; with higher p r o c e s s i n g temperatures,
d i f f e r e n c e s i n degree of f r a c t u r i n g are not so apparent.
Samples of each of the s h a l e s , r i g i d l y clamped both across and
along laminations a l s o e x h i b i t e d extensive f r a c t u r i n g . Immedi-
a t e l y upon recovery from the r e a c t o r , the samples are so
b r i t t l e as to be e a s i l y broken with the f i n g e r s ; a f t e r standing
f o r a time, the samples become s l i g h t l y l e s s b r i t t l e but a l l
f r a c t u r i n g i s maintained. Although no q u a n t i t a t i v e t e s t s of
mechanical p r o p e r t i e s have been made, i t appears t h a t l i t t l e of
the r e s i l i e n c e and s l i p p e r y n e s s of the o r i g i n a l shales i s r e -
t a i n e d . Surfaces of the processed samples have a s o f t l u s t e r o u s
appearance.
Shale samples were subjected to treatment with other f l u i d s
at 25°C to provide comparative data on t h e i r a b i l i t y to f r a c t u r e
these s h a l e s . From among these f l u i d s o n l y gaseous SO2, l i q u i d
NH3, and methylene c h l o r i d e were e f f e c t i v e f r a c t u r i n g agents
under these c o n d i t i o n s . The r e s u l t s are summarized i n Table I I .
Under the same c o n d i t i o n s of temperature and pressure, gaseous
SO2 i s l e s s e f f e c t i v e than the l i q u i d i n producing f r a c t u r e s .
Both l i q u i d NH3 and methylene c h l o r i d e produce roughly the same
degree of f r a c t u r i n g as l i q u i d SO2. L i q u i d NH3, however, appears
to produce the greatest f r a c t u r i n g with Antrim shale and the

Table I. T y p i c a l Composition of O i l Shales Examined
Green River (Colorado)

d e
Organic Matter: 14%
(mostly a l i p h a t i c ) '
Oil Yield: ^25
gal/ton
Dolomite and C a l c i t e : 43%
Feldspar and P l a g i o c l a s e : 16%
I l l i t e , M o n t m o r i l l i n i t e , Muscovite: 13%
Quartz: 9%
c
Antrim (Michigan)
d e
Organic Matter: 9% 9
(1:1 a l i p h a t i c / a r o m a t i c )
Oil Yield: VL0
gal/ton
Illite: 45%
Quartz: 30%
Pyrite: 5%
Carbonates: 5%
Moroccan
d e
Organic Matter: 11%
(3:1 a l i p h a t i c / a r o m a t i c ) *
Oil Yield: vL8
gal/ton

a. Samples provided by F. M i k n i s , LETC
b. Ref. 8.
c. Ref. 9.

d. Ref. 10.
e. A l i p h a t i c / a r o m a t i c r a t i o e s t a b l i s h e d from s o l i d s t a t e C nmr
s p e c t r a , Ref. 10.
BUROW AND SHARMA Fracturing of Oil Shale
Figure 1. Representative examples of the fracturing of oil shales by liquid S0 ;

2
(left) treated samples; (right,) untreated samples; (a) Antrim shale treated at 170°C
for 2 h; (b) Green River shale treated at 70°C for 2 h; (c) Moroccan shale treated
at 70°Cfor2 h.

3
Table I I . F r a c t u r i n g o f O i l Shales by Various F l u i d s
3
Shales*
Fluid Antrim Green R i v e r Moroccan
Gas (^3 atm) - MF,E -

L i q u i d (-78°C) N MF,E HF,E
L i q u i d (25°C) MF,E HF,E HF,E
L i q u i d (70°C) HF,E HF,E HF,E
S u p e r c r i t i c a l (170°C) HF,E HF,E HF,E
C0 2 ( L i q u i d , ^60 atm) N N N
NH 3 ( L i q u i d , VL0 atm) HF,E HF,E HF,E
H 0 2 - N -
CH CN 3 - N -
DMSO - N -
DMF - N -
HMPA - N -
C H
N -
6 6

-
H CC1
2 2 - HF,E -

a. Except f o r l i q u i d S 0 , t e s t s were run a t 25°C f o r 2
2
days.
b. N: no apparent f r a c t u r i n g , MF: moderate f r a c t u r i n g ,
HF: extensive f r a c t u r i n g , E: e x t r a c t observed.
l e a s t with Moroccan shale; t h i s trend i s j u s t the opposite o f

that observed with l i q u i d SO2. Our r e s u l t s with l i q u i d CO2 are
i n apparent c o n f l i c t w i t h r e s u l t s reported by M i l l e r , et a l . (11)
for treatment o f Devonian shales with CO2 f l u i d s . From among
the f l u i d s t e s t e d , l i q u i d SO2 has s e v e r a l advantages as a
f r a c t u r i n g agent f o r o i l s h a l e s : i t i s low i n c o s t , i t i s
a v a i l a b l e i n q u a n t i t y , i t i s not d e r i v e d from e i t h e r petroleum
or n a t u r a l gas, and i t i s r e a d i l y manipulated due t o i t s moderate
vapor pressure.
The s u l f u r content of the shales i s increased somewhat by
p r o c e s s i n g i n l i q u i d SO2; r e s i d u a l s u l f u r i n c r e a s e s s i g n i f i c a n t l y
with the temperature of the treatment, however. For example,
at room temperature, r e s i d u a l s u l f u r i n c r e a s e s by 1-2% but a t
170°C, i t i n c r e a s e s by 5-10%. Comparison of i n f r a r e d s p e c t r a of
untreated and t r e a t e d shale samples (Figures 2-4, A and B)

i n d i c a t e s that t h i s increased s u l f u r content i s due to formation
of sulfur-oxygen c o n t a i n i n g r e s i d u e s , probably s u l f i t e s and/or
s u l f a t e s , i n the s h a l e s . I t might appear that the increase i n
s u l f u r content o f any shale f r a c t u r e d by l i q u i d SO2 would be
d e l e t o r i o u s to o i l produced i n a subsequent r e t o r t i n g step.
However, s i n c e t h i s r e t a i n e d SO2 appears t o be i n the i n o r g a n i c
part o f the shale as adsorbed SO2, s u l f i t e s , or s u l f a t e s , l i t t l e
contamination o f the r e t o r t e d o i l should occur: adsorbed SO2
can be removed i n a m i l d preheating step and the s u l f i t e / s u l f a t e
species are s u f f i c i e n t l y s t a b l e to remain i n t a c t during any
r e t o r t i n g step. S u l f u r elemental and i n f r a r e d analyses o f
t r e a t e d shale samples, performed before and a f t e r m i l d h e a t i n g ,
demonstrated that adsorbed SO2 can be removed e a s i l y .
P r e l i m i n a r y SEM/EDXA r e s u l t s f o r Green River Shale i n d i c a t e
that these sulfur-oxygen r e s i d u e s are apparently a s s o c i a t e d with
s e l e c t e d i n o r g a n i c c o n s t i t u e n t s of the s h a l e . EDXA o f untreated
Green River shale samples i n d i c a t e d a Si/Ca r a t i o o f c a . 1.5;
t h i s r a t i o corresponds c l o s e l y to that expected from the b u l k
composition o f the shale (Table I ) . The s u l f u r which i s present
i n untreated samples was observed to be c o r r e l a t e d with Ca
r a t h e r than Fe l o c a t i o n s , suggesting that l i t t l e p y r i t i c s u l f u r
was present i n these p a r t i c u l a r samples. Treated samples of
Green River shale e x h i b i t e r o s i o n and p i t t i n g o f the s u r f a c e i n
Ca r i c h areas but no apparent changes i n S i r i c h areas. The
p i t s have diameters i n the 2-10 ym range. In t r e a t e d samples,
the Si/Ca r a t i o was o f t e n found to be s i g n i f i c a n t l y higher than
i n untreated samples; t h i s observation suggests that l i q u i d SO2
causes a surface d e p l e t i o n o f Ca i o n s . The increased s u l f u r
content of t r e a t e d samples i s r e a d i l y apparent i n the EDXA
r e s u l t s ; t h i s increased S content i s a s s o c i a t e d with Ca r i c h but
not S i or Fe r i c h regions i n the s h a l e . These SEM/EDXA data
suggest that l i q u i d SO2 a t t a c k s the c a l c i t e and/or dolomite
c o n s t i t u e n t s o f Green River shale and, perhaps, thereby causing
the observed f r a c t u r i n g . S i m i l a r data on the other shales were
not obtained during t h i s e x p l o r a t o r y work.

to
F
on
ssr
w
Η
>
υ
>
σ

w
>
Η
W

α
>
Η
W
Figure 2. IR spectra of Green River oil shale: (a) untreated sample; (b) sample treated with liquid
2 2
S0 at 70°C for 2 h; (c) sample treated with S0 fluid at 170°C for 2 h; (d) extract isolated from r
treatment in b. on

W A V E N U M B E R (CM)

Figure 3. IR spectra of Morrocan oil shale: (a) untreated sample; (b) sample treated with liquid
2
SO at70°C for 2 h; (c) extract isolated from treatment in b.
Ο
Ρ
a
r
w
Η
>
GO
>
Ζ
>

Η
W
σ

Figure 4. IR spectra of Antrim oil shale: (a) untreated sample; (b) sample treated with liquid >
Η
2
SO at70°C for 2 h; (c) extract isolated from treatment in b. W
00
F r a c t u r i n g of Model M i n e r a l s . Further i n s i g h t i n t o the p r o -

cesses r e s p o n s i b l e f o r l i q u i d SO2 f r a c t u r i n g of these shales i s
provided by the behavior of s e v e r a l m i n e r a l s when subjected to
l i q u i d SO2. Authenic samples of c a l c i t e ( c r y s t a l s ) , dolomite
(hard lumps), gypsum (hard lumps), and i l l i t e (hard lumps) were
t r e a t e d with l i q u i d SO2 at 25°C f o r 2-5 hours; a f t e r removal of
the SO2, the t r e a t e d minerals were heated f o r 2 hours at 100°C;
i n f r a r e d s p e c t r a and s u l f u r analyses were then obtained. Calcite
c r y s t a l s developed numerous f i n e cracks and a f i n e powder f l a k e d
off. Although the powder contained no s u l f u r (elemental
a n a l y s i s ) or S-0 m o i e t i e s (IR s p e c t r a ) , the cracked c r y s t a l s were
shown to c o n t a i n 0.18% s u l f u r i n the form of sulfur-oxygen
s t r u c t u r e s . Although these data are c o n s i s t e d w i t h a 0.7% con-
version v i a
O p
Z5 ±
CaC0 (s) + S 0 U )
3 2 - > CaS0 (s) + C 0 ( s )
3 2
other processes cannot he excluded at t h i s stage. Dolomite, on

the other hand, d i d not appear to be e f f e c t e d by l i q u i d SO2 under
the c o n d i t i o n s employed: t r e a t e d dolomite e x h i b i t e d no f r a c t u r -
ing, no s u l f u r content, and no mass change. Gypsum chunks were
f r a c t u r e d by l i q u i d SO2. I n f r a r e d and s u l f u r analyses i n d i c a t e
that l i q u i d S0 i n t e r a c t s with gypsum i n two ways: f i r s t ,
2
simple e x t r a c t i o n o f water of c r y s t a l l a t i o n and, second, r e a c t i o n

with a p o r t i o n of the remaining water of c r y s t a l l a t i o n to form
+
H and HSO3. Large cracks develop and a powder f l a k e s o f f when
i l l i t e lumps are t r e a t e d with l i q u i d SO2; s u l f u r analyses i n d i -
cate approximate compositions to be iKAl^SiAK^o(OH)4]•(SO2)0.3
(lumps) and [KAli SiA10 o(OH)i ] • (S0 ) o.> (powder). I n f r a r e d
t 2 + 2
s p e c t r a l changes suggest p a r t i a l r e a c t i o n of the OH groups to

form SO3H groups.
F r a c t u r i n g Mechanisms. These observations with model

minerals suggest that s e v e r a l mechanisms be considered f o r the
observed f r a c t u r i n g of o i l shales by l i q u i d SO2. P a r t i a l con-
v e r s i o n of carbonates to s u l f i t e s could d i s r u p t m i c r o c r y s t a l l i n e
l a t t i c e s i n carbonate r i c h s h a l e s . P a r t i a l r e a c t i o n of the OH
groups i n a l l u m i n o s i l i c a t e s could cause s i m i l a r changes i n
s i l i c e o u s s h a l e s . E x t r a c t i o n of or r e a c t i o n with water of
c r y s t a l l i z a t i o n i n shale components could be o p e r a t i n g i n both
types of s h a l e . P u r e l y p h y s i c a l processes, perhaps i n v o l v i n g
p e n e t r a t i o n o f pores and m i c r o s c o p i c vacancies w i t h subsequent
a d s o r p t i o n to modify surfaces or d i s p l a c e s u r f a c e water, need to
be considered as w e l l . F i n a l l y , our observations that the
v i t r i n i t e s are e x t e n s i v e l y f r a c t u r e d when c o a l s are t r e a t e d with
l i q u i d SO2 (.5, 6) suggests that s w e l l i n g and/or e x t r a c t i o n of
organic c o n s t i t u e n t s of the shale may a l s o p l a y a r o l e . At t h i s
stage, i t i s b e l i e v e d that the f r a c t u r i n g of a p a r t i c u l a r type
of o i l shale by l i q u i d S0 i s probably due to a combination of
2
s e v e r a l of these modes.
I n i t i a l comparison of the f r a c t u r i n g r e s u l t s obtained v i a

l i q u i d SO2 treatment with those obtained v i a l i q u i d NH3 t r e a t -

ment might suggest that the d i f f e r e n c e s could be a t t r i b u t e d
simply to d i f f e r e n c e s i n the acid/base c h a r a c t e r i s t i c s of the
l i q u i d s and the s h a l e s . Further c o n s i d e r a t i o n of the p o s s i b l e
mechanisms i n v o l v e d i n l i q u i d SO2 f r a c t u r i n g , however, would
suggest such an explanation to be o v e r l y s i m p l i s t i c . E s t a b l i s h -
ment of f r a c t u r i n g mechanisms f o r these f l u i d s must await the
r e s u l t s of f u t u r e experiments.
Extracted M a t e r i a l . E x t r a c t s , comprising 2-4% of the o r i g -

i n a l shale mass, were i s o l a t e d by f i l t e r a t i o n and subsequent
evaporation of the l i q u i d SO2 s o l u t i o n s which were i n contact
with these s h a l e s . Although no attempt was made to e x t r a c t
these shales e x h a u s t i v e l y , i t i s apparent that a p p r e c i a b l y more
m a t e r i a l can be e x t r a c t e d by l i q u i d SO2 under r a t h e r mild c o n d i -

t i o n s . The bulk (90% or more) of the e x t r a c t i s organic although
some water i s removed and small amounts of c o l o r l e s s or l i g h t
brown c r y s t a l l i n e m a t e r i a l are found i n the cracks and f i s s u r e s
of t r e a t e d s h a l e s . I n f r a r e d s p e c t r a (Figures 2-4) of the e x t r a c t
r e v e a l s a l i p h a t i c CH and carbonyl groups i n the Green River shale
e x t r a c t ; the Moroccan shale e x t r a c t has a s i m i l a r content. These
e x t r a c t s represent bitumen p o r t i o n s of the shale. Kerogen
f r a c t i o n s , presumably, remain i n the shale; i n f r a r e d s p e c t r a
(Figures 2 and 3, Traces B) i n d i c a t e considerable organic
content remaining i n the t r e a t e d s h a l e s . The e x t r a c t from the
Antrim shale i s somewhat d i f f e r e n t from that of the other two
shales i n that both a l i p h a t i c and aromatic C-H but l i t t l e
carbonyl i s present (Figure 4C). The aromatic content of t h i s
e x t r a c t i s not unexpected s i n c e the organic c o n s t i t u e n t s of
Antrim shale are h i g h l y aromatic (Table I ) . Although more
d e f i n i t i v e data i s necessary to s u b s t a n t i a t e the p r o p o s i t i o n ,
i t would appear (Figure 4, A and B) that a s i g n i f i c a n t p o r t i o n of
the organic matter i s removed from Antrim shale by treatment w i t h
l i q u i d SO2.
E x t r a c t s of organic m a t e r i a l were a l s o obtained with other
f l u i d s as i n d i c a t e d i n Table I I . Although no d e t a i l e d analyses
of these e x t r a c t s were obtained, i t would appear that these
e x t r a c t s are of the bitumen f r a c t i o n as expected.
Summary
P r e l i m i n a r y experiments have demonstrated that l i q u i d SO2 i s

e f f e c t i v e i n f r a c t u r i n g and e m b r i t t l i n g both carbonaeceous and
s i l i c e o u s o i l s h a l e s . L i q u i d SO2 has advantages over other f l u i d
f r a c t u r i n g agents, v i z . , low c o s t , a v a i l a b i l i t y i n q u a n t i t y , and
non-petroluem or n a t u r a l gas o r i g i n . Several p o s s i b l e mechan-
isms f o r shale f r a c t u r i n g have been suggested f o r f u t u r e e x p l o r a -
t i o n . Organic components can be removed from the shale under
mild c o n d i t i o n s . On the b a s i s of these r e s u l t s , f u r t h e r e f f o r t s
i n the use of l i q u i d SO2 f o r o i l shale p r o c e s s i n g are j u s t i f i e d .
The general a p p l i c a b i l i t y or l i m i t a t i o n s of these procedures

need to be established; a knowledge of the mechanisms of shale

fracturing would aid in this development. Enhancement of organic
constituent recovery needs to be explored. Adaptation of these
procedures to practical and economical processes in both surface
processing and in situ recovery could result. Several of these
areas will be discussed in future reports.
Acknowledgement s
The support of this research by the U. S. Department of

Energy under Contract No. ET-78-G-01-3316 is gratefully acknow-
ledged. Provision of o i l shale samples and documentation by
Dr. F. P. Miknis (LETC), mineral samples by Dr. W. A. Kneller,
preliminary SEM/EDXA results by Dr. S. N. K. Chaudhari, and aid
in obtaining the mineral/S02 results by Mr. R. Carter are also

gratefully acknowledged.
Literature Cited
1. Perrini, E. M. "Oil from Shale and Tar Sands," Chemical Tech.
Rev. No. 51, Noyes Data Corp.: Park Ridge, N. J . , 1975.
2. Yen, T. F. "Shale Oil, Tar Sands, and Related Fuel Sources,"
Adv. Chem. Series, No. 151, American Chemical Society:
Washington, D. C., 1976.
3. Yen, T. F.; Chilingarian, G. V., Dev. Pet. Sci., Vol. 5,
Elsevier: Amsterdam, 1976.
4. Matzick, A.; Dannenberg, R. O.; Guthrie, B. "Experiments in
Crushing Green River Oil Shale," Bureau of Mines Report No.
5563, 1958.
5. Burow, D. F.; Glavincevski, B. M. "Preprints", Div. of Fuel
Chemistry, American Chemical Society, Vol. 25, No. 2, 1980,
p. 153.
6. Burow, D. F.; Sharma, R. K. "Liquid Sulfur Dioxide Treatment
of Coal," Conf. Chem. Phys. of Coal Utilization, Morgantown,
W. Virginia, 1980, Paper T-4.
7. Burow, D. F., In "Chemistry of Non-Aqueous Solvents";
Lagowski, J. J . , Ed.; Academic: New York, 1970, Vol. III,
Chapter 2.
8. Yen, T. F.; Chilingarian, G. V. Ref. 3, Chapter 1.
9. Musser, W. N., Dow Chemical Co. Report FE-310, 1976.
10. Miknis, F. P., private communication.
11. Miller, J. F.; Boyer, J. P.; Kent, S. J.; Snyder, M. J.
Morgantown Energy Technol. Center, Spec. Publ. (METC/SP-79/6)
1976, 473; Chem. Abstr. 1980, 93, 49920j.

4
Chemistry of Shale Oil Cracking
A. K. BURNHAM
Lawrence Livermore National Laboratory, University of California,
Livermore, CA 94550
Oil shale contains organic material consisting mostly

kerogen (a solid polymer) and a small amount of bitumen (a
soluble, high-molecular-weight material) (1). Most currently
proposed methods for recovering the energy from oil shale involve
the pyrolysis of kerogen (and bitumen) to shale o i l at
temperatures of about 400 to 550°C. Depending on the processing
conditions, part of this oil may be degraded into less desirable
products: coke and gas (2-11). Previous work here at Lawrence
Livermore National Laboratory (LLNL) developed a quantitative
kinetic scheme for the degradation of liquid o i l to mostly solid
products (coking) at temperatures below 450°C (9,12). We now
describe a kinetic scheme for the degradation of vapor-phase o i l
into mostly gaseous products (cracking) at temperatures above
500°C.
Shale o i l cracking can be significant in an indirect-heat
retort in which the o i l shale is pyrolyzed by contact with hot
solids or hot oxygen-free gas. To minimize the shale residence
time in surface processes, the retorting temperature is
frequently maintained above 500°C. The residence time of the
shale o i l vapor in the reactor may be long enough that a
significant amount of thermal cracking may occur, especially in a
hot-solids retort to which no sweep gas is added.
Significant shale o i l cracking can also take place in an
in-situ retort in which thermal cracking may occur both inside
large shale blocks and in the gas stream. If the thermal
gradient within a block is large, o i l produced near the center of
the block can crack (mostly to form gas) as it travels to the
hotter block surface. More important, the o i l emerging from the
block enters a gas stream that may be 200°C hotter than the block
surface (13) . Because this gas stream may also contain oxygen,
high-temperature oil-yield loss in the gas stream may take place
by both combustion and associated cracking.
In this work, we report kinetics for the thermal cracking of
shale o i l over shale. The data are most appropriate for thermal
cracking inside large blocks during in-situ processing and in the
TOSCO-II and Lurgi processes, where relatively low temperatures
0097-6156/81/0163-0039$05.50/0

40 OIL SHALE, T A R SANDS, A N DRELATED MATERIALS
(500 to 600°C), r e l a t i v e l y long residence times ( s e v e r a l

seconds), and n e a r l y autogenous c o n d i t i o n s p r e v a i l . We
p r e v i o u s l y gave a more d e t a i l e d report of our k i n e t i c
measurements (JA) . We a l s o demonstrate the e f f e c t o f thermal
c r a c k i n g on shale o i l composition and present r e s u l t s of C, H,
and N a n a l y s i s , c a p i l l a r y - c o l u m n gas chromatography (GC), and
GC/MS. We compare the compositions of shale o i l samples produced
under l a b o r a t o r y c o n d i t i o n s with those of samples produced i n
l a r g e - s c a l e experiments. A more d e t a i l e d i n v e s t i g a t i o n of o i l
p r o p e r t i e s i n c l u d i n g IR and 13c NMR spectra (_15) and a
r e s u l t i n g d i a g n o s t i c method based on o i l composition (16) have
been reported e a r l i e r .
Experimental
Figure 1 shows the apparatus used i n the c r a c k i n g

experiments. T h i s assay apparatus i s a m o d i f i c a t i o n of the LLNL
modified F i s c h e r assay apparatus described p r e v i o u s l y (17). I t
i s used f o r a complete mass- and carbon-balanced assay under
various heating schedules. For the c r a c k i n g experiments, a
second furnace and reactor were added. Both r e a c t o r s were made
of Type 304 s t a i n l e s s s t e e l . A 165-ym s t a i n l e s s s t e e l f r i t
(6.3 mm high by 32 mm i n diam) allowed gases but not shale to
pass through the bottom of the r e a c t o r s .
Raw shale samples were taken from a 92-litre/Mg (22-gal/ton)
master batch (17) o f Mahogany Zone o i l shale mined from the
Department o f Energy f a c i l i t y at A n v i l P o i n t s , Colorado. The raw
shale had been ground to pass a 20-mesh screen (< 841 pm) and
then s p i n - r i f f l e d to obtain 95-g a l i q u o t s . The shale contained
9.9% organic carbon (12.2% kerogen), 22.2% acid-evolved C 0 2
(48.3% c a l c i t e and dolomite), and the remainder mostly quartz and

s i l i c a t e s . A l l percentages are c a l c u l a t e d on a weight b a s i s .
Organic carbon i s determined by the d i f f e r e n c e between t o t a l
carbon and carbon from acid-evolved CO2.
Raw shale contained i n the top furnace and r e a c t o r was
r e t o r t e d at a l i n e a r heating r a t e . Gases and vapors evolved
during r e t o r t i n g passed through the second reactor at 504 to
610°C where the o i l was thermally cracked. Temperatures were
measured at the center of the bottom r e a c t o r by a
s t a i n l e s s - s t e e l - s h e a t h e d thermocouple (Type K). Temperature
v a r i a t i o n across the r e a c t o r was less than 3°C. To simulate
c o n d i t i o n s i n s i d e a shale block, the bottom reactor contained
pieces o f shale. We used burnt shale (mostly s i l i c a t e s and MgO)
i n most o f the experiments because i t i s thermally s t a b l e above
500°C. In two experiments, we used r e t o r t e d shale (2.7% organic
carbon, 24.4% acid-evolved CO2) and no shale, r e s p e c t i v e l y .
The r a t e o f gas e v o l u t i o n was monitored by a pressure
transducer i n the c o l l e c t i o n b o t t l e . The r a t e of gas e v o l u t i o n
peaked sharply during the kerogen p y r o l y s i s at about 460°C. To
minimize d i f f e r e n c e s i n residence times caused by the

4. BURNHAM Chemistry of Shale Oil Cracking 41
3
A r g o n , 3 t o 10 c m / m i n
Heated t o 5 0 0 ° C (
O i l generated
at 6 and 1 2 ° C / m i n j
Isothermal, ) 0 II cracked
u , , c r a c k e d
504to610°C (
Gas
collection
system
Ice baths
Figure 1. Experimental apparatus used in the gas-phase cracking of shale oil over
shale

42 OIL SHALE, TAR SANDS, A N D R E L A T E D MATERIALS
time-dependent gas e v o l u t i o n r a t e , we purged the r e a c t o r with a

slow sweep of argon (3 to 10 cm^/min). (The argon c o n s t i t u t e d
10 to 20% of the c o l l e c t e d gases.) The average residence time
was v a r i e d by changing both the h e a t i n g rate and the volume of
the second r e a c t o r .
Products were c o l l e c t e d and weighed to determine a mass
balance. Except f o r two experiments, i n which the volume of
gases exceeded the capacity of the gas c o l l e c t i o n system and the
l a s t p o r t i o n was vented, the mass balance ranged from 95 to 98%
(_14). We measured C, H, N, and acid-evolved C0 content for 2
a l l r e t o r t e d shales and f o r some burnt shales from the c r a c k i n g

experiments. O i l s were analyzed f o r C, H, and N. Gases were
analyzed by gas chromatography (thermal c o n d u c t i v i t y detector f o r
H2, CO, CO2, N , and CH4; flame i o n i z a t i o n detector f o r
2
hydrocarbons) and by mass spectrometry. The analyses permitted

an organic carbon balance to be c a l c u l a t e d for the four
experiments i n which the shale i n the bottom reactor was
analyzed; values from 100 to 105% were obtained (14).
Further measurements were made on the o i l samples. In
a d d i t i o n to the samples prepared on the above apparatus, other
011 samples were obtained from the LLNL 6-ton r e t o r t , the Laramie
Energy Technology Center (LETC) 150-ton r e t o r t , the 1972 TOSCO-II
semi-works operation, O c c i d e n t a l O i l Shale's modified i n - s i t u
1
experiment No. 6, and LETC s Rock Springs No. 9 true i n - s i t u
experiment. Spectroscopic techniques used were c a p i l l a r y - c o l u m n
GC/MS, IR, and 13c NMR spectroscopy. These studies have been
reported i n d e t a i l p r e v i o u s l y (15). Only c a p i l l a r y - c o l u m n gas
chromatography r e s u l t s are reported i n d e t a i l here.
A Hewlett-Packard Model 5880 chromatograph with a
f l a m e - i o n i z a t i o n detector (FID) was used f o l l o w i n g a p r e v i o u s l y
described procedure (16) . Samples were made by d i s s o l v i n g about
0.5 ml of neat shale o i l in 2 ml of CS . 2 A Quadrex
f u s e d - s i l i c a column (0.23 mm i . d . by 50 m) coated with SP2100
(methyl s i l i c o n e o i l ) was used. The temperature was programmed
from 60°C to 275°C at the rate of 4°C/min and held at 275°C f o r
30 min.
Result s
K i n e t i c Measurements. The r e s u l t s of the shale o i l cracking

experiments are summarized i n Table I . O i l y i e l d s are reported
as a percentage of the LLNL assay r e s u l t on both a condensed-oil
b a s i s and a C5+ b a s i s . To conduct the k i n e t i c a n a l y s i s , an
e f f e c t i v e residence time had to be determined. I t was assumed
for s i m p l i c i t y that the gas-and-oil e v o l u t i o n p r o f i l e could be
approximated by a square pulse. The average residence time was
c a l c u l a t e d by m u l t i p l y i n g the void volume of the bottom r e a c t o r
by the time i n t e r v a l over which three-fourths of the products
were evolved and then d i v i d i n g by the t o t a l volume of gases and
vapors at the c r a c k i n g temperatures (14). The void volume was

Table I: Conditions for p r e p a r a t i o n of l a b o r a t o r y o i l samples.
Temperature Shale i n Oil yield

Experiment of bottom Residence bottom (wt% of assay)
number reactor (°C) t ime (s) reactor Condensed C5+
111 508 7.0 Burnt 95 96

113 610 3.8 Burnt 55 59
115 505 10.4 Spent 90 91
119 558 4.9 Burnt 81 83
121 504 9.3 Burnt 91 92
123 585 2.5 Burnt 77 82
125 585 2.7 Empty 87 89

127 610 2.0 Burnt 68 74
determined by s u b t r a c t i n g the volume of the burnt or r e t o r t e d

shale from the volume of the empty r e a c t o r . (The former value
was c a l c u l a t e d by d i v i d i n g the weight of shale by i t s d e n s i t y ,
which was determined by mercury porosimetry).
T h i s method of determining the residence time was checked
f o r Experiment 115 by using a more complicated method. A
time-dependent gas and o i l - v a p o r e v o l u t i o n r a t e was estimated
from oil-and-gas e v o l u t i o n r a t e measurements (12,18). Residence
times c a l c u l a t e d from t h i s r a t e ranged from 80 s at 350°C to
about 6 s at 450°C. A weighted average of t h i s residence-time
d i s t r i b u t i o n gave an average residence time of 11 s, which was i n
s u r p r i s i n g l y good agreement with the value of 10.4 s determined
by the simple method. However, the more complicated method i s
a l s o approximate because the c a l c u l a t i o n of the residence time
does not allow the extent of c r a c k i n g during the experiment (and
hence instantaneous product volume) to depend on the
instantaneous residence time. For t h i s reason, we have used the
simpler method to estimate residence time. T h i s introduces a
systematic u n c e r t a i n t y into the k i n e t i c parameters.
In our previous report (_14), we determined a global r a t e
constant at each temperature on the b a s i s of the y i e l d of
condensed o i l . The r e s u l t i n g four r a t e constants were then
f i t t e d to an Arrhenius expression. In the present r e p o r t , we use
a s l i g h t l y d i f f e r e n t technique. The t y p i c a l f i r s t - o r d e r r a t e
expression,
-B/T
yAe (1)
dt
can be rearranged to give

In = In k = In A - B/T , (2)
where y i s the y i e l d of shale o i l and A and B are Arrhenius

parameters. In e f f e c t , a f i r s t - o r d e r r a t e constant i s determined
from each experiment, and a r a t e expression can be determined
from a t y p i c a l Arrhenius p l o t . The r e s u l t i n g p l o t i s shown i n
F i g u r e 2 f o r the y i e l d of C5+ o i l . T h i s gives a r a t e
expression o f
k f
1
( s " ) = 4.8 x 10 8
exp (-19340/T) (3)
T h i s r a t e constant has a s l i g h t l y higher a c t i v a t i o n energy and i s

1.2 times less at 550°C than the r a t e constant reported
p r e v i o u s l y (14) f o r the y i e l d of condensed o i l . Given the

systematic u n c e r t a i n t y i n the residence time, the d i f f e r e n c e s are
not s i g n i f i c a n t .
Two a d d i t i o n a l cautions should be mentioned concerning the
use of Equation ( 3 ) . Experiment 125 (no shale i n the bottom
r e a c t o r ) was used i n n e i t h e r k i n e t i c a n a l y s i s because the
conversion was s u b s t a n t i a l l y lower than expected on the b a s i s o f
the other experiments. T h i s discrepancy may have r e s u l t e d from
e i t h e r a c a t a l y t i c e f f e c t of the shale or a h e a t - t r a n s f e r
l i m i t a t i o n . In a d d i t i o n , Dickson and Yesavage (_19) found that
there i s a 60 to 70% conversion l i m i t f o r shale o i l c r a c k i n g .
T h i s r e s u l t s from the presence and a d d i t i o n a l formation of
aromatics, which are r e s i s t a n t to c r a c k i n g . T h i s implies that
our expression w i l l f a i l at high conversions.
Table I I gives the product d i s t r i b u t i o n f o r thermal c r a c k i n g
o f shale o i l . We defined o i l as the sum of condensed o i l and
C5-C9 hydrocarbons i n the gas. The amount of each gaseous
product was determined from the slope of the curve p l o t t i n g gas
production versus cracking l o s s (conversion) (14). The amount of
coke produced was determined by d i f f e r e n c e , but i t agreed w e l l
with the measured value f o r the few experiments i n which carbon
was analyzed i n the shale from the bottom r e a c t o r . The
alkene/alkane r a t i o s i n the gas depended more s t r o n g l y on the
c r a c k i n g temperature than on the extent of conversion. This
t o p i c i s discussed i n greater d e t a i l i n another paper published
in these proceedings (20).
O i l P r o p e r t i e s of Laboratory Samples. The p r o p e r t i e s of the

l i q u i d a l s o change during the conversion o f a hydrocarbon l i q u i d
to gas and s o l i d . S p e c i f i c a l l y , the H/C r a t i o decreases and the
concentration of aromatic molecules increases g r e a t l y . Elemental
and spectroscopic analyses confirmed these trends f o r the shale
o i l s produced i n our experiments.
The H/C r a t i o and percentage n i t r o g e n are p l o t t e d i n
Figure 3 as a f u n c t i o n of conversion to gas and coke. I t i s

Temperature, ° C
600 550 500

I l I I I
1.1 1.2 1.3
1
1000/T, k"
Figure 2. Arrhenius plot of shale oil cracking data from which the rate expression
in Equation 3 was determined
O i l c r a c k i n g loss, % O i l cracking loss, %
Figure 3. The effect of oil cracking on the H/C atomic ratio and nitrogen content
of the shale oil. The data points indicate cracking over burnt shale (O), retorted
shale (%), and in an empty reactor ([J). The H/C ratio is probably a function of
both cracking temperature and loss. Aromatic nitrogen compounds are concen-
trated selectively by cracking.

Table II. Products from s h a l e oil cracking. 3
Compound Volume (cm3/g t a STP) Weight (g/g)
H 2 184 0.02
CO 22 0.03
CH 4 151 0.11
c 2 155 0.20
85 0.16
C
4 68 0.17
Coke 0.31
a
C+ 5 = oil.
evident that the H/C r a t i o decreases as c r a c k i n g i n c r e a s e s . Of

f u r t h e r i n t e r e s t i s the increase i n n i t r o g e n content as c r a c k i n g
i n c r e a s e s . T h i s increase occurs because the n i t r o g e n in shale
o i l i s contained i n aromatic molecules O ) , which are r e s i s t a n t
to c r a c k i n g ( i . e . , thermodynamically more s t a b l e ) . As the
alkanes and alkenes are p a r t i a l l y converted to gases, the
n i t r o g e n compounds become s e l e c t i v e l y concentrated. Therefore, a
50% c r a c k i n g conversion r e s u l t s i n a doubling of the n i t r o g e n
content.
The trends reported here for c r a c k i n g are the d i r e c t
opposite of those observed by Stout et a l . (8) for o i l coking
(Figure 4). O i l coking i s caused by liquid-phase polymerization
and condensation r e a c t i o n s . I t i s most important at low
temperatures and slow h e a t i n g r a t e s — c o n d i t i o n s under which
residence times i n the l i q u i d phase are g r e a t e s t . Nitrogen
content i n the o i l i s reduced and the H/C r a t i o i s increased by
o i l coking because the aromatic n i t r o g e n compounds are apparently
the most s u s c e p t i b l e to coking r e a c t i o n s . Lower temperatures
a l s o favor alkane rather than alkene formation i n the o i l , as
demonstrated elsewhere for ethane and ethene (200 •
In Figures 5a and 5b, we compare the FID chromatogram of o i l
produced under F i s c h e r assay c o n d i t i o n s with o i l that has
undergone extensive thermal c r a c k i n g at 610°C. S p e c i f i c aromatic
compounds formed i n shale o i l by thermal c r a c k i n g were i d e n t i f i e d
by IR and c a p i l l a r y column GC/MS (15) ; a l k y 1 - s u b s t i t u t e d
aromatics are e s p e c i a l l y p r e v a l e n t . Because of t h e i r usefulness
as i n d i c a t o r s i n combustion r e t o r t s (16) , we show three
1-alkene/n-alkane r a t i o s and the naphthalene/(C;Q + C i ) 2
r a t i o , r e s p e c t i v e l y , as a f u n c t i o n of o i l - y i e l d loss by c r a c k i n g
( F i g u r e s 6 and 7). (In t h i s case, C]_]_ i s the sum of n-undecane
and 1-undecene and C^ 2 i s the sum of n-dodecane and
1-dodecene.) Alkene/alkane r a t i o s are shown for Cg, C i , and 2
Ci8 because these regions of the chromatograms appeared to be

BURNHAM Chemistry of Shale Oil Cracking
Figure 4. The effect of oil coking on the H/C atomic ratio and nitrogen content
of the shale oil. Coking reduces the alkene and aromatic nitrogen content of the oil.
American Chemical
Society Library
1155 16th St. N. w.
Washington,
In Oil Shale, Tar Sands, 0.
and C. 20030
Related Materials; Stauffer, H.;
S1VIH3JLVJM Q31V13H QNV 'SCINVS tfVl '31VHS 1IO

b) 41% o i l cracking loss

Figure 5. A comparison of the FID chromatograms of (a) shale oil produced under Fischer assay
conditions and (b) shale oil that has undergone extensive thermal cracking (41% conversion to gas

and coke). The proportion of aromatic hydrocarbons in the cracked oil has increased dramatically.
i 1 1 r
O i l cracking loss, %
Figure 6. Effect of the extent of cracking (condensed-oil basis) on three 1-alkene/

n-alkane ratios. The ratios were determined by capillary column chromatography
with an FID detector. C (%); C (O); C
8 12O- 18
0 10 20 30 40
Oil crackingtoss,%
Figure 7. Effect of the extent of cracking (condensed-oil basis) on a naphthalene/

(Cii + C ), where C and C are the sums of the respective n-alkanes and 1-
12 u 12
alkenes. Comparing these results with those in Figure 6 shows that cracking to
30% conversion produces primarily alkenes and that further cracking produces
primarily aromatic compounds.

p a r t i c u l a r l y free o f i n t e r f e r i n g compounds. For Cg, the

1-alkene/n-alkane r a t i o increases with conversion. For longer
chains, the r a t i o becomes constant or even decreases at the
highest conversion. For comparison, the ethene/ethane r a t i o
seemed to c o r r e l a t e b e t t e r with c r a c k i n g temperature than with
the extent of conversion ( c r a c k i n g l o s s ) .
We a l s o made two q u a l i t a t i v e observations on o i l q u a l i t y .
F i r s t , the v i s c o s i t y of the o i l appeared to decrease with
c r a c k i n g . A small amount of c r a c k i n g to reduce v i s c o s i t y
( v i s - b r e a k i n g ) i s a common i n d u s t r i a l process (21). Second, the
o i l s with 19% or more cracking loss d i d not s o l i d i f y on c o o l i n g
to -15°C. T h i s might be expected since the pour point i s
dominated by long-chain alkane components (wax), which are the
most s u s c e p t i b l e to c r a c k i n g r e a c t i o n s (21).
P i l o t and F i e l d Retort O i l Samples. The data we have

presented to t h i s point are for o i l c r a c k i n g at r e l a t i v e l y low
temperatures (500 to 610°C) and long residence times (2 to 11
seconds) under an e s s e n t i a l l y autogenous atmosphere. These
c o n d i t i o n s e x i s t i n at l e a s t two aspects of o i l shale r e t o r t i n g :
1) a h o t - s o l i d s r e t o r t such as TOSCO-II or L u r g i , and 2) the
i n t e r i o r of large blocks i n an i n - s i t u r e t o r t . In the TOSCO-II
process, ceramic b a l l s heated to 600°C are mixed with raw shale
to heat i t to about 500°C (22). L o c a l hot spots or long
residence times can cause shale o i l c r a c k i n g . For large b l o c k s
i n an i n - s i t u r e t o r t , the temperature of the i n t e r i o r t y p i c a l l y
lags that o f the surface by 200°C. O i l generated i n the i n t e r i o r
can be cracked as i t migrates to the hot block surface. However,
we demonstrate below that high-temperature c r a c k i n g i n the gas
stream i s more important i n combustion r e t o r t s .
We f i r s t consider the o i l from the 1972 operation o f the
TOSCO-II semi-works. F i g u r e 8 shows the FID chromatogram o f t h i s
oil. In comparison to F i s c h e r assay o i l , s i g n i f i c a n t l y higher
concentrations o f aromatics are evident. We determined
1-alkene/n-alkane and n a p h t h a l e n e / ( C ^ + C12) r a t i o s from the
FID chromatogram. We obtained C g C\2, and C18 r a t i o s o f
5
1.36, 1.22, 1.05, and a naphthalene/(C^^ + C12) r a t i o of

0.047. These r a t i o s a l s o i n d i c a t e a y i e l d o f from 75 to 85% on a
condensed-oil b a s i s and 80 to 85% on a C5+ b a s i s . In c o n t r a s t ,
TOSCO r e p o r t s a 93% y i e l d f o r i t s 1972 run (22).
A probable source o f t h i s discrepancy i s the d i f f e r e n c e i n
p y r o l y s i s temperature. There i s nothing i n the mechanism
described i n our i n t r o d u c t i o n that r e q u i r e s absence of o i l coking
in a F i s c h e r assay (12°C/min). In f a c t , i t has been demonstrated
that y i e l d s greater than 100% of F i s c h e r assay ( i . e . , l e s s coking
than i n F i s c h e r assay) might be obtained under very f a s t h e a t i n g
r a t e s and higher p y r o l y s i s temperatures (10, 23). However, our
experiments were conducted so that the maximum p o s s i b l e y i e l d (no
cracking) would be 100% o f F i s c h e r assay. T h i s i s not
n e c e s s a r i l y true i n the TOSCO-II process. Therefore, f u r t h e r

to
g
P
a
-15 "19
>
"16 w
H
>
C/J
^M/W >
o
Retention time- >
a
Figure 8. FID chromatogram of TOSCO-II oil from the 1972 semiworks operation. Thel-alkene/ m

n-alkane ratios and aromatic hydrocarbon content are high compared with those of the Fischer assay r
>
oil fsee Figure 5a). H
w
a

>
H
W
2
> 1
r
experiments are required to develop a q u a n t i t a t i v e method to

determine o i l y i e l d from o i l composition f o r h o t - s o l i d s r e t o r t s .
We next compare the compositions o f our cracked shale o i l s
with those from combustion r e t o r t s . We show i n F i g u r e 9 the FID
1
chromatogram of shale o i l from Rock Springs No. 9, one of LETC s
true i n - s i t u experiments. Several d i f f e r e n c e s are evident
between the chromatogram of t h i s sample and those shown i n
Figure 5. O i l s produced by combustion r e t o r t i n g u s u a l l y have
much lower C^-Cg content than those produced i n r e t o r t i n g
experiments with no sweep gas. A corresponding increase i s
observed i n the C5-C9 content of the offgas from combustion
r e t o r t s compared to the gas c o l l e c t e d from the laboratory
experiments. I t should be noted that some of the l i g h t ends of
the laboratory-produced samples evaporated during h a n d l i n g .
The low 1-alkene/n-alkane r a t i o s i n d i c a t e that more than 20%

of the o i l generated was converted to coke because o f the low
r e t o r t i n g temperature. The high concentration of naphthalenes
i n d i c a t e s that high-temperature thermal cracking occurred to part
of the generated o i l . However, t h i s thermal c r a c k i n g occurred i n
such a way that e s s e n t i a l l y no 1-alkenes were formed. As
discussed below, t h i s i s c h a r a c t e r i s t i c of o i l burning i n a
combustion r e t o r t .
The c a p i l l a r y GC/MS was quite h e l p f u l i n e s t a b l i s h i n g the
d i f f e r e n c e between o i l c r a c k i n g i n our laboratory experiments and
that associated with o i l burning i n a combustion r e t o r t (15).
Naphthalene/2-methylnaphthalene r a t i o s were determined from the
r e l a t i v e 128- and 142-m/e peak heights i n s p e c i f i c - i o n - c u r r e n t
chromatograms from the GC/MS when the concentrations were too low
to be measured a c c u r a t e l y from the FID chromatogram. To convert
the ion r a t i o s to weight r a t i o s , we compared the ion r a t i o s to
area r a t i o s from the FID chromatogram o f Samples 113, Oxy No. 6,
and Rock Springs No. 9. In Table I I I we l i s t the
naphthalene/2-methylnaphthalene weight r a t i o s determined f o r
these and other samples. We a l s o l i s t some previous r e s u l t s
obtained by Dinneen (24).
One trend that stands out from Dinneen's data and from
Experiments 113 and 127 i s that the naphthalene/2-methy1-
naphthalene r a t i o depends strongly on the temperature at which
o i l c r a c k i n g occurs and only weakly on the amount of c r a c k i n g .
T h i s apparently occurs because the a c t i v a t i o n energy for
d e a l k y l a t i o n of aromatics i s higher than for aromatic formation.
Even at very high conversions, t h i s r a t i o i n o i l s cracked near or
below 600°C i s not d r a m a t i c a l l y d i f f e r e n t than that i n assay
o i l — e v e n though the amount o f naphthalene has increased t e n f o l d .
The naphthalene/2-methylnaphthalene r a t i o i n o i l s from
combustion r e t o r t s i n which a s i g n i f i c a n t amount o f o i l burning
has occurred i s s u b s t a n t i a l l y higher than the r a t i o i n assay
oil. T h i s i n d i c a t e s that most cracking i n i n - s i t u r e t o r t s occurs
at high temperatures associated with combustion. Preferential
o x i d a t i o n of a l k y l aromatics may a l s o c o n t r i b u t e . A t these high

<0 r -
c <a
i— -C
>> +->
+J Q.
21 C
I 1—
JLLJJIJJ.«J1WI»1 Xki

Retention time-
F/gwre 9. Chromatogram of shale oil from Rock Springs No. 9, a true in situ experiment. The

alkene/alkane ratios are very low (coking) and the naphthalene content are very high (combustion
and associated cracking). The naphthalene/methylnaphthalene ratios are high compared with the
cracked shale oil in Figure 5b.
Table I I I . E f f e c t of p y r o l y s i s c o n d i t i o n s on the
naphthalene/2-methylnaphthalene r a t i o .
Y i e l d (% of
Sample Heat Source F i s h e r assay) Ratio
Assay (~470°C) Inert 100 0.4

Exp 127 (610°C) Inert 68 0.6
Exp 113 (610°C) Inert 55 0.7
TOSCO-II Inert 93 0.6
LLNL L - l 'Combustion 72 1.4
LLNL L-4 Combustion 85 1.3
LETC R-14 Combustion 43 1.8

Oxy No. 6 Combustion 40a 2.2
Rock Springs No. 9 Combustion <10a 2.0
Dinneen 650°C Inert 51 1.1
Dinneen 815°C Inert 53 2.0
Dinneen 925°C Inert 39 50
a
These y i e l d s include losses r e s u l t i n g from poor sweep and
inefficient collection.
temperatures, the severe c r a c k i n g c o n d i t i o n s completely convert

the long-chain hydrocarbons to gases so that e s s e n t i a l l y no long-
chain alkenes are formed. As a r e s u l t , the only s i g n i f i c a n t
product of the severe c r a c k i n g c o n d i t i o n s a s s o c i a t e d with
combustion are aromatics, most of which are d e a l k y l a t e d . These
aromatics are c a r r i e d i n the gas stream to mix with uncracked o i l
downstream. In t h i s way, the recovered o i l contains aromatic
compounds i n d i c a t i v e of o i l combustion while r e t a i n i n g the
o r i g i n a l information about heating rate (and hence coking)
contained i n the 1-alkene/n-alkane r a t i o s .
Discussion
We can devise the general mechanism f o r o i l generation and

d e s t r u c t i o n by combining the information about shale o i l c r a c k i n g
with p r e v i o u s l y published information about coking (Figure 10).
The r a t e constants for the i n d i c a t e d r e a c t i o n s are given i n
Table IV. O i l generation from kerogen and bitumen precursors can
be described under most circumstances by a s i n g l e f i r s t - o r d e r
r a t e constant, k^ (12).
The generated o i l e x i s t s i n three p h y s i c a l s t a t e s : gaseous
o i l (components whose b o i l i n g points are less than the generation
temperature), l i q u i d o i l ( o i l whose b o i l i n g point i s greater than
the generation temperature), and o i l vapor (gaseous o i l i n
e q u i l i b r i u m with the l i q u i d phase). O i l gases and vapors are

OIL SHALE, TAR SANDS, AND RELATED MATERIALS
• Oil generation
k d
(Kerogen- Bitumen) • Oil (£,v, g) + Gas + Char
• Oil coking
Oil(g)-^T*i Oil (v) • Oil produced
1
• mostly coke
• Oil cracking
k
f
Oil (v, g) 1—• mostly gas
• Oil combustion
Oil (v, g) + 0 - * - C O
2 x + H 0
2
Figure 10. Mechanism for oil generation and degradation developed at LLNL.
Oil coking occurs inside the particles whereas oil cracking and combustion occur
mostly outside the particles.

Table IV: Summary of r a t e constants f o r proposed mechanism

a
o i l generation and d e s t r u c t i o n shown i n Figure 10.
Reaction Rate Expression
(Kerogen-B i tumen) - 1
krfCs" ) = 2.8 x 1013 exp(-26370/T)
[l-x(T)]-oil* x(T) = 0.38 + (T-325)*0.0035, T > 2 1 7 ° C
g
+ x(T)*oil = 1.00, T > 500°C
Oil^ 0.75 coke 1

k c C s " ) = 3.1 x 10 7
exp(-17615/T)
+0.20 CH 4
+ 0.05 H 2
k&
Oil* oil produced 1
k^Cs" ) = 0 . 1 2 C ' h e a t i n go _1
rate
OilS oil produced k g » k , k , k£

d c
OilS 0.31 coke 1

k f C s " ) = 4.8 x 108 exp(-19340/T)
+ 0.02 H 2
+ 0.03 CO
+ 0.11 CH 4
+0.53 C H X
a
S t o i c h i o m e t r i c s are given on a mass b a s i s .
swept out of the o i l shale p a r t i c l e by co-generated low-molecular-

weight gases. L i q u i d o i l i s subjected to condensation and
polymerization r e a c t i o n s ( c h a r a c t e r i z e d by k ) i n which c
aromatic n i t r o g e n compounds form mostly s o l i d products (coke).

These r e a c t i o n s cause a decrease i n n i t r o g e n content o f the o i l
as y i e l d decreases ( 8 ) .
O i l coking can be minimized by decreasing the liquid-phase
residence time, which, i n turn, can be accomplished by u s i n g high
p y r o l y s i s temperatures and/or an i n e r t sweep gas (SO. Because
1-alkene/n-alkane r a t i o s depend on p y r o l y s i s temperature and
h e a t i n g r a t e , they are good i n d i c a t o r s of o i l coking (16, 25,
26). However, i f the temperature becomes too high, gas-phase o i l
c r a c k i n g r e a c t i o n s occur ( c h a r a c t e r i z e d by k f ) . In these
r e a c t i o n s , long-chain hydrocarbons are converted to low-molecular-
weight hydrocarbons. C y c l i c compounds are dehydrogenated to form
aromatics. Aromatic n i t r o g e n compounds are concentrated i n the
remaining o i l , causing an increase i n n i t r o g e n content. Under
the severe c r a c k i n g c o n d i t i o n s a s s o c i a t e d with combustion, a l k y l -
s u b s t i t u t e d aromatics are d e a l k y l a t e d . T h i s r e s u l t s i s a
r e l a t i o n s h i p between naphthalene content i n the o i l and the
amount o f o i l burning i n a combustion r e t o r t c o n t a i n i n g Mahogany
Zone o i l shale ( 1 6 ) .

Summary
We have presented results for thermal cracking of shale o i l
vapor over shale. Cracking temperatures of 504 to 610°C and
residence times of 2 to 11 seconds were studied. A first-order
Arrhenius rate expression and associated stoichiometry were given.
We also discussed changes in o i l properties caused by
thermal cracking. Cracking increases nitrogen content and
decreases the H/C ratio and pour point of the recovered o i l .
Spectroscopic evidence related the decrease in H/C ratio to an
increase in aromatic and alkene content of the o i l . We
contrasted gas-phase oil cracking to liquid-phase o i l coking as a
loss mechanism in o i l shale retorting. We also compared our
results for oils prepared in the laboratory with oils prepared in
the TOSCO-II semi-works and in modified and true in-situ

combustion retorts. We demonstrated that the
naphthalene/2-methylnaphthalene ratio is a good indicator of
cracking temperature in an oil shale retort.
Acknowledgments
We appreciate the capillary GC work of J. Clarkson and the

helpful discussions with J. Campbell, J. Raley, and J. Carley.
Also gratefully acknowledged are M. Atwood of TOSCO and A. Harak
and D. Latham of LETC for supplying oil samples.
This work was performed under the auspices of the U.S.
Department of Energy by the Lawrence Livermore National
Laboratory under contract number W-7405-ENG-48.
Literature Cited
1. Robinson, W. E. "Kerogen of the Green River Formation" in

Organic Geochemistry, G. Eglington and M. I. J. Murphy,
Eds.; Springer-Verlag, New York, NY, 1969; p. 161.
2. Sohns, H. W.; Jukkola, E. E.; Cox, R. J.; Brantley, F. E.;
Collins, W. G.; Murphy, W. I. R. "Entrained-Solids
Retorting of Colorado Oil Shale: Equipment and Operation,"
Ind. Eng. Chem. 1955, 47, 461.
3. Tihen, S. S.; Brown, J. F.; Jensen, H. B.; Tisot, P. R.;
Melton, N. M.; Murphy, W. I. R. "Entrained-Solids Retorting
of Colorado Oil Shale: Product Yields and Properties," Ind.
Eng. Chem. 1955, 47, 464.
4. Hubbard, A. B.; Robinson, W. E. "A Thermal Decomposition
Study of Colorado Oil Shale," Bureau of Mines, R.I. 4744,
1950.
5. Allred, V. D.; "Kinetics of Oil Shale Pyrolysis," Chem.
Eng. Progress 1966, 62, 55.

6. Johnson, W. F.; Walton, D. K.; Keller, H. H.; Couch, E. J.

"In-Situ Retorting of Oil Shale Rubble: A Model of Heat
Transfer and Product Formation in Oil Shale Particles,"
Colorado School of Mines Quart. 1975, 70, 237.
7. Jensen, H. B.; Poulson, R. E.; Cook, G. L.
"Characterization of a Shale Oil Produced by In-Situ
Retorting," ACS Div. Fuel Chem. Preprint 1971, 15(1), 113.
8. Stout, N. D.; Koskinas, G. J.; Raley, J. H.; Santor, S. D.;
Opila, R. J.; Rothman, A. J. "Pyrolysis of Oil Shale:
Effects of Thermal History on Oil Yields," Colorado School
of Mines Quart. 1976, 71, 153.
9. Campbell, J. H.; Koskinas, G. J.; Stout, N. D. "Oil Shale
Retorting: Effects of Particle Size and Heating Rate on Oil
Evolution and Intraparticle Oil Degradation," In-Situ 1978,
2, 1.
10. Wallman, P. H.; Tamm, P. W.; Spars, B. G. "Oil Shale
Retorting Kinetics," ACS Div. Fuel Chem. Preprint 1980,
25(3), 70.
11. Bae, J. H. "Some Effects of Pressure on Oil-Shale
Retorting," Soc. Petrol. Eng. J. Sept. 1969.
12. Campbell, J. H.; Koskinas, G. J.; Stout, N. D. "Kinetics of
Oil Generation from Colorado Oil Shale," Fuel 1978, 57, 372.
13. Raley, J. H. "Monitoring Oil Shale Retorts by Off-gas
Alkene/Alkane Ratios," Fuel 1980, 59, 419.
14. Burnham, A. K.; Taylor, J. R. "Shale Oil Cracking.
1. Kinetics," Lawrence Livermore National Laboratory,
Livermore, CA, UCID-18284 (1979).
15. Burnham, A. K.; Sanborn, R. H.; Crawford, R. W.; Newton,
J. C.; Happe, J. A. "Shale Oil Cracking. 2. Effect on Oil
Composition," Lawrence Livermore National Laboratory,
16. Burnham, A. K.; Clarkson, J. E. "Determination of Process
Yield for Oil Shale Retorting Using Oil Analysis by
Capillary Column Chromatography," Proc. 13th Oil Shale
Symp., J. H. Gary, Ed.; Colorado School of Mines Press:
Golden, CO, 1980; p. 269.
17. Stout, N. D.; Koskinas, G. J.; Santor, S. "A Laboratory
Apparatus for Controlled Time/Temperature Retorting of Oil
Shale," Lawrence Livermore National Laboratory, Livermore,
CA, UCRL-52158 (1976).
18. Campbell, J. H.; Koskinas, G. J.; Gallegos, G.; Gregg, M.
"Gas Evolution During Oil Shale Pyrolysis I. Non-Isothermal
Rate Measurements," Fuel 1980, 59, 718.
19. Dickson, P. F.; Yesavage, V. F. "The Utilization of Shale
Oil as a Feedstock for Steam Pyrolysis and Petrochemical
Intermediate Production," Quarterly Progress Report,
December 1978 to February 1979; Colorado School of Mines,
Golden, CO.

20. Burnham, A. K.; Ward, R. L. "A Possible Mechanism of

Alkene/Alkane Production in Oil Shale Retorting," Lawrence
Livermore National Laboratory, Livermore, CA, UCRL-84048,
(1980); also ACS Div. Fuel Chem. Preprint, Fall 1980.
21. Nelson, W. L. "Petroleum Refinery Engineering"; McGraw-Hill,
New York, NY, 1958.
22. Witcombe, J. A.; Vawter, R. G. "The TOSCO-II Oil Shale
Process," in Science and Technology of Oil Shale, T. F. Yen,
Ed.; Ann Arbor Science, Ann Arbor, MI, 1976; p. 47.
23. Hinds, G. P. "Effect of Heating Rate on the Retorting of
Oil Shale," presented at 71st Annual Meeting of AIChE, Nov.
1978.
24. Dinneen, G. U.; Smith, J. R.; Bailey, C. W. "High
Temperature Shale Oil: Product Composition," Eng. Chem.
1952, 44, 2647.

25. Coburn, T. T.; Bozak, R. E.; Clarkson, J. E.; Campbell,
J. H. "Correlation of Shale Oil l-Alkene/n-Alkane Ratios
with Process Yield," Anal. Chem. 1978, 50, 958.
26. Evans, R. A.; Campbell, J. H. "Oil Shale Retorting: A
Correlation of Selected Absorbance Bands with Process
Heating Rates and Oil Yield," In-Situ 1979, 3, 33.
DISCLAIMER
This document was prepared as an account of work sponsored by an agency of the United
States Government. Neither the United States Government nor the University of California
nor any of their employees, makes any warranty, express or implied, or assumes any legal
liability or responsibility for the accuracy, completeness, or usefulness of any information,
apparatus, product, or process disclosed, or represents that its use would not infringe pri-
vately ownedrights.Reference herein to any specific commercial products, process, or
service by trade name, trademark, manufacturer, or otherwise, does not necessarily consti-
tute or imply its endorsement, recommendation, or favoring by the United States Govern-
ment or the University of California. The views and opinions of authors expressed herein
do not necessarily state or reflect those of the United States Government thereof, and shall
not be used for advertising or product endorsement purposes.

5
Hydrogen Sulfide Evolution from
Colorado Oil Shale
A. K. BURNHAM, N. KIRKMAN BEY, and G. J. KOSKINAS
Livermore, CA 94550
Because traditional oil resources are declining, new-found

attention is being focused on oil shale, coal, and oil sand as
potential supplies of future energy. Unfortunately, extensive
use of coal and oil shale could cause severe environmental
problems. For example, oil shale retorting produces significant
amounts of hydrogen sulfide and other gaseous sulfur species,
e.g., 1.3 g H S/100 g shale oil (1). In addition, evolution of
2
H S from oil shale retorted in the presence of steam is greater

2
than in other gas environments (2).

In our study, we have measured the dependence of H S 2
evolution on gas atmosphere. The gas environments used were

argon, autogenous (self-generated), and steam-argon mixtures, a l l
at atmospheric pressure. The samples used in these experiments
were Green River oil shale from Colorado. In Green River oil
shale, sulfur occurs in both inorganic and organic combinations.
According to Smith et al. (3), the Green River oil shale rocks
are basically siliceous dolomite that contain varying amounts of
organic matter. They suggest that H S was generated by
2
bacterial attack on the organic matter. Pyrite (FeS ) then 2
formed by the low-temperature reaction of iron and H S. Smith 2
et al. (3) and Young (4) have shown that 70 to 85% of the sulfur
is present as pyrite; most of the remaining sulfur is present as
organic sulfur. The iron sulfide minerals have a median particle
size of about 20 μm (5). Atwood et al. (6) found a correlation
(r = 0.95) between oil shale grade and pyritic sulfur.
During pyrolysis, H S could be formed from the reaction of
2
pyrite with hydrocarbons, hydrogen, or water, and from cracking

of organosulfur compounds. Our objective was to determine the
importance of these various reactions and to report the amounts
of H S evolved from oil-shale samples obtained from locations
2
in Colorado.
0097-6156/81/0163-0061$05.00/0

Experimental
Sample Preparation and Apparatus. The o i l - s h a l e samples

used i n t h i s study were taken from the A n v i l P o i n t s mine, T r a c t
C-a, Logan Wash, and the Colony mine. Table I gives the
p r o p e r t i e s of the shale samples. The shale samples were crushed
and sieved to less than 841 um diam. A p o r t i o n of Sample AP22
was doped with 1 wt% f i n e l y ground (<53 pm) p y r i t e . The
sample was mixed thoroughly f o r several days on a r o t a t i n g
tumbler.
For each experiment i n an argon atmosphere, a small o i l - s h a l e
sample (about 0.20 to 0.55 g) was removed from the sample b o t t l e
by spatula and t r a n s f e r r e d i n t o a r e a c t o r v e s s e l c o n t a i n i n g
s i l i c a wool as a support. A Chrome1-Alumel thermocouple was
placed i n t o the sample r e g i o n . In the i n i t i a l experiments, the

thermocouple was fastened to the outside of the r e a c t o r , and
subsequent measurements showed these temperatures were w i t h i n a
few degrees C e l s i u s of the measurements w i t h i n the sample. The
ends of the furnace around the r e a c t o r v e s s e l were packed with
F i b e r f a x to reduce heat l o s s . The furnace was heated at a n e a r l y
constant r a t e (4.8°C/min). The furnace was c o n t r o l l e d by a Data-
trac 5300 programmer and Lindberg 59344 c o n t r o l l e r (power s u p p l y ) .
The l a r g e s t power input was near the ends of the furnace to give
a more uniform temperature p r o f i l e . A gas flow of 1 l i t r e / m i n
was used. The argon contained less than 10 ppm each of oxygen
and water vapor. About h a l f of the gas was pumped through an
InterScan LD-17 H S monitor, which was used as the d e t e c t o r .
2
Table I . P r o p e r t i e s of o i l - s h a l e samples used i n t h i s study.
Sample Source 3
Grade Org. C Acid C0 2
litre/Mg gal/ton (wt%) (wt%)
AP9 I 38 9 4.7 21.2

AP22 I 91 21.8 9.9 22.2
AP25 I 104 25.0 10.4 17.5
AP61 I 255 61.1 27.0 12.3
CA19 lib 78 18.6 8.8 19.5
CA36 lie 152 36.4 17.3 15.8
LW15 III 62 14.8 5.2 19.1
TC32 IV 134 32.2 14.7 20.2
a
I . A n v i l P o i n t s Mine. I I . Rio Blanco mine shaft on T r a c t C-a.
I I I . Logan Wash, O c c i d e n t a l O i l Shale, Inc. IV. TOSCO, Colony
Mine.
b 560 f t .
c 432 f t .

5. BURNHAM ET AL. Hydrogen Sulfide Evolution 63
(The LD-17 i s an e l e c t r o c h e m i c a l v o l t a m e t r i c detector operating

under d i f f u s i o n - c o n t r o l l e d c o n d i t i o n s . ) The e f f l u e n t H S
2
concentration never exceeded 250 ppm and was u s u a l l y l e s s than 50

ppm. E v o l u t i o n p r o f i l e s were recorded by a s t r i p - c h a r t recorder.
F i g u r e 1 shows the schematic diagram of the H S e v o l u t i o n2
system.
For the autogenous experiments, the sample procedure was the
same as with argon except that the a l i q u o t was t r a n s f e r r e d into a
6 by 15-mm quartz capsule. The capsule was covered by a loose
cap to allow gases from the r e a c t i o n to escape. The capsule was
placed i n s i d e the reactor v e s s e l and supported by s i l i c a wool.
The evolved autogenous gases were swept through the r e a c t o r v e s s e l
by a constant flow of argon (1 l i t r e / m i n ) . The remaining
procedure i s the same as that used i n the argon and hydrogen
experiments.
In the experiments using steam as the gas environment, the
sample was supported as i n the argon and hydrogen experiments.
Steam was generated i n a c o i l e d s t a i n l e s s - s t e e l tube placed
i n s i d e the r e a c t o r v e s s e l . The tube was connected to a M a s t e r f l e x
p e r i s t a l t i c pump that regulated the water flow at 0.4 or 0.45
cm^/min. The steam was swept through the reactor v e s s e l by
argon flowing at 1 l i t r e / m i n . The r e a c t o r was heated to 200°C
before the water flow was s t a r t e d . The temperature was allowed
to s t a b i l i z e before the l i n e a r heating began. The average
heating rate i n the steam experiments was 5.5°C/min.
Temperatures were again measured by a thermocouple i n the sample
r e g i o n . The e f f l u e n t water was a c i d i f i e d with d i l u t e s u l f u r i c
a c i d (0.1 M) to prevent the H S from d i s s o l v i n g . The part of
2
the apparatus enclosed by the dashed l i n e was a l t e r e d f o r the

steam experiments.
Results
Argon. The rate of H S e v o l u t i o n from Sample AP61 i s

2
shown i n Figure 2. The maximum r a t e of H S e v o l u t i o n occurs at

2
about 400°C before s u b s t a n t i a l amounts of hydrocarbons have been

evolved. A second H S peak i s observed between 450 and 475°C,
2
about the same temperature that o i l and gas e v o l u t i o n peak. A

t h i r d peak, the smallest, i s observed between 500 and 525°C.
S i m i l a r H S e v o l u t i o n p r o f i l e s were a l s o observed f o r Samples
2
AP9, AP22, and LW15. In general, the t o t a l amount of H S 2
evolved was p r o p o r t i o n a l to the grade of the shale.

Two samples from T r a c t C-a were a l s o i n v e s t i g a t e d (CA19 and
CA36). These samples evolved s u b s t a n t i a l l y more H S than samples
2
of s i m i l a r grade from other l o c a t i o n s . Moreover, Sample CA19 was

the only sample i n v e s t i g a t e d that evolved a large f r a c t i o n of i t s
H S between 480 and 550°C (Figure 3 ) . The same behavior was ob-
2
served, however, f o r Sample AP22 doped with f i n e l y d i v i d e d p y r i t e .

F i g u r e 4 shows that most of the increase i n H S e v o l u t i o n r e s u l t i n g
2
from a d d i t i o n of f i n e l y d i v i d e d p y r i t e comes at about 500°C.

r Distilled water T C readout
Argon
Steam coil
- Sample
0.1 M Programmable
H S0
2 4 power s u p p l y
(5°C/min)
-Furnace
Ice w a t e r -
To LD-17
vent" H S2
detector
Figure 1. Apparatus used to measure the rate of H S evolution from oil shale in
2
argon, autogenous, and steam atmospheres. For the autogenous experiments, the sam-
ple was contained in a capsule. In the argon experiments, the sample was suspended in
the silica wool for good gas-solid contact. The part of the apparatus enclosed by the
dashed line was changed for the steam experiments. The steam was generated in a coil
within the reactor; 0.1 M sulfuric acid was added to the condensing effluent to prevent
the H S from dissolving.
2

5. BURNHAM E TA L . Hydrogen Sulfide Evolution 65
200 300 400 500 600

Temperature (°C)
Figure 2. Rate of H S evolution from a powdered sample of 61-gal/ton

2 Anvil
Points oil shale (AP61) in an argon atmosphere. A gas flow of 1 L/min and a heat-
ing rate of 4.8°C/min were used.
Figure 3. Rate of H S evolution from a 19-gal/ton

2 Tract C-a sample of oil shale
heated at 4.8°C/min in an argon atmosphere

Autogenous. F i g u r e 5 shows the r a t e of H2S e v o l u t i o n i n an

autogenous atmosphere from A n v i l P o i n t s samples of 9-, 22-,
25-, and 61-gal/ton o i l shale. The maximum rate of H S e v o l u t i o n 2
occurs between 440 and 475°C, depending on the grade of the s h a l e .

The gas evolves at a lower temperature f o r the r i c h e r o i l shale
samples. T h i s general p r o f i l e of H S e v o l u t i o n i n the
2
autogenous atmosphere was a l s o observed f o r Samples CA19, CA36 ,

LW15, and TD32.
F i g u r e 6 shows the increase i n H S e v o l u t i o n from o i l
2
shale to which f i n e l y d i v i d e d p y r i t e was added when heated i n an

autogenous atmosphere. In contrast to the r e s u l t s shown i n
F i g u r e 4, only the magnitude (and not the p r o f i l e ) of the H S 2
e v o l u t i o n changes. Comparing the r e s u l t s f o r Sample AP22 (both

with and without added p y r i t e ) i n F i g u r e s 4 and 6 shows that the
three-peaked e v o l u t i o n observed i n an argon atmosphere merges

i n t o a s i n g l e peak i n the autogenous atmosphere at a temperature
between the f i r s t two peaks i n an argon atmosphere. The same
observation can be made f o r Sample AP61 by comparing the r e s u l t s
in Figures 2 and 5.
Steam. The H S e v o l u t i o n i n a steam environment i s much

2
greater than that seen i n an argon and/or autogenous gas

environment. In Figures 7 through 10, the H S e v o l u t i o n i n
2
argon and i n a 40%-steam atmosphere are compared for Samples

AP22, AP61, CA36, and CA19. The l a r g e s t increase i n 40% steam
comes at temperatures over about 475°C. In each case, the H S 2
e v o l u t i o n r a t e i n steam peaks at about 500°C. In Figure 11, we

see the increase i n H S e v o l u t i o n from Sample AP22 with the
2
a d d i t i o n of 1 wt% of p y r i t e . These r e s u l t s demonstrate that the

major source of increase i n H S i n the steam atmosphere i s the
2
r e a c t i o n of steam with p y r i t e . We a l s o note that upon c l o s e r

examination, the samples with l o o s e l y held p y r i t e (CA19 and doped
AP22) appear to have two peaks near 500°C. T h i s may i n d i c a t e
that the l o o s e l y held p y r i t e i s somewhat more r e a c t i v e towards
steam than p y r i t e i n t i m a t e l y mixed with the kerogen.
T o t a l Evolved H?S. Table I I summarizes the t o t a l amount

of H S evolved from o i l shale i n argon, autogenous, and
2
40%-steam atmospheres. We can compare our autogenous H S 2
r e s u l t s with TOSCO-Material-Balanced Assay (TMBA) r e s u l t s i n

three cases. For the TC32 sample, TOSCO reports that 28% of the
o r i g i n a l s u l f u r i s evolved as H S i n a TMBA. T h i s compares
2
favorably with the 24% we obtained. We can also compare our

r e s u l t s on T r a c t C-a shales i n d i r e c t l y with TMBA data obtained
from Rio Blanco O i l Shale Company. Figure 12 shows the
d i s t r i b u t i o n of the t o t a l s u l f u r i n the gaseous ( e s s e n t i a l l y
H S ) , l i q u i d , and s o l i d products of the TMBA. Our r e s u l t s
2
(•) f o r H S e v o l u t i o n f a l l g e n e r a l l y on the curve r e l a t i n g

2
the f r a c t i o n of s u l f u r i n the gas to the organic carbon content

of the raw shale.

BURNHAM E T AL. Hydrogen Sulfide Evolution
Figure 5. Rate of H S evolution from Anvil Points (AP) samples of varying

2
grades (e.g., Sample AP61 is 61 gal/ton). The samples were heated in an autoge-
nous atmosphere at 4.8°C/min. The temperature of the peak evolution rate in-
creases as grade decreases.

1.5
Temperature ( ° C )
Figure 6. Demonstration of the increase in H S evolution

2 in an autogenous atmos-
phere with added pyrite
Figure 7. Comparison of H S evolution from Sample AP22 heated in argon and

2
40% steam atmospheres. The fraction of total sulfur evolved as H S increases from
2
20% in the argon atmosphere to 76% in the 40% steam atmosphere. The H S 2
evolution in argon shown here is from a different run than that shown in Figure 4.

BURNHAM E T AL. Hydrogen Sulfide Evolution
300 400 500 600 700
Figure 8. Comparison of H S evolution rate from Sample AP61 heated in argon

2
and 40% steam atmospheres. The fraction of total sulfur evolved as H S increased2
from 12% to 76%.
200 300 400 500 600 700 800
Figure 9. Increase in H S evolution in the presence of steam for Sample

2 CA36
(Tract C-a, 36 gal/ton). The fraction of total original sulfur evolved as H S in- 2
creased from about 60% to nearly 100%c.

300 400 500 600 700 800
Figure 10. A comparison of the H S evolution from Sample CA19 in argon and
2
40% steam atmospheres. The fraction of total sulfur evolved as H S increased

2
from 19%o to 49%).
Figure 11. Demonstration of the importance of the pyrite—steam reaction for oil
shale heated at 5.5°C/min in a 40%) steam, 60% argon atmosphere. The general
increase in the H S evolution profile indicates that the steam-pyrite reaction is a
2
major source of H S. The total amount of H S evolved demonstrates that the reac-
2 2
tion goes significantly beyond the FeS state.

S* a
s
?
ν: ^
^£
£1
ss
ε
S" ^ '
^§
^ s a.
: Iδ
HL »
ν:
3 52 Ο
•g ^ a
S Λ g-
îsï
Cfc Co* ^
^ S~
o> δ" «s
Ο^ s
§ S'
Ο* ^
R Ο

Table II. Dependence o f total e v o l v e d H2S on gas atmosphere.
Sample Total S Percent of t o t a l S evolved as HS

2
(wt%)
Argon Autogenous Steam
AP9 0.26 7 5
AP22 0.31 20 20 76
AP22* 0.84 12 13 99
—
AP25 0.66 12 16
AP61 0.98 12 19 76
CA19 1.70 19 24 49
CA36 1.05 61 41 100

—
LW15 0.40 11 10
—
TC32 0.82 24
1% added pyrite.
The amount of H S evolved i n argon and autogenous

2
atmospheres i s comparable, although the e v o l u t i o n p r o f i l e s are

d i f f e r e n t . The amount of H S evolved i n the presence of steam
2
i s s u b s t a n t i a l l y greater. Within the accuracy of the r e s u l t s , we

conclude that 75 + 25% of the i n i t i a l s u l f u r ends up as H S i n 2
a steam atmosphere.
Discussion
Several r e a c t i o n s can produce H S. 2 H S may evolve

2
during p y r o l y s i s of s u l f u r - c o n t a i n i n g portions of the kerogen or

during secondary p y r o l y s i s of evolved organosulfur compounds.
H S may a l s o a r i s e from the r e a c t i o n of p y r i t e with kerogen,
2
l i q u i d and gaseous hydrocarbons from kerogen p y r o l y s i s ,

carbonaceous residue from kerogen p y r o l y s i s , water from kerogen
p y r o l y s i s or dehydration of analcime and c l a y s , or hydrogen from
p y r o l y s i s of kerogen and carbonaceous r e s i d u e . A l l these sources
together provide f o r the p o s s i b i l i t y of H S production from
2
room temperature to 1000°C.

In an autogenous atmosphere, the temperature of the peak
e v o l u t i o n rate v a r i e s from 440 to 475°C. The peak temperature
increases with a decrease i n sample grade (Figure 5 ) . A p o s s i b l e
explanation for t h i s e f f e c t i s that the greater a v a i l a b i l i t y of
hydrocarbons i n the r i c h shale enables the p y r i t e to react at a
lower temperature.
A r e l a t e d trend has been found i n TMBA r e s u l t s f o r T r a c t C-a
shale, which were made a v a i l a b l e by Rio Blanco O i l Shale Company.
In Figure 12, the fate of s u l f u r i n a TMBA i s shown as a f u n c t i o n
of the organic carbon (hence, grade) of the shale. In general,

the f r a c t i o n of the o r i g i n a l t o t a l s u l f u r remaining i n the spent

shale decreases with increases i n grade and the f r a c t i o n evolved
i n l i q u i d and gaseous ( e s s e n t i a l l y H2S) products increases with
increases i n grade. Our two H S r e s u l t s on T r a c t C-a shales
2
agree reasonably w e l l with the TMBA r e s u l t s .

At very high grades, the f r a c t i o n remaining i n the spent
shale reaches a lower l i m i t of about 50%. Since most of the
o r i g i n a l s u l f u r i s i n the form of p y r i t e , t h i s corresponds
q u a l i t a t i v e l y to the l i m i t under assay c o n d i t i o n s of
FeS 2 + 2H * FeS + H S 2 , (1)
where the source of hydrogen i s not w e l l - c h a r a c t e r i z e d . T h i s i s

c o n s i s t e n t with previous knowledge that i t i s very d i f f i c u l t to
remove the second s u l f u r i n a reducing atmosphere (_7). A c t u a l l y ,

the l i m i t i n g product i s probably p y r r h o t i t e ( F e r j ^ S ) according
to Mbssbauer studies ( 8 ) . In a d d i t i o n , we never observed a
s i g n i f i c a n t amount of H S evolved i n an autogenous atmosphere
2
at temperatures from 550 to 950°C, even though hydrogen e v o l u t i o n

continues to above 900°C ( 9 ) . T h i s i n d i c a t e s that i f any f u r t h e r
i r o n s u l f i d e r e a c t i o n s occur, they probably lead to s u l f a t e
formation (10).
Another comparison can be made with the Mbssbauer
spectroscopy r e s u l t s of Williamson et a l . ( 8 ) . For "TOSCO-II
shale" with a grade of 40 g a l / t o n , they report that about 75% of
the p y r i t e i s converted to p y r r h o t i t e during F i s c h e r assay.
Considering that some of t h i s s u l f u r may be incorporated i n t o the
o i l and that some H S i s produced by kerogen p y r o l y s i s , t h i s
2
r e s u l t agrees with the r e s u l t s shown i n F i g u r e 12.

The H S e v o l u t i o n i n an argon atmosphere i s more complex.
2
H S i s evolved at a lower temperature than i n an autogenous

2
atmosphere. Perhaps t h i s r e s u l t s from i n h i b i t i o n of H S- 2
producing r e a c t i o n s i n the autogenous atmosphere because the

product H S i s not removed r a p i d l y enough by other evolved
2
gases. We do not know why the rate of H S e v o l u t i o n decreases

2
above 400°C i n an argon sweep. I t could be a t t r i b u t a b l e to

e i t h e r disappearance of a reactant or a decrease i n the
r e a c t i v i t y of the p a r t i a l l y reacted p y r i t e . Several authors
(11-14) have noted that the r e d u c t i o n of F e S to FeS i s 2
c h a r a c t e r i z e d by a f a s t (low-temperature) rate process and a slow

(high-temperature) rate process. The pronounced H S e v o l u t i o n 2
between 475 and 525°C from o i l shale i n the argon sweep probably
r e s u l t s from the r e a c t i o n of p a r t i a l l y reduced p y r i t e with
hydrogen from the carbonaceous residue remaining a f t e r kerogen
p y r o l y s i s . T h i s i s e s p e c i a l l y apparent f o r samples c o n t a i n i n g
p y r i t e that i s not a s s o c i a t e d with the kerogen.
For Sample CA36, our r e s u l t s i n d i c a t e that 61% of the s u l f u r
i s evolved as H S. 2 On the surface, t h i s appears i n c o n s i s t e n t
with Reaction ( 1 ) . However, i f 20% of the o r i g i n a l s u l f u r i s
organic and i s completely removed during p y r o l y s i s , as suggested

by Mbssbauer studies ( 8 ) , more than h a l f the s u l f u r could be

evolved as H S without reducing FeS.
2 In a d d i t i o n , the
d i f f e r e n c e between 50 and 60% of the s u l f u r forming H S i s on 2
the border of experimental e r r o r .

Although the organic matter i n o i l shale, p a r t i c u l a r l y i n
r i c h samples, produces H S by reducing a s u b s t a n t i a l q u a n t i t y
2
of the i n i t i a l p y r i t e to p y r r h o t i t e , steam can p o t e n t i a l l y

increase H s production from an o i l shale r e t o r t by o x i d i z i n g
2
both i r o n s u l f i d e s . While i n v e s t i g a t i n g the steam-carbon

r e a c t i o n i n spent o i l shale (15), a n o t i c e a b l e amount of H S 2
was evolved near and below 500°C. In a d d i t i o n , H S emissions 2
from LLNL Retort Run L-2 (50% steam; 50% a i r ) were about three
times higher than from LLNL Retort Run L - l (100% a i r ) ( 2 ) . These
two runs used s i m i l a r grades of A n v i l P o i n t s s h a l e .
Although there are numerous p o s s i b l e r e a c t i o n s i n v o l v i n g

steam and p y r i t e , one that produces H S and FeS i s 2
H02 + FeS 2 + C * HS2 + FeS + CO. (2)
Reaction (2) i s b a s i c a l l y the production of hydrogen from carbon

g a s i f i c a t i o n followed by Reaction ( 1 ) . The water-gas s h i f t
r e a c t i o n may provide a d d i t i o n a l hydrogen. At 427°C, the
e q u i l i b r i u m constant c a l c u l a t e d from thermodynamic information i n
2
the JANAF tables (16) i s K = 2.6 x 10~ atm, where K i s
2 2
the e q u i l i b r i u m constant f o r Reaction ( 2 ) . Assuming u n i t s o l i d

a c t i v i t i e s and t y p i c a l r e t o r t gas compositions, we f i n d that
2 x 10 atm.
Because t h i s value i s s u b s t a n t i a l l y smaller than K , the 2
r e a c t i o n i s allowed thermodynamically (but not n e c e s s a r i l y

k i n e t i c a l l y ) i n 50% steam i f the products are removed.
The p o s s i b i l i t y a l s o e x i s t s f o r producing more H S from
2
the FeS. Depending on the e f f e c t i v e p a r t i a l pressure of oxygen

determined by the steam/hydrogen r a t i o , the i r o n may be o x i d i z e d
to FeO, Fe304, or Fe 03 (17). 2 The r e a c t i o n s are:
FeS + H 0 2 FeO + H S 2 , (3)
FeS + ;r (4)
FeS + - (5)

Reactions (4) and (5) have free energy changes at 427°C of 10.35
and 12.97 kcal/mol FeS, r e s p e c t i v e l y ( 6 ) . At t h i s temperature,
a n d F e
FeO decomposes to Fe3(>4 « These free energies r e s u l t
i n e q u i l i b r i u m constants of 6 x 10~4 and 9 x 10~"5. Under the
c o n d i t i o n s of our experiments, the i r o n could be oxidized to
^ 2®3*
e
Using approximate concentrations of- 100 ppm H and 2
10 ppm H S, which are t y p i c a l for our experiments, we f i n d

2
1 / 2
1/2
(V)( H ) P
2
- 5
<1°" M1°" > 4
4 x Iff 7
m
(V)
3 / 2 3 / 2
(0.4)
Because 4 x 10~? i s s u b s t a n t i a l l y smaller than the e q u i l i b r i u m

-
constant ( K ^ ^ I O ^ ) , conversion of the second p y r i t e s u l f u r
to H S and the accompanying o x i d a t i o n of i r o n are thermo-
2
dynamically allowed for our experimental c o n d i t i o n s . The f a c t

that we see most of the s u l f u r evolved as H S implies that 2
these r e a c t i o n s are a l s o allowed k i n e t i c a l l y .

The next question i s whether t h i s r e a c t i o n proceeds i n a
retort. Since the gas compositions change with l o c a t i o n i n the
r e t o r t , t h i s question i s not answered e a s i l y . I f we use a
t y p i c a l offgas composition with steam d i l u t i o n of 40% steam and
5% hydrogen, we f i n d , using the expression for K4, that
P m u s t
H S 2 be l e s s than 500 ppm. T h i s i n d i c a t e s that the
r e a c t i o n would be severely l i m i t e d thermodynamically. At 727°C ,
AG for Reaction (4) i s 11.71 kcal/mol, which r e s u l t s i n K4 =
3 x 10~3. Again, using 40% steam and 5% hydrogen, we f i n d that
PH S 2
m u s t
be l e s s than 0.3%. This i s a small but s i g n i f i c a n t
c o n t r i b u t i o n . In a d d i t i o n , the hydrogen concentration i s l e s s at
t h i s point in the r e t o r t than at the e x i t because the kerogen
p y r o l y s i s c o n t r i b u t i o n enters the gas downstream. T h i s implies
m a
that Pfl s y reach l e v e l s greater than 0.3% at 727°C.
2
However, i t does appear q u i t e p o s s i b l e that thermodynamic

l i m i t a t i o n s cause Reactions (3) through (5) to.be l e s s important
than Reaction ( 2 ) . Further work must be done to c h a r a c t e r i z e the
s p e c i f i c r e a c t i o n s that are o c c u r r i n g . In a d d i t i o n , o x i d a t i o n
r e a c t i o n s leading to COS, S0 , and s u l f a t e formation w i l l 2
require further c h a r a c t e r i z a t i o n .
Summary
Most of the s u l f u r i n o i l shale occurs i n p y r i t e and a

smaller amount i s contained i n the kerogen. The major source o f
H S during o i l shale p y r o l y s i s appears to be the r e a c t i o n of
2
p y r i t e with organic matter. In an autogenous atmosphere, most of

the H S evolves between 400 and 500°C. A d d i t i o n of f i n e l y
2
ground p y r i t e increases the amount of H S evolved but does not 2
change the e v o l u t i o n p r o f i l e . In an argon atmosphere, however,

added p y r i t e causes a s u b s t a n t i a l increase i n H S e v o l u t i o n 2

only between 475 and 525°C. Similar reaction characteristics

were observed with large-grained natural pyrite in Tract C-a
shale. The argon results demonstrate the importance of intimate
contact between the pyrite and organic material. In a steam
atmosphere, pyrite is oxidized to iron oxides and the H S 2
evolution increases substantially. In some samples, essentially

all the initial sulfur is evolved as H S at temperatures below
2
800°C. However, thermodynamics may limit the amount of H S 2
produced from pyrrhotite under retort conditions.

Acknowledgments
We thank Rio Blanco Oil Shale Company for providing the TMBA
results on Tract C-a shale, R. Ward for his help in setting up
the H S detector, and J. Huntington of TOSCO for providing

2
information concerning the TOSCO shale.

This work was performed under the auspices of the U.S.
Department of Energy by the Lawrence Livermore National
Laboratory under contract number W-7405-ENG-48.
Literature Cited
1. Goodfellow, L.; Atwood, M. T. "Fischer Assay of Oil Shale

Procedures of the Oil Shale Corporation," Proc. 7th Oil
Shale Symposium, Quart. Colo. School Mines 1974 69, 205.
2. Unpublished results from LLNL pilot retorts.
3. Smith, J. W,; Young, N. B.; Lawlor, D. L. "Direct
Determination of Sulfur Forms in Green River Oil Shale,"
Anal. Chem. 1964 36, 618.
4. Young, N. B.; Laramie Energy Technology Center, private
communication, 1980.
5. Cole, R. D.; Liu, J. H.; Smith, G. V.; Hinckley, C. C.;
Saporoschenko, M. "Iron Partitioning in Oil Shale of the
Green River Formation, Colorado: A Preliminary Mössbauer
Study," Fuel 1978, 57, 514.
6. Atwood, M. T.; Goodfellow, L.; Kauffman, R. K. "Chemical
and Physical Properties of Oil Shale Dust and Correlations
with Laboratory Fire and Explosivity Test Results," in Proc.
12th Oil Shale Symp., J. H. Gary, Ed.; Colorado School of
Mines Press: Golden, CO, 1979; p. 299.
7. Attar, A. "Chemistry, Thermodynamics, and Kinetics of
Reactions in Coal-Gas Reactions: A Review," Fuel 1978, 57,
201.
8. Williamson, D. L.; Melchior, D. C.; Wildeman, T. R.
"Changes in Iron Minerals During Oil-Shale Retorting," Proc.
13th Oil Shale Symp., J. H. Gary, Ed.; Colorado School of
Mines Press: Golden, CO, 1980; p. 337.
"Gas Evolution During Oil Shale Pyrolysis: Part 1.
Nonisothermal Rate Measurements," Fuel 1980, 59, 718.

10. Smith, J. W.; Robb, W. A.; Young, N. B. "High Temperature

Reactions of Oil Shale Minerals and Their Benefit to Oil
Shale Processing in Place," Proc. 11th Oil Shale Symp.,
J. H. Gary, Ed.; Colorado School of Mines Press: Golden, CO,
1978; p. 100.
11. Schwab, G. M.; Philnis, J. "Reactions of Iron Pyrite: Its
Thermal Decomposition, Reduction by Hydrogen, and Air
Oxidation," J. Amer. Chem. Soc. 1947, 69, 2588.
12. Vdinterva, V. C.; Tchuparoff, G. I. Zh. Prikl. Khim. 1941,
14(1), 3.
13. Yergey, A. L.; Lampe, F. W.; Vestal, M. L.; Day, A. G.;
Fergusson, G. J.; Johnston, W. H.; Snyderman, J. S.;
Essenhigh, R. H.; Hudson, J. E. "Nonisothermal Kinetic
Studies of the Hydrodesulfurization of Coal," Ind. Eng.
Chem. Process Des. Dev. 1974, 13, 233.

14. Maa, P. S.; Lewis, C. R.; Hamrin, C. E., Jr. "Sulfur
Transformation and Removal for Western Kentucky Coals," Fuel
1975, 54, 62.
15. Burnham, A. K. "Reaction Kinetics Between Steam and
Oil-Shale Residual Carbon," Fuel 1979, 58, 719.
16. "JANAF Thermochemical Data"; Dow Chemical Company: Midland,
MI; 1977.
17. Fast, J. D. "Interaction of Metals and Gases"; Academic
Press: New York, NY, 1965; p. 67.
DISCLAIMER
vately owned rights. Reference herein to any specific commercial products, process, or

6
A Possible Mechanism of Alkene/Alkane
Production
A. K. BURNHAM and R. L. WARD
Livermore, CA 94550
Alkene/alkane ratios have been used extensively as indicators

of oil-shale retorting conditions. Jacobson, Decora, and Cook
(1) developed a retorting index that relates the ethene/ethane
ratio to temperature, and Campbell and coworkers related
ethene/ethane and propene/propane ratios (2), C to C 7 12
1-alkene/n-alkane ratios (3), and total 1-alkene/n-alkane ratios

(4) to the logarithm of the heating rate during retorting. In
addition, Raley (5) worked out a relationship between the
ethene/ethane and propene/propane ratios and the yield loss in
the combustion retorts at Lawrence Livermore National Laboratory
(LLNL). Uden et al. (6) reported how the C to C alkene/alkane 2 5
ratios change with a change in the amount of the oxygen present

during retorting. Finally, Burnham (7) demonstrated that the
ethene/ethane ratios are related to the oil-cracking temperature.
Our objective was to clarify the reaction mechanisms that
determine the observed alkene/alkane ratios under various
conditions, and the results are reported here. When oil shale is
pyrolyzed either isothermally or nonisothermally, the hydrocarbon
and hydrogen concentrations are all time dependent. To determine
if the alkene-alkane-hydrogen system is at equilibrium, we heated
oil shale at a constant rate and measured the C to C hydro- 1 3
carbons and hydrogen over time. We also measured the effect of

an inert sweep gas on the time-dependent ethene/ethane and
propene/propane ratios and the integral 1-alkene/n-alkane ratios
in the o i l . We determined that the C H -C H -H system
2 4 2 6 2
is not at thermal equilibrium and interpret our results in terms

of a nonequilibrium free-radical mechanism proposed by Raley (8).
Pyrolysis of both kerogen and shale oil breaks larger
molecules into smaller ones. For the alkene-alkane-hydrogen
system to be at equilibrium, the reactions that lead to this
equilibrium must be faster than those producing the smaller
molecular fragments. To reach equilibrium, the ethene/ethane
ratio must satisfy the condition:
0097-6156/81/0163-0079$05.00/0

= K
eq
(V )(\) 4
Because the enthalpy change f o r the C2H4 plus H r e a c t i o n 2
is 34 kcal/mol (9^, the ethene/ethane r a t i o must be a f u n c t i o n o f

temperature when other c o n d i t i o n s are constant. In a d d i t i o n , the
r a t i o should be p r o p o r t i o n a l to the amount of i n e r t d i l u e n t when
the system i s at or near e q u i l i b r i u m , because the e q u i l i b r i u m
expression has u n i t s of r e c i p r o c a l pressure.
More g e n e r a l l y , a r a t i o of alkene to alkane i s determined by
the r e l a t i v e production rate of each. During f r e e - r a d i c a l
c r a c k i n g , p y r o l y s i s of alkanes y i e l d s e i t h e r alkenes by
unimolecularly decomposing free r a d i c a l s , alkanes by f r e e

r a d i c a l s a b s t r a c t i n g a hydrogen from another source, or both. For
example, ethene can be formed by decomposition of primary
radicals (including ethyl),
R-C-C* R* + C=C
and
-
C-C H* + C=C ,
and ethane from e t h y l r a d i c a l s by hydrogen abstraction,
C-C* + R C-C + R* .
S i m i l a r l y , propene can form by decomposition of primary propyl

r a d i c a l s and secondary free r a d i c a l s . Propane can form by propyl
r a d i c a l s a b s t r a c t i n g hydrogen from another source.
The f r e e - r a d i c a l hypothesis leads to two i n t e r e s t i n g
p r e d i c t ions:
a) The alkene/alkane r a t i o s depend on t o t a l organic
concentration, because alkene formation i s a unimolecular
r e a c t i o n and alkane formation a bimolecular r e a c t i o n . An i n e r t
sweep gas increases the alkene/alkane r a t i o s by d i l u t i n g the
organic content of the gas phase.
b) The alkene/alkane r a t i o s depend on r e t o r t i n g temperature,
because the a c t i v a t i o n energies f o r alkene formation are greater
than those f o r alkane formation. Alkene formation i s favored at
higher temperatures.
Therefore, both the e q u i l i b r i u m and f r e e - r a d i c a l hypotheses
p r e d i c t that the ethene/ethane r a t i o s depend on p y r o l y s i s
temperature and i n e r t d i l u e n t . However, the p r e d i c t i o n s are
q u a n t i t a t i v e l y d i f f e r e n t and can be t e s t e d .

6. B U R N H A M A N D WARD Alkene/Alkane Production 81
Experimental
Our s t a r t i n g m a t e r i a l was o i l shale from the A n v i l P o i n t s

Mine near R i f l e , Colorado, that had been ground and sieved to
<0.84 mm diam. T h i s was then assayed and found to have an o i l
content of 22 g a l / t o n . The samples used i n our experiments were
pyrolyzed and analyzed i n the apparatus diagrammed i n Figure 1.
A sample, ranging i n weight from 14 to 40 g, was placed i n a
s t a i n l e s s s t e e l can with a porous f r i t i n the bottom that allowed
gas and o i l to escape. I t was then heated at a constant rate of
1.0 or 1.5°C/min i n a programmable furnace. A constant flow of
nitrogen or argon entered the system e i t h e r near the bottom or
through the top of the sample can. The r e t o r t i n g occurred under
a self-generated atmosphere (autogenous c o n d i t i o n s ) i f the sweep

gas entered from below. The sweep gas passed d i r e c t l y through
the sample i f the i n e r t gases entered from the top. Hydrocarbons
were detected with a f l a m e - i o n i z a t i o n gas chromatograph; hydrogen,
n i t r o g e n , and carbon monoxide were detected using a thermal-
c o n d u c t i v i t y gas chromatograph. Two traps ( i c e water and Dry
Ice-isopropanol) preceded the chromatographs.
Results
The rates of ethene and ethane e v o l u t i o n , the r a t i o of

ethene to ethane, and the p a r t i a l pressure of hydrogen ( r e l a t i v e
e v o l u t i o n r a t e of hydrogen to t o t a l gas) are shown i n F i g u r e 2
for o i l shale heated at 1.5°C/min under an autogenous atmosphere.
The ethene/ethane r a t i o reaches a f i r s t minimum before the peak
r a t e of C e v o l u t i o n . I t then increases s l i g h t l y before
2
reaching a second minimum at about 540°C. A more pronounced

v a r i a t i o n i n the propene/propane r a t i o was observed at l°C/min
(Figure 3 ) .
I f the ethene/ethane r a t i o s are combined with the hydrogen
p a r t i a l pressures, we can demonstrate that the ethene-hydrogen-
ethane system i s f a r from thermal e q u i l i b r i u m under the c o n d i t i o n s
of the experiment shown i n Figure 2. The experimental value of
P c P c h P h s c o m a r e c l n
^ 2H6^^ 2 4^ 2^ * P ^ F i g u r e 4 with the value of
K q.
e Only at temperatures near and above 600°C, at which the
C e v o l u t i o n rate i s n e g l i g i b l e , does the ethene/ethane r a t i o
2
approach e q u i l i b r i u m . Therefore, a nonequilibrium explanation o f

the observed alkene/alkane r a t i o s i s r e q u i r e d .
The f r e e - r a d i c a l mechanism a l s o p r e d i c t s that the
ethene/ethane r a t i o should increase i f i n e r t d i l u e n t i s added
(Figure 5 ) . The a d d i t i o n of an i n e r t sweep causes both the
instantaneous values above 450°C and the i n t e g r a l values of the
ethene/ethane r a t i o to increase. The i n t e g r a l value of the
ethene/ethane r a t i o increased from 0.21 under autogenous
c o n d i t i o n s to 0.29 i n the slow-sweep experiment and to 0.33 i n
the fast-sweep experiment. We determined a value of 0.34 at

Thermocouples
Thermocouple
readout
Temperature
programmer
and controller
Gas c h r o m a t o g r a p h s
Flame-ionization
detector f o r
C 1 to C 3 hydrocarbons
Thermal-conductivity
detector for
N , H , CO
2 2
- T o vent
D r y Ice trap
Figure 1. Apparatus used to measure the rate of evolution of gases from oil shale
during retorting at a constant heating rate

6. BURNHAM A N DWARD Alkene/Alkane Production 83
300 400 500 600
Temperature, ° C
Figure 2. Product measurements for oil shale heated at 1.5°C/min under an

autogenous atmosphere: (a) rate of C evolution; (b) ethene/ethane
2 ratio; (c) partial
pressure of hydrogen released.
300 400 500 600
Temperature, ° C
Figure 3. Propene/propane ratios for oil shale heated at l°C/min under an

autogenous atmosphere

Temperature, ° C
600 500 400

Figure 4. Arrhenius plot for the time and temperature dependence of [H ][C H ]/2 2 ]l
[C H ] evolved from 22 gal/ton oil shale heated at 1.5°C/min

2 G under an autogenous
atmosphere. The maximum rate of gas evolution, which corresponds to the mini-
mum residence time, is shown.

6. B U R N H A M A N DWARD Alkene/Alkane Production 85
i n f i n i t e d i l u t i o n by p l o t t i n g the ethene/ethane r a t i o s against

the sample-size/sweep-rate r a t i o and e x t r a p o l a t i n g to zero.
The 1-alkene/n-alkane r a t i o s i n the o i l , measured by
c a p i l l a r y - c o l u m n gas chromatography/mass spectroscopy, also
increase with the a d d i t i o n of i n e r t d i l u e n t (Figure 6 ) . T h i s
e f f e c t and the p r e v i o u s l y demonstrated dependence on h e a t i n g rate
are c o n s i s t e n t with a f r e e - r a d i c a l mechanism. In a d d i t i o n , we
noted that alkene/alkane r a t i o s for even-numbered hydrocarbons
are s i g n i f i c a n t l y higher the r a t i o s f o r odd-numbered ones. We do
not understand t h i s e f f e c t at t h i s time but suspect that i t i s
r e l a t e d to the s t r u c t u r e of kerogen and the mechanism of i t s
pyrolysis.
Discussion
To form an alkane by the f r e e - r a d i c a l mechanism, there must

be a source of r e a c t i v e hydrogen. I f t h i s source i s constant,
the ethene/ethane r a t i o would increase continuously with
temperature. However, the compositions of the gas and the s o l i d
are continuously changing, which makes the problem more d i f f i c u l t .
The f i r s t minimum i n the ethene/ethane r a t i o occurs before the
maximum o i l e v o l u t i o n but near the temperature of maximum
hydrogen s u l f i d e e v o l u t i o n (10). Hydrogen s u l f i d e i s a good
donor of hydrogen to free r a d i c a l s (11). The second minimum
observed i n the alkene/alkane r a t i o s occurs at about the same
temperature as the maximum rate of hydrogen e v o l u t i o n from
secondary char p y r o l y s i s ( 2 ) . The second minimum may occur
because e i t h e r e t h y l r a d i c a l or ethene undergoes a d d i t i o n a l
r e a c t i o n with l a b i l e hydrogen i n the char or because the
temperature i s high enough f o r the gas-phase r e a c t i o n of ethene
and hydrogen to proceed r a p i d l y .
The general observation that temperature and i n e r t d i l u e n t
a f f e c t the ethene/ethane r a t i o i s u s e f u l f o r c o r r e l a t i n g v a r i o u s
data i n the l i t e r a t u r e . In Figure 7, we show ethene/ethane
r e s u l t s from a s e r i e s of s h a l e - o i l cracking experiments (J) • The
ethene/ethane r a t i o i s p l o t t e d against the cracking conversion
and the logarithm of the ethene/ethane r a t i o against the
r e c i p r o c a l cracking temperature (Arrhenius p l o t ) . In the
Arrhenius p l o t , we note a higher c o r r e l a t i o n , i n d i c a t i n g that
temperature rather than conversion i s the c o n t r o l l i n g f a c t o r .
From i t s slope, we c a l c u l a t e an e f f e c t i v e a c t i v a t i o n energy o f
12.4 kcal/mol.
In a r e l a t e d matter, Campbell and coworkers found that the
ethene/ethane r a t i o (2^) and higher alkene/alkane r a t i o s (3_, 4)
produced during kerogen p y r o l y s i s could be c o r r e l a t e d with the
logarithm of the h e a t i n g r a t e i n a nonisothermal p y r o l y s i s
experiment. T h i s can be understood i f we consider the
transformation of kerogen to o i l and gases as a thermal c r a c k i n g
r e a c t i o n . A change i n the heating r a t e , D, causes a change i n

o.o I 1 1 1 1 1 1 L_
300 400 500 600
Temperature, ° C
Figure 5. Effect of inert sweep gas on the time-dependent ethene/ethane ratio for
oil shale heated at 1.5°C/min under autogenous conditions. The slow-sweep sample
size and flow rate were 28 g and 50 cm /min,
3
respectively. The fast-sweep sample
size and flow rate were 14 g and 100 cm /min, 3
respectively. Most of the ethene
and ethane was evolved between 400° and 500°C.
C a r b o n number
Figure 6. Effect of inert sweep gas during retorting on the 1 -alkene/n-alkane

ratios in shale oil. The ratios at the peaks were determined on samples from capil-
lary column GC by total-ion MS.

6. B U R N H A M A N D WARD Alkene IAlkane Production 87
the average temperature at which the r e a c t i o n occurs. The

r e a c t i o n rate i s given by
dc
* Ac Q e x p [ - | j - -fi^ exp(-E/RT)] . (1)
dt
The r e a c t i o n rate i n i t i a l l y increases with time as the temperature
increases, and then peaks and drops to zero as the reactant i s
consumed. The temperature at the maximum r e a c t i o n r a t e , Tp, can
be used as the e f f e c t i v e temperature f o r the r e a c t i o n . We can
c a l c u l a t e T from the rate parameters by d i f f e r e n t i a t i n g the
p
right-hand side of Equation (1) with respect to T, s e t t i n g the

d e r i v a t i v e equal to zero, and f i n d i n g the roots of the r e s u l t i n g
equation
/ 2RT \
0 = -55- + (i - _ E 1 exp(-E/RT ) . (2)
ART P
P
The root was found i t e r a t i v e l y on a programmable hand
c a l c u l a t o r using the r a t e parameters described by Campbell et a l .
(_12). We p l o t t e d the ethene/ethane r a t i o as a function of y i e l d ,
the logarithm of the heating r a t e , and an Arrhenius p l o t u s i n g
Tp (Figure 8 ) . The s t r a i g h t l i n e i n the Arrhenius p l o t
(Figure 8c) again i n d i c a t e s that p y r o l y s i s temperature i s an
important f a c t o r f o r determining alkene/alkane r a t i o s .
We combined the r e s u l t s shown i n Figures 7b and 8c with
other data (I, 13) on a s i n g l e Arrhenius p l o t (Figure 9 ) . From
t h i s p l o t we can see the dependence of the ethene/ethane r a t i o on
both temperature and sweep gas. The r a t i o from a l l r e t o r t i n g and
c r a c k i n g experiments under autogenous, or n e a r l y autogenous,
c o n d i t i o n s can be p r e d i c t e d to w i t h i n 20% by a s i n g l e Arrhenius
expression having an a c t i v a t i o n energy of 11 kcal/mol. T h i s
energy i s s u b s t a n t i a l l y lower than the enthalpy of the ethane-
hydrogen-ethene r e a c t i o n , i . e . , 34 kcal/mol.
The ethene/ethane r a t i o s obtained by Sohns et a l . from an
e n t r a i n e d - s o l i d s (steam) r e t o r t (13) are two to three times
l a r g e r than the r a t i o s from autogenous experiments at the same
temperature. We do not agree with the o r i g i n a l i n t e r p r e t a t i o n o f
Jacobson et a l . (I) that longer residence times and more secondary
cracking cause t h i s e f f e c t . We showed i n Figure 7 that the
ethene/ethane r a t i o produced during c r a c k i n g at constant
temperature depends only s l i g h t l y on residence time and extent o f
c r a c k i n g . Instead, the elevated ethene/ethane r a t i o s i n the
e n t r a i n e d - s o l i d s r e t o r t are most l i k e l y caused by the steam
d i l u e n t , as implied by P r e d i c t i o n (a) above. To confirm our
explanation, the ethene/ethane r a t i o from the i n f i n i t e d i l u t i o n
e x t r a p o l a t i o n of our nitrogen-sweep experiments i s roughly
c o n s i s t e n t with an e x t r a p o l a t i o n of the e n t r a i n e d - s o l i d s data to
low temperature (the black c i r c l e i n F i g u r e 9 ) .

Figure 7. Effect of cracking on the ethene/ethane ratios of the total evolved gases,
shown as a function of (a) cracking losses and (b) cracking temperature. The result
indicated by A is for a Fischer assay. The other points indicate cracking over
burnt shale (O), retorted shale (%), and in an empty reactor ([J). The ratios corre-
late better with the cracking temperature than with the cracking losses.
90 95 100 0.2 1.0 10 1.3 1.4 1.5

1
Y i e l d , % Fisher assay Heating rate, ° C / m i n 1000/T , K"
D
Figure 8. Ethene/ethane ratio as a function of (a) yields as a percentage of Fischer

assay (FA), (b) the logarithm of the heating rate, and (c) an Arrhenius plot using T . p

BURNHAM A N D WARD Alkene/Alkane Production
Temperature, ° C
800 700 600 500 400

I I -
- • I nsert sweep -
- • • E n t r a i n e d solids (steam) -
- A • L L N L nonisothermal -
&
- infinite d i l u t i o n ( N ) 2 -
A
- • -
- •
v •
_
Autogenous
o •
O
O L L N L nonisothermal
- — Retorting index ( L E T C )
° oo -
• Cracking ( L L N L )
o
A Cracking ( L E T C )
0.1 1 I
II
1.0 1.2 1.4
1 0 0 0 / T , K"
Figure 9. Effect of temperature and inert sweep gas on the ethene/ethane ratio
from retorting oil shale. Results are shown for work at LLNL and LETC. The
temperature dependence of the ethene/ethane ratio can be characterized by an
activation energy of about 11 kcal/mol.

These f i n d i n g s have c e r t a i n i m p l i c a t i o n s f o r using

ethene/ethane r a t i o s as i n d i c a t o r s of r e t o r t i n g c o n d i t i o n s . The
r e t o r t i n g index of Jacobson et a l . (I) should work w e l l for
r e t o r t i n g under autogenous c o n d i t i o n s , as i n e i t h e r a TOSCO-II o r
L u r g i process ( J ^ ) . I t does not work where i n e r t d i l u e n t i s
added, as i n a f l u i d i z e d bed. Here, the r e l a t i o n s h i p between
r e t o r t i n g temperature and ethene/ethane r a t i o probably depends on
both g a s - t o - s o l i d r a t i o s and p a r t i c l e s i z e .
The s i t u a t i o n i s more complicated i n a combustion r e t o r t .
For p a r t i c l e s i z e s greater than 2 or 3 cm, r e t o r t i n g occurs under
autogenous c o n d i t i o n s , regardless of sweep, because there are
d i f f u s i o n l i m i t a t i o n s . When o i l combustion occurs, s h a l e - o i l
c r a c k i n g a l s o occurs i n the gas stream at the i n t e r f a c e of the
combustion and kerogen p y r o l y s i s zones. T h i s produces l o c a l l y
high ethene/ethane r a t i o s r e s u l t i n g from high temperatures, i n e r t

d i l u e n t , and, perhaps, o x i d a t i v e dehydrogenation. The
ethene/ethane r a t i o at the e x i t depends on the amount of C2
hydrocarbons produced by both kerogen p y r o l y s i s and s h a l e - o i l
c r a c k i n g i n the gas stream and on the c o n d i t i o n s e x i s t i n g at each
l o c a t i o n . Low ethene/ethane r a t i o s produced when heating rates
are slow and i n t r a p a r t i c l e coking occurs can be overshadowed by
high r a t i o s produced during o i l c r a c k i n g i n the gas stream.
Therefore, any e m p i r i c a l r e l a t i o n s h i p between o i l d e s t r u c t i o n i n
a combustion r e t o r t and the ethene/ethane r a t i o must be used with
caution when both coking and cracking occur.
Summary
When o i l shale i s heated at a constant r a t e , the

alkene/alkane r a t i o s i n the evolved hydrocarbon gases change with
time. In a d d i t i o n , the alkene/alkane r a t i o s i n both the gas and
the o i l are a f f e c t e d by an i n e r t sweep gas. The ethene/ethane
r a t i o i s not determined by e q u i l i b r i u m with hydrogen, and we
i n t e r p r e t t h i s phenomenon i n terms of a f r e e - r a d i c a l c r a c k i n g
mechanism. The i m p l i c a t i o n i s that alkene/alkane r a t i o s ,
e s p e c i a l l y the ethene/ethane r a t i o , can be used as an i n d i c a t o r
of r e t o r t performance only i f the c o r r e c t r e l a t i o n s h i p s are used
for each set of r e t o r t c o n d i t i o n s .
Acknowledgments
We thank J . H. Raley f o r h i s many h e l p f u l d i s c u s s i o n s '

concerning t h i s work and R. W. Crawford f o r the gas
chromatography/mass spectroscopy r e s u l t s .
T h i s work was performed under the auspices of the U. S.
Department of Energy by the Lawrence Livermore N a t i o n a l
Laboratory under c o n t r a c t number W-7405-ENG-48.

6. BURNHAM AND WARD AlkeneIAlkane Production 91
Literature Cited
1. Jacobson, I. A., Jr.; Decora, A. W.; Cook G. L. "Retorting
Indexes for Oil Shale Pyrolysis from Ethene/Ethane Ratios of
Product Gases," in Science and Technology of Oil Shale, T. F.
Yen, Ed.; Ann Arbor Sciences Publishers: Ann Arbor, MI, 1976;
p. 103.
"Gas Evolution During Oil Shale Pyrolysis: Part 1.
Nonisothermal Rate Measurements," Fuel 1980, 59, 718.
3. Coburn, T. T.; Bozak, R. E.; Clarkson, J. E.: Campbell,
J. H. "Correlation of Shale Oil l-Alkene/n-Alkane Ratios
with Process Yield," Anal. Chem. 1978, 50, 958.
4. Evans R. A.; Campbell, J. H. "Oil Shale Retorting: A
Correlation of Selected Absorbance Bands with Process

Heating Rates and Oil Yield," In-Situ 1979, 3, 33.
5. Raley, J. H. "Evaluation of Retort Performance from Gas
Data," in 12th Oil Shale Symposium Proceedings, J. H. Gary,
Ed.; Colorado School of Mines Press: Golden, CO, 1979;
p. 342.
6. Robillard, M. V.; Siggia, S.; Uden, P. C. "Effect of Oxygen
on Composition of Light Hydrocarbons Evolved in Oil Shale
Pyrolysis," Anal. Chem. 1979, 51, 435.
I. Kinetics," Lawrence Livermore National Laboratory,
8. Raley, J. H. "Monitoring Oil Shale Retorts by Off-Gas
Alkene/Alkane Ratios," Fuel 1980, 59, 419.
9. American Petroleum Institute, Research Project 44, (Carnegie
Institute of Technology, Pittsburgh, PA, 1952).
10. Burnham, A. K.; Kirkman Bey, N.; Koskinas, G. J. "Hydrogen
Sulfide Evolution from Colorado Oil Shale," in Proceedings
of Symposium on Oil Shale, Tar Sands, and Related Materials,
ACS Symposium Series; American Chemical Society: Washington,
DC, 1981.
11. Trotman-Dickenson A. F.; Milne, G. S. "Tables of
Bimolecular Gas Reactions"; National Bureau of Standards,
Gaithersburg, MD, NSRDS-NBS 9 (1967).
12. Campbell, J. H.; Koskinas, G. J.; Stout, N. D. "Kinetics of
Oil Generation from Colorado Oil Shale," Fuel 1978,57,372.
13. Sohns, H. W.; Jukkola, E. E.; Murphy, W. I. R. "Development
and Operation of an Experimental, Entrained-Solids,
Oil-Shale Retort"; U. S. Bureau of Mines, Washington, DC,
Report of Investigations 5522 (1959).
14. Baughman, G. L., Ed. "Synthetic Fuels Data Handbook,"
2nd ed.; Cameron Engineers, Inc.: Denver, CO, 1978; p. 81.

DISCLAIMER
vately owned rights. Reference herein to any specific commercial products, process, or


7
Oil Shale Retorting Kinetics
P. H. WALLMAN, P. W. TAMM, and B. G. SPARS
Chevron Research Company, 576 Standard Avenue, Richmond, CA 94802
Several aboveground oil shale retorting processes are

characterized by rapid heating of the shale followed by
pyrolysis of the kerogen at essentially isothermal condi-
tions. The objective of this study is to investigate the
retorting kinetics applicable to processes characterized both
by rapid heating of relatively small particles and by rapid
sweeping of the produced hydrocarbon vapors out of the
retort. Rather surprisingly, accurate kinetics for these con-
ditions are not available in the literature.
Several previous investigators have taken an isothermal
approach but have failed to eliminate significant heatup
effects in the measured kinetics. The important investigation
by Hubbard and Robinson (1) is in this category. Attempts were
made to correct the Hubbard and Robinson data for the heatup
effects by Braun and Rothman (2) and Johnson et al. (3).
Allred (4) took new isothermal data with increased accuracy,
but his results also suffered from interfering heat-transfer
dynamics. Weitkamp and Gutberlet (5) used both isothermal and
nonisothermal techniques but covered only low temperatures and
presented no kinetic model.
A frequent characteristic of past investigations is exces-
sive complexity of the proposed kerogen pyrolysis models. The
works of Fausett et al. (6) and Johnson et al. (3) belong in
this category. A goal of the present investigation is to keep
the model as simple as possible.
One previous investigation that deserves special attention
is that by the Lawrence Livermore Laboratory (LLL) described in
Campbell et al. (7) and Campbell et al. (8). The LLL group
determined retorting kinetics by both isothermal and
0097-6156/81/0163-0093$05.25/0

nonisothermal experiments with reasonable agreement between the

two approaches. However, the LLL work was d i r e c t e d toward
i n - s i t u r e t o r t i n g where heating rates are i n h e r e n t l y low. Low
heating rates were found to decrease the o i l y i e l d below
F i s c h e r Assay l e v e l s by i n c r e a s i n g coke formation. For small
p a r t i c l e s , the detrimental e f f e c t of slow heating could be
e l i m i n a t e d by sweeping the sample with an i n e r t gas implying
that the coking was a s s o c i a t e d with holdup i n a l i q u i d s t a t e .
Such coking i s not of importance i n the present i n v e s t i g a t i o n
where the sample i s w e l l swept, and heatup r a t e s ar.e three
orders of magnitude higher than t y p i c a l i n - s i t u r a t e s .
The LLL k i n e t i c model p r e d i c t s that the maximum achievable
o i l y i e l d i s that of F i s c h e r Assay and that the coke associated

with F i s c h e r Assay i s s t o i c h i o m e t r i c a l l y r e l a t e d to the kero-
gen. T h i s assumption may be appropriate f o r i n - s i t u r e t o r t i n g ,
but i t i s not a p p l i c a b l e to the present c o n d i t i o n s where o i l
y i e l d s higher than F i s c h e r Assay are measured. O i l y i e l d s as
high as 110% of F i s c h e r Assay have been reported f o r high
heating rates (Hinds, j [ ) . Therefore, another o b j e c t i v e of t h i s
work i s to extend the k i n e t i c s of o i l production beyond the
F i s c h e r Assay l i m i t .
Experimental Technique
A bench-scale f l u i d i z e d bed r e a c t o r shown i n Figure 1 was

used to r e t o r t small samples o f o i l shale p a r t i c l e s . The g l a s s
r e a c t o r held a bed of i n e r t s o l i d s such as glass beads or sand
that was continuously f l u i d i z e d by a c o n t r o l l e d flow of helium
or any other gas. A weighed sample of shale i n an amount no
greater than 2% of the bed was dropped i n t o the preheated
r e a c t o r , producing a n e g l i g i b l e drop i n bed temperature. Heat
t r a n s f e r i n the f l u i d i z e d bed was very r a p i d , and the v o l a t i l e
products were r a p i d l y swept out by the f l u i d i z i n g gas. The
vapor residence time i n the r e a c t o r was t y p i c a l l y 3 seconds. A
small sample stream was d i v e r t e d to a flame i o n i z a t i o n detector
(FID i n Figure 1). The FID produced a s i g n a l p r o p o r t i o n a l to
the concentration of t o t a l hydrocarbon. Heteroatom content of
evolved products was assumed constant with time. Since the
hydrocarbon concentration dropped to very low l e v e l s at the end
of the r e t o r t i n g r e a c t i o n , the s e n s i t i v i t y of the detector had
to be increased by at l e a s t a f a c t o r of ten as the r e t o r t i n g
progressed. This increased s e n s i t i v i t y made i t p o s s i b l e to

7. WALLMAN ET A L . Oil Shale Retorting Kinetics 95

record the f u l l product-evolution curve i n c l u d i n g the long

" t a i l " which contains information on the k i n e t i c s at high con-
v e r s i o n l e v e l s . Attempts were made to use the FID f o r quanti-
t a t i v e determination of v o l a t i l e hydrocarbon y i e l d s , but the
r e s u l t s were of i n s u f f i c i e n t accuracy. The area under the
curve d i d , however, give an approximate y i e l d which was used as
an experimental check.
O i l and gas y i e l d s were obtained from another branch of
the apparatus shown i n Figure 1. The o i l was condensed i n a
c o l d trap, and the gases were c o l l e c t e d i n a gas c y l i n d e r by
l i q u i d displacement. The amount of o i l was determined g r a v i -
m e t r i c a l l y , and the amount of hydrocarbon gas was determined
from the t o t a l volume of gas c o l l e c t e d and the gas composi-

t i o n . The o i l was recovered by CS2 e x t r a c t i o n and subjected to
GC a n a l y s i s , standardized against n - p a r a f f i n s . F i n a l l y , to
c l o s e the hydrocarbon balance, the e n t i r e bed c o n s i s t i n g of
i n e r t p a r t i c l e s and r e t o r t e d shale was recovered and i t s hydro-
carbon content determined by burning o f f the organic matter and
measuring the amount of oxygen consumed.
The o i l c o l l e c t i o n trap shown i n Figure 1 proved to be a
c r i t i c a l part of the apparatus. The product o i l tended to form
a s t a b l e aerosol making i t d i f f i c u l t to c o l l e c t . T h i s problem
was overcome by a trap design where the condensation occurred
under a steep thermal g r a d i e n t . The i n s i d e w a l l of the cold
trap was kept at 300°F while the opposite w a l l was i n contact
with a bath at 5°F. A thermally induced outward r a d i a l flow
promoted f i l m condensation on the c o l d w a l l . Interestingly,
t h i s design eliminated aerosol formation when using helium as
the f l u i d i z i n g gas; but with heavier gases such as argon,
n i t r o g e n , and even methane, a e r o s o l formation s t i l l occurred.
The cause of t h i s e f f e c t was not i n v e s t i g a t e d , but i t could be
r e l a t e d to d i f f e r e n c e s i n c o n d u c t i v i t y between the gases. The
s e l e c t e d bath temperature of 5°F proved p r a c t i c a l because no
butanes condensed, and only a small p o r t i o n of l i g h t o i l
(C5-C7) was l o s t to the gas. This l i g h t o i l was accounted f o r
by use of the gas a n a l y s i s .
Another area of experimental d i f f i c u l t y was gas analy-
s i s . At low temperatures r e q u i r i n g long r e a c t i o n times, l a r g e
amounts of helium were necessary; and the hydrocarbon products
were i n very low c o n c e n t r a t i o n . This d i f f i c u l t y was overcome
by r e c y c l i n g the gas back i n t o the f l u i d i z e d bed and thereby
allowing the hydrocarbon c o n c e n t r a t i o n to b u i l d up. Some o i l
vapor was undoubtedly r e c y c l e d i n c r e a s i n g the p o s s i b i l i t y of
thermal c r a c k i n g .

7. WALLMAN ET AL. Oil Shale Retorting Kinetics 97
The shale samples used i n t h i s work were obtained by

screening from a s i n g l e bulk sample of Colorado o i l shale
( A n v i l Points Mine, courtesy of Development Engineering
Incorporated and the U.S. Department of Energy). The F i s c h e r
Assay o i l y i e l d was 10.5 wt % based on f r e s h shale (27.5
gallons/ton) f o r the l a r g e r p a r t i c l e s and somewhat lower f o r
the f i n e r s i z e cuts, f o r example, 10.15 wt % f o r 100 um
particles.
Yield Results
Experiments were conducted to determine the e f f e c t of o i l

shale p a r t i c l e s i z e on product y i e l d s at 930°F. The y i e l d s

obtained f o r p a r t i c l e s of s i x d i f f e r e n t s i z e s are compared with
F i s c h e r Assay y i e l d s i n Figure 2. I t i s apparent that o i l
y i e l d s higher than F i s c h e r Assay are obtained f o r small p a r t i -
c l e s ; whereas large p a r t i c l e s produce F i s c h e r Assay y i e l d . The
incremental o i l produced from small p a r t i c l e s i s balanced by a
decreased coke make while the gas make remains constant. The
o i l y i e l d appears to have a l i m i t at about 110 wt % F i s c h e r
Assay, but t h i s may be e n t i r e l y due to the l i m i t e d range of
p a r t i c l e s i z e s i n v e s t i g a t e d . I t i s p o s s i b l e that the o i l y i e l d
would increase f u r t h e r f o r , say, 10 \m or 1 um p a r t i c l e s .
However, p a r t i c l e s of t h i s s i z e could not be studied i n the
apparatus of t h i s work.
Not only do smaller p a r t i c l e s produce more o i l , but there
i s a l s o a change i n the o i l composition. The c o n c e n t r a t i o n of
C c o m o n e n t
29+ P s i n the product o i l i s shown i n Figure 3.
Increased o i l y i e l d s are accompanied by increased heavy ends.
Hence, the c o n c l u s i o n i s that the incremental o i l obtained from
small p a r t i c l e s i s of higher molecular weight.
The e f f e c t of r e t o r t i n g temperature on the y i e l d s obtained
from 0.4 mm p a r t i c l e s and the accompanying change i n o i l compo-
s i t i o n are shown i n Figures 4 and 5. The important f i n d i n g s
here are that coke y i e l d i s unaffected by r e t o r t i n g temperature
and that o i l y i e l d i s increased due to decreased gas make at
the lower temperatures. This second f i n d i n g suggests decreased
c r a c k i n g since Figure 5 shows that a l i g h t e r o i l product i s
obtained at the higher temperatures. I t w i l l a l s o be noted
that the data set shown i n Figure 4 has some " e x t r a " cracking
i n comparison with the data of Figure 2. This i s due to the
f a c t that the r e s u l t s of Figure 4 were obtained i n the r e c y c l e
gas mode where r e c y c l i n g of a small p o r t i o n of the o i l

mm 9 • -* Total Hydrocarbon
ir" C 5
+
Oil
100 /im 1 mm 10 mm
Particle Size
Figure 2. Particle-size effect on hydrocarbon yields at 930°F: fluidized-bed retort

(• ); Fischer assay retort ( ).
iio r
106 -
102-
4 10 12
_L
14
J
16
Wt % C 2 9
+
in Oil
Figure 3. Correlation between oil yield and oil composition

WALLMAN E TAL. Oil Shale Retorting Kinetics
Total
— Hydrxarbon
C 0il5
+
800 850 900 950 1000

Retorting T e m p . , °F
Figure 4. Temperature effect on hydrocarbon yields for OA-mm particles: Fischer

assay ( ).
25
20
N
+
o \ C
+
* 15
o
O
^ 10
C C
5 8
0 J L J
800 900 1000

Retorting Temp., °F
Figure 5. Oil composition as a function of retorting temperature

occurred. In general, the gas make was found to be very s e n s i -

t i v e to equipment c o n d i t i o n s such as the temperature of the
product l i n e leading to the condenser.
Kinetic Results
The k i n e t i c complement to the y i e l d r e s u l t s discussed

above was obtained from the FID response curve. I n t e g r a t i o n of
t h i s curve gave the f r a c t i o n a l conversion. F i g u r e 6 shows the
r e s u l t s of the p a r t i c l e - s i z e e f f e c t experiments p l o t t e d as the
logarithm of the f r a c t i o n unconverted hydrocarbon versus
time. I t appears that the r e s u l t s can be described by a p a i r
of f i r s t - o r d e r processes since the curves can be approximated

by two s t r a i g h t - l i n e segments. By comparing the slopes of the
two segments, the rates of the two processes are found to d i f -
f e r by a f a c t o r of ten. This i s an important f i n d i n g with con-
sequences f o r the p y r o l y s i s model to be proposed i n a subse-
quent s e c t i o n .
The small d i f f e r e n c e s between the i n i t i a l segments of the
k i n e t i c curves i s due to d i f f e r e n c e s i n heatup time f o r the
d i f f e r e n t p a r t i c l e s i z e s . However, heatup time i s r e l a t i v e l y
unimportant even f o r the 3 mm p a r t i c l e s because the s t r a i g h t -
l i n e segment extrapolates to only 15 seconds on the time
axis. T h i s "experimental" heatup time i s about what one would
c a l c u l a t e using a heat t r a n s f e r c o e f f i c i e n t of 100 Btu/hr f t ^
°F.
An important feature of the r e s u l t s shown i n Figure 6 i s
that the slope of the l a t t e r segment of the curve changes f o r
p a r t i c l e s of d i f f e r e n t s i z e . The process corresponding to t h i s
segment appears to be slower f o r the small p a r t i c l e s than f o r
the large ones. T h i s unexpected c h a r a c t e r i s t i c i s at f i r s t
surprising. I t i s , however, a consequence of the d i f f e r e n t
y i e l d s f o r d i f f e r e n t p a r t i c l e s i z e s shown i n F i g u r e 2. The
y i e l d d i f f e r e n c e s do not enter the k i n e t i c r e s u l t s of Figure 6
because the ordinate i s normalized by the t o t a l hydrocarbon
evolved ( t h i s type of p l o t i s required f o r determination of the
rate constants).
The k i n e t i c and y i e l d data are combined i n Figure 7 f o r
the 0.4 mm and 3 mm p a r t i c l e s . This f i g u r e shows that the
hydrocarbon e v o l u t i o n i s e s s e n t i a l l y independent of p a r t i c l e
s i z e up to 100% F i s h e r Asay o i l y i e l d . At t h i s l e v e l the o i l
production stops f o r large p a r t i c l e s , whereas i t continues f o r
small p a r t i c l e s at a reduced r a t e .

WALLMAN E T AL. Oil Shale Retorting Kinetics 101
Figure 6. Particle-size effect on retorting kinetics at 930°F

0 0 l 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Retorting Time, Min.
Figure 7. Oil production kinetics at 930°F

The e f f e c t of temperature on the r e t o r t i n g k i n e t i c s i s

shown i n Figure 8 f o r the 1 ram p a r t i c l e s . Both processes
respond to temperature but the fast one more so than the slow
one.
Table I
Rate Expressions f o r Hydrocarbon

Production from Kerogen
(C I n i t i a l Kerogen Content)
Q
L i g h t Hydrocarbon Production:
f k k t
Rate = i " i ' C *e" 1
1
Amount - f " i ' C * ( l - e"" ^) 0
Primary Heavy O i l Production:
# , # k + k ) t
Rate = f 2 k 2 C 0 e~( 2 c
k + k t
Amount = f ^ - r — C *[1 - e~( 2
9 c) ]
1 J
^ k. + k o
2 c
I n t r a p a r t i c l e Coke Production:
f # k C # e ( k 2 k c ) t
Rate = f 2 * c c* o "" *
(k + k ) t :
Amount = f * f . 9 ^ - r — C *[1 - e"" 2 c ]
L J
^ c k 0 + k o
I c
Kerogen P y r o l y s i s Model
The combined k i n e t i c and y i e l d data can be c o r r e l a t e d with

the p y r o l y s i s model shown i n Figure 9. Here kerogen decomposes
i n t o a " l i g h t " hydrocarbon product and a heavy intermediate
product, "bitumen." The l i g h t product i s l a r g e l y a vapor a t
r e t o r t i n g conditions and i s , t h e r e f o r e , produced r a p i d l y with-
out s i g n i f i c a n t secondary r e a c t i o n s . The bitumen, on the other
hand, i s of high b o i l i n g range and remains i n the p a r t i c l e f o r
s i g n i f i c a n t periods of time. I t becomes subject to two com-
peting processes: (1) heavy o i l production and (2) i n t r a p a r -
t i c l e (liquid-phase) coking. The r e l e a s e d heavy o i l i s f u r t h e r

Reaction Time, M i n .
Figure 8. Temperature effect on retorting kinetics for 1-mm particles

7. WALLMAN ET A L . Oil Shale Retorting Kinetics 105

subjected to thermal cracking i n the vapor phase surrounding

the p a r t i c l e s .
F i r s t - o r d e r rate expressions are proposed i n Table I f o r
the three p r i n c i p a l steps: l i g h t hydrocarbon production
(equals kerogen decomposition), primary heavy o i l production,
and coking.
The model accounts f o r the dramatic change i n o i l produc-
t i o n rate which i s observed. The f a s t i n i t i a l r a t e i s governed
by the rate constant kj_ ( f i r s t order i n kerogen c o n t e n t ) . The
l a t t e r slow rate i s governed by the sum of the two bitumen
r e a c t i o n s , which are assumed f i r s t order i n the i n t r a p a r t i c l e
bitumen content and have rate constants k and k . 2 At the
Q
temperatures of i n t e r e s t , k i s much greater than k + k so

1 2 c
that the f i r s t step of the r e a c t i o n goes v i r t u a l l y to comple-

t i o n before there i s any a p p r e c i a b l e conversion of the bitumen.
Table I I
L i g h t Hydrocarbon F r a c t i o n , f ^
Total Light
Volatile- Hydrocarbon
Hydrocarbon Y i e l d , % of L i g h t Hydrocarbon
Particle Yield, Total Volatile Y i e l d , % of
S i z e , mm % of Kerogen Hydrocarbon Kerogen
3 68.8 90 61.9
2 70.0 87 60.9
1 71.1 87 61.9
0.4 74.4 83 61.8
Avg =61.6
The r e l a t i v e y i e l d s of the kerogen decomposition products

are expressed as the f r a c t i o n s f ^ , f , and f i n F i g u r e 9.
2 w The
(H 0, CO, C0 ) f r a c t i o n was set equal to that of F i s c h e r Assay
2 2
because the amount of water i n the l i q u i d product could not be

e a s i l y determined i n the y i e l d experiments. The l i g h t hydro-
carbon f r a c t i o n , f ^ , was determined by a combination of the
y i e l d and the k i n e t i c data. The l i g h t hydrocarbon y i e l d s as

f r a c t i o n s of t o t a l v o l a t i l e hydrocarbon were obtained by e x t r a -

p o l a t i n g the slow r e a c t i o n segments of Figure 6 to zero time
and reading the f r a c t i o n s o f f the o r d i n a t e . The r e s u l t s are
shown i n Table I I . The values of f ^ obtained f o r the four par-
t i c l e s i z e s are s u f f i c i e n t l y constant to j u s t i f y an average
value of 61.6%. The l i g h t hydrocarbon y i e l d f r a c t i o n f-^ i s
a l s o seen to be approximately independent of temperature from
F i g u r e 8 where a l l the slow reactor segments extrapolate back
to approximately the same point on the o r d i n a t e , namely 87%
l i g h t hydrocarbon. The bitumen f r a c t i o n f i n F i g u r e 9 i s
2
obtained by d i f f e r e n c e and equals 24%. Hence, f i s constant 2
with both p a r t i c l e s i z e and temperature at l e a s t i n the range

of 900-1000°F. F i n a l l y , a r a t i o between coke and gas i n the

coking r e a c t i o n of 80:20 was set on the assumption that the gas
y i e l d at 800°F i n Figure 4 i s the r e s u l t of coking alone.
Campbell et a l . (8) used e s s e n t i a l l y the same coke-gas r a t i o
f o r a s i m i l a r r e a c t i o n i n t h e i r r e a c t i o n sequence.
In a d d i t i o n to the coking r e a c t i o n , vapor-phase c r a c k i n g
of the heavy o i l released from the p a r t i c l e i s a source of
gas. Cracking of the l i g h t hydrocarbon f r a c t i o n i s a l s o pos-
s i b l e ; but because i t occurs to a l e s s e r extent, i t has been
assumed to be zero. The k i n e t i c s of the cracking r e a c t i o n l i e
o u t s i d e the scope of the present i n v e s t i g a t i o n , but t h i s impor-
tant r e a c t i o n has been studied by Burnham and T a y l o r (10). A
t h i r d source of gas i s the i n i t i a l decomposition of kerogen
itself. However, the c o n t r i b u t i o n of each gas-generation step
cannot be determined i n the present i n v e s t i g a t i o n because of
the i n a b i l i t y of the FID detector to d i s t i n g u i s h between gas
and o i l .
The kerogen decomposition rate constant, k^, and the
bitumen disappearance r a t e constant ( k + k ) are obtained
2 c
d i r e c t l y as the slopes of the two s t r a i g h t - l i n e segments of

Figures 6 and 8 (and s i m i l a r graphs f o r the other p a r t i c l e
s i z e s ) . Figure 10 shows the temperature dependence of these
r a t e constants. I t i s also seen that k^ i s independent of
p a r t i c l e s i z e . This implies that there i s no s i g n i f i c a n t
r e s i s t a n c e to the transport of l i g h t hydrocarbons from the
i n t e r i o r of the p a r t i c l e into the bulk of the c a r r i e r gas.
This c o n d i t i o n i s a consequence of the high vapor pressure of
the l i g h t hydrocarbon f r a c t i o n . Because of the r a p i d transport
out of the p a r t i c l e , t h i s f r a c t i o n has no p o s s i b i l i t y to
coke. The bitumen, on the other hand, i s viewed as a high
b o i l i n g l i q u i d which can undergo i n t r a p a r t i c l e coking. The

Figure 10. Pyrolysis rate constants

p a r t i c l e size dependence of ( k + k ) i n F i g u r e 10 suggests 2 Q
that a d i f f u s i o n a l r e s i s t a n c e may come into play i n the heavy

o i l production step. A l s o , the a c t i v a t i o n energy f o r the reac-
tions governing bitumen disappearance i s only 22.6 kcal/mole as
compared to 43.6 kcal/mole f o r the kerogen decomposition
reaction.
In order to determine k and k i n d i v i d u a l l y , the 2 Q
k i n e t i c a l l y determined values f o r the sum ( k + k ) must be 2 Q
used i n consort with the expression f o r the coke y i e l d

#
0.8 f *k /(k +k ).
2 c 2 The c a l c u l a t e d values of the r a t i o
c
k / ( k + k ) together with the k i n e t i c a l l y obtained values of

c 2 c
( k + k ) are given i n the Appendix.

2 c The r e s u l t i n g k and k 2 c
values show some i n t e r e s t i n g c h a r a c t e r i s t i c s : k i s indepen- 2
dent of p a r t i c l e s i z e whereas k i s p r o p o r t i o n a l to p a r t i c l e c
s i z e . Both have the same temperature dependence because the

coke y i e l d i s constant with temperature. The temperature
dependence and the p a r t i c l e s i z e dependence of k are shown Q
e x p l i c i t l y i n Table I I I . k i s seen to dominate over k c even 2
f o r the 0.4 mm p a r t i c l e s . For the 3 mm p a r t i c l e s , k i s i n s i g - 2
n i f i c a n t i n r e l a t i o n to k implying complete coking of the

Q
bitumen.
Table I I I
1
Rate Constants (Min." )
Kerogen Decomposition:
12
k x = 5.78-10 exp (- *3.6 kcal/mole }
R *T
Heavy O i l Production:
i i o.m5 ,22.6 J kcal/mole
k^2 = 1.8 10 exp (
2
N
)
R*T
Coking:
, . A 22.6 kcal/mole e N
k = A *exp (-
c c )
R*T
where A Q P a r t i c l e Size, mm
isTo 5
3
5
9*10 2
5
5-10 1
5
3*10 0.4

Discussion
As part of t h i s i n v e s t i g a t i o n , kerogen p y r o l y s i s models

d i f f e r e n t from the one proposed here were considered. One such
model of t h e o r e t i c a l appeal i s s i m i l a r i n s t r u c t u r e to the one
given i n Figure 9 but with a pure d i f f u s i o n process f o r the
heavy o i l production. However, t h i s a l t e r n a t i v e model i s
incompatible with some experimental f i n d i n g s : It predicts
lower coke concentrations on the surface of the p a r t i c l e than
i n the i n t e r i o r , whereas microprobe r e s u l t s i n d i c a t e a uniform
coke d i s t r i b u t i o n . Further, t h i s d i f f u s i o n model p r e d i c t s zero
coke y i e l d f o r i n f i n i t e l y small p a r t i c l e s , whereas the l i m i t e d
amount of data a v a i l a b l e f o r small p a r t i c l e s i z e s suggest a

l e v e l i n g - o f f of the coke y i e l d below a p a r t i c l e s i z e of 0.4 mm.
The approach to F i s c h e r Assay y i e l d s t r u c t u r e with
i n c r e a s i n g p a r t i c l e s i z e i s accounted f o r i n the proposed model
by complete coking of the bitumen f r a c t i o n . The model p r e d i c t s
a coke y i e l d of 19% of the kerogen when the bitumen i s com-
p l e t e l y coked, w e l l w i t h i n F i s c h e r Assay range. Therefore,
f l u i d - b e d and F i s c h e r Assay r e t o r t i n g give d i f f e r e n t y i e l d s f o r
small p a r t i c l e s only. The i n t e r p r e t a t i o n of t h i s i s that i n a
F i s c h e r Assay r e t o r t small p a r t i c l e s produce the same amount of
coke as large p a r t i c l e s because there i s no sweep gas to
f a c i l i t a t e o i l removal from the small p a r t i c l e s . The f l u i d bed
r e t o r t i n g experiments have shown that a d d i t i o n a l o i l can indeed
be produced from small p a r t i c l e s .
The proposed model can be compared with both the model of
A l l r e d (4) and that of Campbell et a l . A l l r e d ' s model
does not have the feature of competing p a r a l l e l r e a c t i o n s that
i s e s s e n t i a l to the p y r o l y s i s model proposed here. I t does,
however, have the intermediate product bitumen which reaches a
maximum l e v e l almost i d e n t i c a l to the one i n t h i s work. A l l r e d
p o s t u l a t e s that a l l kerogen decomposes i n t o bitumen, whereas
bitumen i n the present work i s the remainder of the kerogen
a f t e r the l i g h t hydrocarbon f r a c t i o n has been s t r i p p e d o f f .
There are some i n t e r e s t i n g s i m i l a r i t i e s and c o n t r a s t s
between the present model and the Lawrence Livermore Laboratory
(LLL) model of Campbell et a l . ( 8 ) The a c t i v a t i o n energy of the
i n i t i a l decomposition i s s i m i l a r i n both models,
48-54 kcal/mole i n the case of LLL and 44 kcal/mole here.
Bitumen i s treated merely as an intermediate i n the kerogen
decomposition by LLL; whereas, here i t i s one of s e v e r a l decom-
p o s i t i o n products. Coking steps are included i n both models,

but the m a t e r i a l involved i s d i f f e r e n t . The coking k i n e t i c s

accounted f o r by LLL only apply to the l i g h t hydrocarbon of the
present model, and t h i s coking r e a c t i o n does not occur here
because of the high heating rate and the sweep gas. The coking
considered i n the present model involves the intermediate
bitumen product and the coking r a t e depends on p a r t i c l e s i z e .
Small p a r t i c l e s produce l e s s coking and; consequently, o i l
y i e l d s higher than F i s c h e r Assay.
Both A l l r e d (4) and Weithamp and Gutberlet (5) observed
the slow o i l production regime. C a l c u l a t i n g a r a t e constant
f o r t h i s slow production regime at 856°F from the r e s u l t s of
the l a t t e r i n v e s t i g a t o r s gives a value of 0.12 rain.~l i d e n t i c a l
to ( k + k ) of t h i s work.
2 c
A p r a c t i c a l i m p l i c a t i o n of the r e s u l t s of t h i s work i s
that F i s c h e r Assay y i e l d i s probably a reasonable upper l i m i t
f o r any r e t o r t i n g process. T h i s work has shown that a very
small p a r t i c l e s i z e increases o i l y i e l d and decreases coke
y i e l d , but long r e a c t i o n times are necessary. A l s o , low coke
y i e l d s may not be d e s i r a b l e from o v e r a l l heat balance c o n s i d -
e r a t i o n s i f the coke i s to be used as an energy source f o r the
process. Lowering the temperature a l s o increases o i l y i e l d but
at the expense of the gas y i e l d and with the requirement of
long r e a c t i o n times.
T h i s work has added to the understanding of the very
complex phenomena o c c u r r i n g during o i l shale r e t o r t i n g . The
simple kerogen p y r o l y s i s model w i l l be u s e f u l i n modeling prod-
uct y i e l d s from r e t o r t i n g processes handling small s i z e par-
t i c l e s at high r e t o r t i n g r a t e s .
Abstract
An isothermal fluid-bed reactor was used to retort small
samples of 0.1-3mmoil shale particles. The rate of volatile
hydrocarbon evolution was measured by a flame ionization
detector. Yields of oil, gas, and residual coke were deter-
mined and the boiling range of the product oil and the composi-
tion of the gas were measured.
Higher oil yields and lower coke yields are obtained for
smaller particles. Retorting temperature in the range 800-
1000°F does not affect coke yield but has an effect on the
relative yield of oil and gas. The experimental data are cor-
related by a simple empirical pyrolysis model where kerogen
decomposes by a first-order reaction into a light hydrocarbon
product and a heavy intermediate product, "bitumen." Subse-
quently, the bitumen is subject to two competing processes:

(1) heavy oil production and (2) intraparticle (liquid-phase)

coking. Both of these processes are modeled as first-order
reactions. The produced oil is also subject to thermal
cracking in the vapor phase surrounding the particles. The
rate constants for the disappearance of bitumen by reactions
(1) and (2) are an order of magnitude smaller than the kerogen
decomposition rate constant which ranges from 1 to 10 min.
over a temperature range of 900-1000°F.
Literature Cited
1. Hubbard, A. B.; Robinson, W. E. "A Thermal Decomposition
Study of Colorado Oil Shale," Report of Investigation

4744, Bureau of Mines, Washington, D.C., 1950.
2. Braun, R. L.; Rothman, A. J. Fuel, 1975, 54, 129.
3. Johnson, W. F.; Walton, D. K.; Keller, H. H.; Couch, E. J.
Quarterly of the Colorado School of Mines, 1975, 70 (3),
237.
4. Allred, V. D. Chem. Eng. Progr., 1966 62, (8), 55.
5. Weitkamp, A. W.; Gutberlet, L. C. Ind. Eng. Chem. Process
Des. Develop., 1970, 9 (3), 386.
6. Fausett, D. W.; George, J. H.; Carpenter, H. C. "Second-
Order Effects in the Kinetics of Oil Shale Pyrolysis,"
Report of Investigation 7889, Bureau of Mines, Washington,
D.C., 1974.
7. Campbell, J. H.; Koskinas, G. H.; Stout, N. D. "The
Kinetics of Decomposition of Colorado Oil Shale: I. Oil
Generation," Report UCRL-52089 Prepared for the U.S.
Energy Research and Development Administration, Lawrence
Livermore Laboratory, June 1976.
8. Campbell, J. H.; Koskinas, G. H.; Coburn, T. T.; Stout,
N. D. "Oil Shale Retorting: The Effects of Particle Size
and Heating Rate on Oil Evolution and Intraparticle Oil
Degradation," Report UCRL-52256 Prepared for the U.S.
Livermore Laboratory, April 1977.

9. Hinds, G. P., "Effect of Heating Rate on the Retorting of

Oil Shale," Paper Presented at the 71st Annual Meeting of
the AIChE, Miami Beach, Florida, November 1978.
1. Kinetics," Report UCID-18284 Prepared for the U.S.
Livermore Laboratory, October 1979.
AJPJ>J:NDJ.X
HEAVY OIL PRODUCTION AND COKING RATE CONSTANTS,

1
k 2 AND k (RATE CONSTANTS IN MIN." ,
Q
COKE YIELDS IN WT % KEROGEN)
Particle
S i z e , mm 900° F 930° F 950°F 980°F 1000°F
k k 2 + c 0.887 1.04
Coke Y i e l d 16.8 16.8
k /(k +
c 2 k 0.875 0.875
c>
k 0.776 0.908
c
k 2
0.111 0.130
k + k
0.442 0.545
2 c
Coke Y i e l d 15.6 15.6
k /(k
c 2 + c>
k 0.813 0.813
k
c 0.359 0.443
k 2 0.083 0.102
k 2 + k 0.186 0.292 0.367 0.378 0.587

Coke Y i e l d 14.5 14.5 14.5 14.5 14.5
k /(k +
c 2 k 0.755 0.755 0.755 0.755 0.755
c>
k 0.140 0.220 0.277 0.285 0.443
c
k 2
0.046 0.072 0.090 0.093 0.144
0.4 k + k
0.197 0.296
2 c
Coke Y i e l d 11.2 11.2
k /(k + k >
c 2 c 0.583 0.583
k 0.115 0.173
c
k 2 0.082 0.123

8
Kinetics of Oil Shale Char Gasification
1
W. J.THOMSON ,M. A. GERBER, M. A. HATTER, and D. G. OAKES
Department of Chemical Engineering, University of Idaho, Moscow, Idaho 83843
During o i l s h a l e r e t o r t i n g , whether i t be by i n - s i t u o r s u r -
face techniques, a c e r t a i n f r a c t i o n o f the o r g a n i c carbon i s l e f t
behind on the r e t o r t e d s h a l e . T h i s "char" c o n t a i n s a s i g n i f i c a n t
f r a c t i o n o f t h e a v a i l a b l e e n e r g y i n t h e raw s h a l e and can a c t u a l l y
supply a l l the energy f o r the r e t o r t i n g process f o r s h a l e s assayed
a t 20 g a l l o n s / t o n o r g r e a t e r ( l _ ) . T o r e c o v e r t h i s e n e r g y , t h e c h a r
can b e b u r n e d i n a i r o r g a s i f i e d i n o x y g e n - s t e a m e n v i r o n m e n t s ; t h e
l a t t e r i n o r d e r t o p r o d u c e a low t o medium BTU gas w h i c h can be
b u r n e d e l s e w h e r e i n t h e p l a n t . C o n s e q u e n t l y we have been c o n d u c -
t i n g k i n e t i c s t u d i e s o f t h e r e a c t i o n s o f o i l s h a l e c h a r i n a n on-
g o i n g r e s e a r c h p r o g r a m . E a r l i e r we r e p o r t e d o n t h e r e s u l t s o f o u r
o x i d a t i o n experiments[2) and h e r e we w i l l d i s c u s s o u r work w i t h
CO2 and s t e a m g a s i f i c a t i o n o f t h e c h a r .
I t s h o u l d be n o t e d t h a t t h e r e has been some p r e v i o u s l y pub-
l i s h e d work d e a l i n g w i t h t h e s e r e a c t i o n s . S t u d i e s a t U n i o n O i l
R e s e a r c h i n t h e e a r l y 1970*5 a p p e a r t o be among t h e f i r s t t o a t -
tempt t h e e x p l o i t a t i o n o f t h e s t e a m - c h a r r e a c t i o n and l e d t o t h e
d e v e l o p m e n t o f t h e SGR r e t o r t i n g p r o c e s s ( 3 j . L a t e r , Burnham a t
L a w r e n c e L i v e r m o r e L a b o r a t o r i e s ( 4 , 5 _ 6 ) c o n d u c t e d b o t h non-
9
i s o t h e r m a l and i s o t h e r m a l e x p e r i m e n t s and o b t a i n e d r e a c t i o n r a t e
e x p r e s s i o n s f o r t h e r a t e o f c h a r c o n s u m p t i o n due t o b o t h r e a c -
tions
COo + C + 2C0
H0
2 + C + CO + H
They observed, a s d i d the e a r l i e r r e s e a r c h e r s a t Union O i l t h a t

t h e w a t e r gas s h i f t r e a c t i o n
CO + H 0 t CO2 + H
2 (3)
1
Current address: Department of Chemical Engineering, Washington State University,
Pullman, WA 99164.
0097-6156/81/0163-0115 $05.00/0

a l s o o c c u r r e d a t a r a p i d r a t e so t h a t t h e primary gaseous products

were e s s e n t i a l l y H a n d C 0 . 2 2
S i n c e we w i l l be c o m p a r i n g o u r c u r r e n t r e s u l t s w i t h t h o s e
m e a s u r e d by Burnham a t L a w r e n c e L i v e r m o r e L a b o r a t o r i e s ( L L L ) , i t
i s a p p r o p r i a t e t o r e p e a t them h e r e . Burnham was b e s t a b l e t o f i t
h i s d a t a by a s s u m i n g t h e p r e s e n c e o f two s e p a r a t e c a r b o n s p e c i e s
w h i c h r e a c t e d i n p a r a l l e l and s u g g e s t e d t h e f o l l o w i n g r a t e e x -
pression
0.2
r = k C + k C ( p )
C0 2 ( l C! 2 c ) 2 C0 2 ' (4)
where C and Cc l i n i t i a l l y r e p r e s e n t e d 7 5 % a n d 25%, r e s p e c t i v e l y ,

C 2
o f t h e t o t a l o r g a n i c c a r b o n . T h e C] s p e c i e s had a h i g h e r a c t i v a -
t i o n e n e r g y (205 k i l o j o u l e s / m o l e v s 134) and was t h u s more s e n s i -

t i v e t o increases i n temperature. T h e i r steam g a s i f i c a t i o n d a t a
were a l s o f i t t o a p a r a l l e l r e a c t i o n r a t e e x p r e s s i o n
r k C ( P 5 +
H 0 2 " 3 cJ H oi" 2 k C 4 C 2 (5)
b u t i n t h i s c a s e C -j a c c o u n t e d f o r 57% o f t h e i n i t i a l o r g a n i c
c
c a r b o n and a g a i n had a h i g h e r a c t i v a t i o n e n e r g y (184 k i l o j o u l e s /

mole v s 1 3 4 ) .
The e m p i r i c a l n a t u r e o f t h e s e e x p r e s s i o n s i s a p p a r e n t and
t h u s a m a j o r g o a l o f o u r work was t o a t t e m p t t o d e r i v e r a t e e x -
p r e s s i o n s more t y p i c a l o f what w o u l d be e x p e c t e d f o r c h a r g a s i f i -
c a t i o n r e a c t i o n s based on t h e c o a l l i t e r a t u r e ^ ) . Another goal
was t o be a b l e t o p r e d i c t make-gas c o m p o s i t i o n s and t h u s a s e p a -
r a t e d e t e r m i n a t i o n o f t h e w a t e r - g a s s h i f t r e a c t i o n r a t e was a l s o
undertaken. F i n a l l y , because o f evidence t h a t the i r o n p r e s e n t
i n t h e s h a l e a c t e d t o c a t a l y z e t h e s h i f t r e a c t i o n , a number o f
o x i d a t i o n / r e d u c t i o n e x p e r i m e n t s were r u n i n o r d e r t o a s s e s s t h e
a b i l i t y o f t h e r e a c t i n g gases t o a f f e c t the o x i d a t i o n s t a t e o f
the i r o n .
S i n c e some o f t h e m i n e r a l s i n d i g e n o u s t o t h e s h a l e c a n a c t a s
c a t a l y s t s , i t i s relevant t o l i s t the pertinent mineral reactions
which can take p l a c e :
CaMg(C0 ) 3 2 + CaC0 + MgO + C 0

3 2 (6)
CaC0 3 t CaO + C 0 2 (7)
CaC0 + S i 0
3 2 + Silicates + C0 2 (8)
CaFe(C0 ) 3 2 + FeO + C a C 0 + C 0 3 2 (9)
E q u a t i o n ( 6 ) , " d o l o m i t e d e c o m p o s i t i o n , " i s i r r e v e r s i b l e and takes

p l a c e a t T >875K. E q u a t i o n ( 7 ) , " c a l c i t e d e c o m p o s i t i o n , " i s
r e v e r s i b l e and c a n be p r e v e n t e d i f t h e r e i s a s u f f i c i e n t C 0 o v e r - 2
p r e s s u r e . E q u a t i o n ( 8 ) , " s i l i c a t i o n , " i s i r r e v e r s i b l e and t a k e s

p l a c e a t h i g h e r t e m p e r a t u r e s (>1050K) p r o v i d e d t h a t c a l c i t e d e -
c o m p o s i t i o n i s p r e v e n t e d . E q u a t i o n (9) o c c u r s a t l o w e r tempera-
t u r e s and i s s i g n i f i c a n t because the i r o n oxides t h a t r e s u l t can

8. THOMSON E T AL. Oil Shale Char Gasification 111
a c t a s c a t a l y s t s d e p e n d i n g on t h e v a l e n c e s t a t e o f i r o n , a n d t h i s
can b e i n f l u e n c e d by t h e t e m p e r a t u r e a n d c o n c e n t r a t i o n o f t h e s u r -
rounding gases.
E x p e r i m e n t a l Equipment and Procedures
Equipment. A l l o f t h e g a s i f i c a t i o n e x p e r i m e n t s were c o n d u c -
t e d w i t h t h e same a p p a r a t u s employed i n t h e e a r l i e r o x i d a t i o n work
and h a s been d e s c r i b e d i n d e t a i l e l s e w h e r e ( 2 j . T h e t e c h n i q u e i n -
v o l v e d s i m u l t a n e o u s measurements o f mass l o s s (TGA) a n d e x i t g a s
c o m p o s i t i o n s (gas c h r o m a t o g r a p h ) i n a v e s s e l w h i c h behaved a s a n
i d e a l b a c k - m i x r e a c t o r . A l l e x p e r i m e n t s were r u n u n d e r i s o t h e r m a l
c o n d i t i o n s . A s b e f o r e , powdered s h a l e samples (200 mesh) o f p r e -
v i o u s l y r e t o r t e d o i l s h a l e f r o m t h e P a r a c h u t e C r e e k member i n
C o l o r a d o were s u s p e n d e d f r o m an e l e c t r o b a l a n c e a n d p l a c e d i n a
f u r n a c e . I n t h i s way c o n t i n u o u s g r a v i m e t r i c r e a d i n g s were a v a i l -
a b l e t o m o n i t o r t h e c o n s u m p t i o n o f t h e c h a r . T h e o f f - g a s e s were
a n a l y z e d on a C a r l e g a s c h r o m a t o g r a p h e q u i p p e d w i t h a C a r b o s i e v e
B column.
P r o c e d u r e s . S i n c e t h e c h a r r e a c t i o n s c a n be a c c o m p a n i e d b y
m i n e r a l d e c o m p o s i t i o n r e a c t i o n s , some o f w h i c h a r e c a t a l y t i c ,
e v e r y a t t e m p t was made t o i s o l a t e t h e p e r t i n e n t r e a c t i o n s . O f
course t h e r e i s always t h e p o s s i b i l i t y t h a t s i g n i f i c a n t i n t e r a c -
t i o n s w i l l be m i s s e d b y t h i s p r o c e d u r e a n d t h u s i t i s i m p o r t a n t
t o s t a t e t h e p r o c e d u r e s w h i c h were employed.
C0
2 - Gasification. The p r e v i o u s l y r e t o r t e d s h a l e (see (8)
f o r d e t a i l s ) was f i r s t r a i s e d t o 900K i n a h e l i u m a t m o s p h e r e t o
allow i r r e v e r s i b l e dolomite decomposition t o take place. F o r
t h o s e e x p e r i m e n t s i n w h i c h CO2 was t h e o n l y s p e c i e s i n t h e f e e d
g a s , t h e r a t e o f CO2 g a s i f i c a t i o n was f o l l o w e d by m o n i t o r i n g t h e
r a t e o f p r o d u c t i o n o f CO; i . e . , f r o m G.C. m e a s u r e m e n t s . However
t h i s was n o t a c c u r a t e i n t h o s e e x p e r i m e n t s w h i c h h a d CO i n t h e
i n l e t g a s , a n d i n t h e s e c a s e s t h e r a t e was d e t e r m i n e d s o l e l y by
g r a v i m e t r i c measurements. A f u r t h e r c o m p l i c a t i o n d u r i n g these
e x p e r i m e n t s was t h e f a c t t h a t t h e p r e s e n c e o f even s m a l l q u a n t i -
t i e s o f CO r e t a r d e d t h e C 0 g a s i f i c a t i o n r a t e t o t h e p o i n t where
2
s i l i c a t i o n r a t e s were on t h e same o r d e r o f m a g n i t u d e . Consequent-

l y t h e sample was p u r p o s e l y p r e t r e a t e d by a l l o w i n g c o m p l e t e s i l i -
c a t i o n t o t a k e p l a c e . T h i s was a c h i e v e d by e x p o s i n g t h e sample
t o a 4 0 % C 0 - 3 0 % CO m i x a t H O O K f o r 8-12 h o u r s . T h e C 0 p r e -
2 2
v e n t e d c a l c i t e d e c o m p o s i t i o n ( e q u a t i o n ( 7 ) ) a n d t h e h i g h CO
c o n c e n t r a t i o n r e t a r d e d C 0 g a s i f i c a t i o n s o t h a t o n l y 5-10% o f
2
t h e c a r b o n was consumed d u r i n g t h e p r e t r e a t m e n t .
Steam Gasification. Because o f t h e temperatures required
f o r steam g a s i f i c a t i o n (>950K), s i g n i f i c a n t C 0 p r e s s u r e s w o u l d b e
2
r e q u i r e d t o p r e v e n t c a l c i t e d e c o m p o s i t i o n . S i n c e we were a t t e m p t -
ing t o study t h e H 0 + C r e a c t i o n i n t h e absence o f C 0 g a s i f i c a -
2 2
t i o n , we d e c i d e d t o a l l o w t h e c a l c i t e t o decompose c o m p l e t e l y t o
t h e o x i d e s . T h i s was done i n a h e l i u m purge s t r e a m a t 975K. T h e
d e c o m p o s i t i o n t i m e and p u r g e r a t e were s u c h t h a t a t t h i s tempera-

t u r e o n l y a b o u t 1 0 % o f t h e c a r b o n was consumed d u e t o CO2 g a s i -

f i c a t i o n . A l t h o u g h t h e k i n e t i c d a t a were t a k e n i n t h e p r e s e n c e
o f o x i d e s , a f e w r u n s were a l s o c o n d u c t e d w i t h s h a l e samples sub-
jected toacid leaching(9).
Water Gas Shift Reaction (WGSR). T h e WGSR was s t u d i e d o v e r
s h a l e samples w h i c h had been p r e v i o u s l y d e c h a r r e d a n d s i l i c a t e d .
A f t e r d e - c h a r r i n g a t 700K i n a 1 0 % 0 s t r e a m , t h e sample was e x -
2
posed t o 4 0 % C 0 a t H O O K f o r 12 h o u r s . Upon c o m p l e t i o n o f
2
s i l i c a t i o n t h e t e m p e r a t u r e was a d j u s t e d t o t h e d e s i r e d v a l u e a n d
t h e s h a l e was e i t h e r o x i d i z e d ( i n a i r o r C 0 ) o r r e d u c e d ( i n H 2 2
o r CO). T h i s was f o l l o w e d by WGSR e x p e r i m e n t s i n w h i c h v a r i o u s

c o n c e n t r a t i o n s o f CO, H 0 , C 0 a n d H were f e d t o t h e r e a c t o r .
2 2 2
=
V a r i a b l e s . C 0 g a s i f i c a t i o n d a t a were o b t a i n e d up t o P c o
2 2
100 kPa a n d a t t e m p e r a t u r e s between 975K a n d H O O K . Steam g a s i -

f i c a t i o n was s t u d i e d a t H 0 p r e s s u r e s between 15 a n d 75 kPa a n d

2
a t t e m p e r a t u r e s between 975K a n d 1150K. T h e k i n e t i c s o f t h e WGSR

were a l s o s t u d i e d o v e r t h i s same t e m p e r a t u r e r a n g e a n d w i t h v a r i -
ous f e e d g a s c o m p o s i t i o n s c o n s i s t i n g o f H 0 , CO, C 0 a n d H . I n 2 2 2
o r d e r t o r e m a i n o n t h e l e f t hand s i d e o f t h e WGSR e q u i l i b r i u m ,
t h e maximum p r e s s u r e s o f C 0 a n d H were 30 kPa. T h e o i l s h a l e
2 2
was f r o m t h e P a r a c h u t e C r e e k Member i n C o l o r a d o a n d a s s a y e d a t
50 g a l l o n s / t o n . O u r e a r l i e r w o r k ( 2 j h a d i n d i c a t e d t h a t t h e r e was
no e f f e c t o f a s s a y o n t h e c h a r o x i d a t i o n k i n e t i c s .
Results
C 0 G a s i f i c a t i o n . The r a t e e x p r e s s i o n which r e s u l t s from an

2
analysis o r t h e u u g a s i f i c a t i o n data i s given i n equation (10).

2
r k P
C0 2 5 C0 2
( 1 0 )
C c 1 + K l P C 0 2 + K P
2 C Q
where
4 1
k, = 7.83 x 1 0 e x p (-184/RT) ( k P a - s e c ) "
1
K? = 0.0495 ( k P a ) -
1
K 2 = 5.0 ( k P a ) "
T h i s f o r m o f t h e r a t e e x p r e s s i o n i s t y p i c a l o f t h a t used t o c o r -
r e l a t e much o f t h e e a r l y g a s i f i c a t i o n d a t a on c o a l . T h e p a r a -
m e t e r s t h e m s e l v e s were o b t a i n e d f r o m a. m u l t i p l e r e g r e s s i o n
a n a l y s i s o f t h e r e c i p r o c a l o f e q u a t i o n ( 5 ) . An i n i t i a l v a l u e o f
t h e a c t i v a t i o n e n e r g y was o b t a i n e d f r o m a power l a w f i t a n d was
t h e n a d j u s t e d by t i r a l a n d e r r o r u n t i l i t was c o m p a t i b l e w i t h t h e
b e s t f i t f r o m t h e r e g r e s s i o n . F i g u r e 1 g i v e s some i d e a o f t h e
a b i l i t y o f t h e equation t o f i t t h e data over a wide C 0 pressure 2
range. Of p a r t i c u l a r s i g n i f i c a n c e i s t h e f i t t o t h e data c o r r e s -
p o n d i n g t o t h e d a s h e d l i n e w h i c h were o b t a i n e d d u r i n g m i n e r a l
d e c o m p o s i t i o n . T h a t i s , t h e o n l y s o u r c e o f C 0 was t h a t r e l e a s e d2

THOMSON ET A L . Oil Shale Char Gasification 1
Figure 1. Arrhenius plot for C0 gasification:

2 1.0 atm CO (^J; 0.5 atm
z C02
(%); 0.1 atm C0 (A); 0.016 atm

2 CO (0). 2

d u r i n g m i n e r a l d e c o m p o s i t i o n and, s i n c e t h e h e l i u m sweep gas

r a t e was h i g h , t h i s r e s u l t e d i n v e r y low CO2 p r e s s u r e s .
The s i m i l a r i t y between t h i s e x p r e s s i o n and r a t e e q u a t i o n s
w h i c h have been d e r i v e d f r o m c o a l c h a r g a s i f i c a t i o n d a t a ( 7 j i n t h e
a b s e n c e o f CO i s s t r i k i n g . A l t h o u g h t h e v a l u e o f Ki i s a l m o s t
i d e n t i c a l t o t h e v a l u e r e p o r t e d by Smoot and P r a t h u ) f o r t h e CO2
g a s i f i c a t i o n o f c h a r , t h e v a l u e o f K2 f o r o i l s h a l e c h a r i s t e n
t i m e s g r e a t e r . C o n s e q u e n t l y , even low p r e s s u r e s o f CO w i l l have
a s t r o n g i n h i b i t i n g e f f e c t o n CO2 g a s i f i c a t i o n . D u r i n g t h e d e r i -
v a t i o n o f e q u a t i o n (10) we a l s o a t t e m p t e d t o f i t o u r d a t a t o t h e
e x p r e s s i o n s u g g e s t e d by E r g u n and Menster(]_0) w h i c h i s s i m i l a r t o
e q u a t i o n (10) e x c e p t t h a t K] Pc02 * ^2 C 0
anc P a r e
t a k e n t o be much
g r e a t e r t h a n 1.0. When t h i s was done, a v e r y p o o r f i t was o b -
t a i n e d and i t was c o n c l u d e d t h a t t h e i r e x p r e s s i o n i s n o t a p p r o -
p r i a t e f o r o i l s h a l e c h a r . I t i s a l s o i n t e r e s t i n g t o compare
e q u a t i o n (10) t o t h e e x p r e s s i o n p r o p o s e d b y Burnham, e q u a t i o n (4).
B e c a u s e o f t h e h i g h v a l u e o f K-|, t h e r e a c t i o n r a t e i s c e r t a i n l y
f r a c t i o n a l o r d e r w i t h r e s p e c t t o CO2 and t h i s e x p l a i n s h i s r e a c -
t i o n o r d e r o f 0.2. T a b l e I shows a c o m p a r i s o n o f o u r i n i t i a l
r a t e s w i t h h i s and, a s can be s e e n , e q u a t i o n (4) c o n s i s t e n t l y
p r e d i c t s a r a t e which i s about f o u r times h i g h e r than ours.
TABLE I
RATES OF C0 GASIFICATION
2
4 1
Rate x 10 (sec" )
T PC0 p
2
CO T h i s Work R e f e r e n c e 5 Charcoal
(K) (kPa)
(kPa) E q . (10) Eq. (4) Ref. ( 7 )
975 10 0 0.75 3.1 0.0076

975
975
10
40
1.0
0
0.17
1.0
-
4.1
0.0027
0.0268
1100 10 0 9.8 53 0.19
Note a l s o t h a t even w i t h a low CO p r e s s u r e o f 1 kPa, t h e CO2

g a s i f i c a t i o n r a t e drops by a f a c t o r o f almost f i v e . R e c a l l t h a t
Burnham p r o p o s e d two p a r a l l e l r e a c t i o n s , p r e s u m a b l y due t o two
separate carbon species o f d i f f e r e n t a c t i v i t y . Since carbon
s p e c i e s ' l ' i s more a c t i v e , one e x p l a n a t i o n c o u l d be t h e f a c t t h a t
we l o s t 5-10% o f t h e c a r b o n d u r i n g p r e t r e a t m e n t and t h e m o s t a c -
t i v e c a r b o n w o u l d be e x p e c t e d t o g a s i f y u n d e r t h o s e m i l d c o n d i -
t i o n s . However t h i s i s s u b s t a n t i a l l y l e s s t h a n t h e 7 5 %
a s s i g n e d t o s p e c i e s '1' b y Burnham and i n o u r o p i n i o n t h e d i f -
f e r e n c e s a r e more l i k e l y due t o t h e s t a t i s c a l a n a l y s e s o f r a t e
data which are d i f f i c u l t t o measure. A t higher carbon c o n v e r s i o n s
t h e two r a t e e x p r e s s i o n s a r e c l o s e r due t o t h e l o w e r a c t i v i t y o f
c a r b o n s p e c i e s '2' i n e q u a t i o n (4).

Steam G a s i f i c a t i o n . The r a t e e x p r e s s i o n f o r steam g a s i f i c a -

t i o n i s given i n equation (11).
r k P
H20 . 6 H20 ( n )
C C
+
1 K P 0
3 H 2
+
h \
where
1
k6 = 6.62 exp (-100.7/RT) ( k P a - s e c ) "
1
K3 = 0.20 exp (-17/RT) ( k P a ) '
K4 = 0.15 ( k P a ) " 1
A g a i n t h e r e a c t i o n r a t e i s f i r s t o r d e r w i t h r e s p e c t t o c h a r and
t h e r e m a i n i n g p a r a m e t e r s were d e t e r m i n e d as d e s c r i b e d a b o v e f o r
C 0 g a s i f i c a t i o n . I t i s i n t e r e s t i n g t h a t t h e v a l u e o f Ko i s
2
such t h a t i t i s e f f e c t i v e l y o n e - h a l f o r d e r w i t h r e s p e c t to H 0, 2
c o n s i s t e n t w i t h t h e f i r s t o f t h e two r e a c t i o n r a t e e x p r e s s i o n s
g i v e n by Burnham(j5).
T a b l e I I shows a c o m p a r i s o n o f t h e r a t e s p r e d i c t e d by
e q u a t i o n (11) w i t h t h o s e p r e d i c t e d by e q u a t i o n (5) and w i t h c h a r -
c o a l as r e p o r t e d by Smoot and P r a t h ( 7 ) . A g a i n Burnham*s r a t e
expression p r e d i c t s higher rates but, i n t h i s case, the d i s c r e -
pancy i s a l m o s t a f a c t o r o f 20 a t t h e h i g h e r t e m p e r a t u r e . T h e
l a t t e r i s due t o t h e v e r y h i g h a c t i v a t i o n e n e r g i e s r e p o r t e d b y
Burnham w h i c h a r e 30-80% h i g h e r t h a n o u r v a l u e s . One p o s s i b l e
e x p l a n a t i o n i s t h a t Burnham b a s e d h i s r a t e e x p r e s s i o n on t h e r a t e
TABLE I I
RATES OF STEAM GASIFICATION
4 - 1
Rate x 1 0 ( s e c )
T P^Q PH T h i s work Reference 6 Char
(K) (kPa) (k?a) Eq. (11) Eq. (5) Ref. (7)
975 30 0 4.64 15.8 0.75

975 30 10 2.50 - 0.21
975 70 0 5.6 19.5 1.33
1150 30 0 26.5 474 53.3
o f H p r o d u c t i o n i n t h e make-gas. As m e n t i o n e d e a r l i e r , . t h e
2
w a t e r gas s h i f t r e a c t i o n i s v e r y f a s t o v e r r e t o r t e d o i l s h a l e and
t h i s w o u l d r e s u l t i n a d d i t i o n a l H t h a n t h a t p r o d u c e d by t h e
2
s t e a m - c h a r r e a c t i o n . What i s more, t h e C 0 - c h a r r e a c t i o n w o u l d
2
a l s o t a k e p l a c e u n d e r t h e s e c o n d i t i o n s and, i n t h e n o n - i s o t h e r m a l
e x p e r i m e n t s employed by Burnham, i t i s d i f f i c u l t t o d i s t i n g u i s h
between them. E q u a t i o n (11) o n t h e o t h e r hand, i s b a s e d s o l e l y
on i n i t i a l r a t e d a t a so t h a t i t a p p l i e s s t r i c t l y t o t h e s t e a m - c h a r
r e a c t i o n . In c o m p a r i n g o u r r e s u l t s t o t h o s e f o r t h e steam
g a s i f i c a t i o n o f c h a r c o a l , i t i s seen t h a t t h e steam g a s i f i c a t i o n

r a t e s f o r o i l s h a l e a r e 5-10 t i m e s h i g h e r a t t h e l o w e r t e m p e r a t u r e
b u t l o w e r b y a f a c t o r o f two a t t h e h i g h e r t e m p e r a t u r e . It is
i n t e r e s t i n g t h a t t h i s i s q u i t e d i f f e r e n t f r o m CO2 g a s i f i c a t i o n
where t h e r a t e s f o r o i l s h a l e c h a r were a l m o s t two o r d e r o f
magnitudes h i g h e r .
R e c a l l t h a t e q u a t i o n (11) i s b a s e d o n d a t a c o l l e c t e d f o r
steam g a s i f i c a t i o n i n t h e p r e s e n c e o f CaO; i . e . , a t h e r m a l l y
d e c a r b o n a t e d s h a l e sample. F i g u r e 2 i s a f i r s t o r d e r p l o t which
compares t h e r a t e o f c h a r c o n s u m p t i o n f o r samples w h i c h were
l e a c h e d i n a c i d w i t h a t h e r m a l l y decarbonated sample under t h e
same c o n d i t i o n s . T h e f a c t t h a t t h e l e a c h e d samples have s i g n i f i -
c a n t l y l o w e r r a t e s i s a p p a r e n t l y d u e t o changes i n d u c e d i n t h e
mineral matrix as a r e s u l t o f t h e acid leaching. This i s b e t t e r
u n d e r s t o o d when t h e r e s u l t s f o r g a s i f i c a t i o n i n t h e p r e s e n c e o f
CO2-H0O m i x t u r e s a r e a n a l y z e d . F i g u r e s 3 a n d 4 show t h e p r e -
d i c t e d a n d e x p e r i m e n t a l r e s u l t s f o r two e x p e r i m e n t s c o n d u c t e d
u n d e r s i m i l a r g a s c o m p o s i t i o n s b u t a t two d i f f e r e n t t e m p e r a t u r e s .
The r e s u l t s shown i n F i g u r e 3 a r e a t a t e m p e r a t u r e o f 980K a n d ,
a t t h i s t e m p e r a t u r e , a CO2 p r e s s u r e o f 10 k P a i s s u f f i c i e n t t o
prevent c a l c i t e decomposition. The p r e d i c t e d r a t e o f char con-
s u m p t i o n i s b a s e d o n a d y n a m i c m a t h e m a t i c a l model w h i c h i n c o r -
p o r a t e s e q u a t i o n s (10) a n d ( 1 1 ) . N o t e t h a t t h e a c t u a l r a t e i s
much s l o w e r t h a n t h a t p r e d i c t e d by e q u a t i o n s (10) a n d ( 1 1 ) . T h e
d a t a shown i n F i g u r e 4 were a l s o o b t a i n e d a t PCO2 = 10 kPa b u t a t
a h i g h e r t e m p e r a t u r e o f 1040K. I n t h i s c a s e a p p r o x i m a t e l y o n e -
h a d
h a l f o f t h e a v a i l a b l e CaC03 decomposed t o CaO and, a s c a n b e
seen, t h e p r e d i c t e d char consumption r a t e s a r e c l o s e t o those
measured. Given these r e s u l t s and t h e lower r a t e s measured w i t h
a c i d l e a c h e d s h a l e (where a l l t h e c a l c i u m i s r e m o v e d ) , i t i s
a p p a r e n t t h a t CaO c a t a l y z e s t h e s t e a m - c h a r r e a c t i o n . T h i s o f
c o u r s e i s no s u r p r i s e t o t h o s e f a m i l i a r w i t h t h e l i t e r a t u r e o n
c o a l g a s i f i c a t i o n where a l k a l i n e e a r t h o x i d e s have been known t o
c a t a l y z e t h e s e v e r y same r e a c t i o n s ( 1 1 ] 2 ) .
9
W a t e r Gas S h i f t R e a c t i o n (WGSRjT AS d e s c r i b e d e a r l i e r , t h e
WGSR was s t u d i e d o v e r d e c h a r r e d a n d t o t a l l y s i l i c a t e d s h a l e sam-
p l e s . E a r l y i n t h e c o u r s e o f t h i s phase o f t h e s t u d y we d i s -
covered t h a t t h e i r o n p r e s e n t i n t h e s h a l e c o u l d be r e v e r s i b l y
o x i d i z e d o r reduced, depending on t h e gas c o m p o s i t i o n and tempera-
t u r e . A l t h o u g h t h e WGSR r a t e s were d e t e r m i n e d o n l y f o r samples
w h i c h h a d been s u b j e c t e d t o r e d u c t i o n i n H2, a l i m i t e d number o f
o x i d a t i o n / r e d u c t i o n e x p e r i m e n t s were a l s o c o n d u c t e d . A g a i n , t h e s e
were a c c o m p l i s h e d i n t h e TGA a p p a r a t u s m e n t i o n e d above. T h e
p r o c e d u r e was t o i n i t i a l l y r e d u c e t h e s a m p l e i n f l o w i n g H2
(100 kPa) p r i o r t o e x p o s i n g i t t o a n o x i d i z i n g a t m o s p h e r e (CO2 o r
a i r ) and t o r e c o r d the weight gain as a f u n c t i o n o f time. Prior
to r e d u c t i o n e x p e r i m e n t s t h e s a m p l e was c o m p l e t e l y o x i d i z e d i n
100 k P a a i r a n d t h e n e x p o s e d t o a r e d u c i n g a t m o s p h e r e (H2 o r C O ) .
The o x i d a t i o n / r e d u c t i o n r a t e s were f o u n d t o be f i r s t o r d e r w i t h
respect t o t h e gas c o n c e n t r a t i o n as well as t o t h e q u a n t i t y o f
unconverted iron present i n t h e shale. Table III gives t h e values

THOMSON E T AL. Oil Shale Char Gasification

01 1 I
0 10 20 30
Time - Min
Figure 4. Mixed gasification-CaO present (?h o = 37 kPa, P o = 10 kPa, T =
2 C 2
1040 K) predicted ( ); experimental data (%).

TABLE I I I
FIRST ORDER RATE CONSTANTS FOR THE
OXIDATION/REDUCTION OF IRON
1
Rate C o n s t a n t (sec" )
C0 2 AIR H 2 CO
Oxidation 0.07 3.18

(T = 980K)
Reduction - - 0.22 0.20

(T = 1040K)
o f t h e f i r s t o r d e r r a t e c o n s t a n t s o b t a i n e d a t two d i f f e r e n t tem-
p e r a t u r e s f o r o x i d a t i o n i n t h e p r e s e n c e o f 10 kPa o f a i r a n d CO2
and f o r r e d u c t i o n a t 10 kPa o f CO a n d H . As w o u l d be e x p e c t e d ,2
t h e r a t e o f o x i d a t i o n i n a i r i s more t h a n an o r d e r o f m a g n i t u d e
h i g h e r t h a n o x i d a t i o n i n CO2 whereas t h e CO a n d H r e d u c t i o n r a t e s 2
are comparable.
E q u a t i o n ( 1 2 ) i s a n e x p r e s s i o n f o r t h e WGSR r a t e . T h e d a t a
were p u r p o s e l y f i t t o t h e e l e m e n t a r y r e a c t i o n r a t e e x p r e s s i o n
g i v e n i n b r a c k e t s s o t h a t t h e r a t e w o u l d go t o z e r o a s e q u i l i b r i -
um was a p p r o a c h e d .
k
7 t C0 H 0 " V K E C 0
R P
2
P
2 V
" W G S R
1 h + P
C0 2
+
h R
H 0
2
3 2
k y = 4.16 X 1 0 ' e x p [ - 8 2 . 1 / R T ] moles/g-kPa -sec
K 5 = .0278 ( k P a ) " 1
K6 = .0492 ( k P a ) - 1
I t s h o u l d be n o t e d t h a t e q u a t i o n (12) p r e d i c t s a n i n h i b i t o r y
e f f e c t o f C 0 on t h e r e a c t i o n r a t e . However j u s t t h e o p p o s i t e
2
was o b s e r v e d f o r C 0 p r e s s u r e s l e s s t h a n 10 kPa a n d c o n s e q u e n t l y
2
>
e q u a t i o n (12) i s o n l y v a l i d f o r Pco? 10 kPa
C a t a l y t i c E f f e c t s . A l t h o u g h f t i s y e t t o b e p r o v e n , we b e -
l i e v e t h a t t h e anomalous b e h a v i o r o f C 0 on t h e WGSR r a t e i s d u e 2
to i t s i n f l u e n c e on t h e o x i d a t i o n s t a t e o f i r o n . In f a c t d u r i n g
t h e WGSR r a t e e x p e r i m e n t s we o b s e r v e d c h a n g e s i n t h e mass o f t h e
s h a l e sample a s t h e g a s c o m p o s i t i o n was v a r i e d . C o n s e q u e n t l y a
c o m p l e t e u n d e r s t a n d i n g o f t h e WGSR i s d e p e n d e n t o n a q u a n t i t a t i v e
knowledge o f how t h e c a t a l y t i c a c t i v i t y o f i r o n v a r i e s w i t h i t s
o x i d a t i o n s t a t e . Once t h i s i s known, r e a c t i o n r a t e e x p r e s s i o n s
f o r t h e o x i d a t i o n / r e d u c t i o n o f i r o n c o u l d be c o m b i n e d w i t h WGSR
r a t e e x p r e s s i o n s t o p r o v i d e a more a c c u r a t e p r e d i c t i o n o f t h e
make-gas c o m p o s i t i o n s .

The r o l e o f CaO a s a c a t a l y s t f o r t h e s t e a m - c h a r r e a c t i o n c a n
be i n f e r r e d f r o m t h e r e s u l t s o b t a i n e d d u r i n g m i x e d CO2-H2O g a s i -
f i c a t i o n ( f i g u r e s 3 a n d 4 ) . I n many r e s p e c t s i t i s d e s i r a b l e t o
p r e v e n t t h e d e c o m p o s i t i o n o f CaC03 t o CaO b e c a u s e o f t h e h i g h
endothermic heats o f r e a c t i o n a s s o c i a t e d with t h i s r e a c t i o n .
However, a s we have shown, t h e steam g a s i f i c a t i o n o f o i l s h a l e
c h a r i s a b o u t t e n t i m e s s l o w e r when CaO i s n o t p r e s e n t . A b e t t e r
e v a l u a t i o n o f t h e i m p o r t a n c e o f CaO r e q u i r e s a knowledge o f t h e
d e p e n d e n c e o f t h e r e a c t i o n r a t e on t h e q u a n t i t y o f CaO p r e s e n t .
Nomenclature
C c - char c o n c e n t r a t i o n , moles/g s h a l e
k - rate constants
K - a d s o r p t i o n c o n s t a n t s , kPa"'
K[: - e q u i l i b r i u m c o n s t a n t
Pi - p a r t i a l p r e s s u r e o f i , kPa
r - r e a c t i o n r a t e s , moles char r e a c t e d / s - g s h a l e
R - g a s c o n s t a n t , 0.008324 k j o u l e s / m o l e - ° K
T - t e m p e r a t u r e , °K
Abstract
The kinetics of oil shale char gasification have been studied
for Colorado oil shale from the Parachute Creek member. Reaction
rate expressions similar to those previously reported for coal
char were obtained f o r the H O-char, CO char and water gas s h i f t
2 2-
reactions. Evidence is presented to suggest that CaO, a product

of mineral decomposition, catalyzes the H O-char reaction and 2
that indigeneous iron catalyzes the water gas s h i f t reaction.

The l a t t e r reaction proceeds rapidly so that the make-gas con-
s i s t s primarily of H and CO .2 2
Literature Cited
1. Dockter, L., paper presented at 68th Annual Meeting of AIChE,
Los Angeles, Ca., November 20, 1975.
2. Soni, Y.; Thomson, W. J., I&EC PROC. DES. & DEV., 1979, 18,
661.
3. OIL & GAS JOURNAL, June 17, 1974, p.26.
4. Burnham, A. K., FUEL, 1979, 58, 285.
5. Burnham, A. K., FUEL, 1979, 58, 713.
6. Burnham, A. K., FUEL, 1979, 58, 719.
7. Smoot, L . K.; Prath, D. T., ''Pulverized Coal Combustion and
Gasification," PLENUM PRESS, N . Y . , 1979.
8. Soni, Y.; Thomson, W. J., "PROC 11TH OIL SHALE SYMP," Colo-
rado State Univ. Press, Golden, C O . , 1978.
9. Thomson, W. J., paper presented at National Meeting of AIChE,
Houston, T X . , March 30, 1979.

8. THOMSON ET AL. Oil Shale Char Gasification 127
10. Ergun, S.; Menster, M., in "Chemistry and Physics of Carbon,"

Vol. 1, (ed. P. L. Walker, Jr.), Marcel Dekker, N.Y., 1965,
p.203.
11. Lewis, W. K.; Gilliland, E. R.; Hipkin, H . , IND & ENG CHEM,
1953, 45, 1697.
12. Eakman, J . M.; Wesselhoft, J . J.; Dunkleman, J. J.;
Vadovic, C. J., paper No. 63d, presented at 72nd Annual
Meeting of AIChE, San Francisco, November 1979.

9
A Comparison of Asphaltenes from Naturally
Occurring Shale Bitumen and Retorted Shale Oils:
The Influence of Temperature on Asphaltene
Structure
FENG FANG SHUE and TEH FU YEN
School of Engineering, University of Southern California, Los Angeles, CA 90007
The majority of the organic material in oil shale is known as

kerogen (organic solvent-insoluble fraction). Bitumen (organic

solvent-soluble fraction) generally comprises only a small part of
the total organic matter in oil shale. During retorting of the
oil shale, kerogen and bitumen undergo thermal decomposition to
oil, gas and carbon residue. According to a number of investiga-
tors (1,2,3), the mechanism for thermal cracking of oil shale is
by decomposition of kerogen to bitumen and subsequently decomposi-
tion of bitumen to oil, gas and coke. Since bitumen is the inter-
mediate formed from kerogen during thermal cracking, it may be
accepted as representative of the natural-occuring organic matter
in oil shale.
According to the solvent fractionation scheme for the fossil
fuel products, asphaltene is defined as the pentane-insoluble and
benzene-soluble fraction. The role of asphaltene is significant
(4). Asphaltene is suggested to be the "transitional stage" in
the conversion of fossil to oil (5). Therefore the structures of
asphaltene fractions produced at various temperatures may be use-
ful indicators of the severity of temperature effects during pro-
cessing. In this research, the asphaltene fractions produced
from natural-occuring shale bitumen and shale oils retorted at
425 and 500°C were compared to investigate structural changes
during thermal cracking. Due to the complexity of the asphaltene
structure, an approach using the so called "average structural
parameters" (6,7) was used to characterize the gross structural
features. The average structural parameters were calculated
principally from proton and carbon-13 NMR data (8-14). Compari-
sons of the relative values of these structural parameters clear-
ly indicate the effects of thermal treatment on asphaltene struc-
tures.
Experimental
Solvent E x t r a c t i o n . A sample o f the Green R i v e r o i l shale

from A n v i l P o i n t s , Colorado was crushed to 8-20 mesh s i z e p r i o r
0097-6156/81/0163-0129$05.00/0

to s o l v e n t e x t r a c t i o n or r e t o r t i n g . Bitumen was e x t r a c t e d from

the shale by exhaustive Soxhlet e x t r a c t i o n with 10% methanol i n
benzene f o r 72 h r s . T o t a l bitumen y i e l d was 2.1% by weight.
Shale R e t o r t i n g . The r e t o r t chamber was a c y l i n d r i c a l quartz

column, 47 mm i n diameter and 300 mm i n length with a screen o f
20 mesh s i z e welded to the bottom. Heat was t r a n s f e r e d to the
shale through the quartz w a l l wrapped with two h e a t i n g wires con-
nected t o a transformer. A s t a i n l e s s s t e e l sheathed chromel-alu-
mel (type k) thermocouple was i n s e r t e d i n the center o f the r e -
t o r t chamber. The temperature was r a i s e d r a p i d l y to 425°C i n one
experiment and to 500°C i n another, and maintained there f o r three
hours. A i r entered through the top o f the chamber at a flow r a t e
o f 1 cc/sec and moved downward together with the product o i l
through the c o o l i n g column. The product o i l was c o l l e c t e d i n t o

the r e c e i v e r and then seaprated from the water phase. The y i e l d s
o f shale o i l s were 10.0% at 425°C and 12.5% at 500°C. Gas and
coke were not analyzed.
I s o l a t i o n o f Asphaltene. Asphaltenes were i s o l a t e d by pre-

c i p t a t i n g with a 2 0 - f o l d volume o f n-pentane. The o i l / r e s i n
f r a c t i o n was separated from the p r e c i p t a t e by f i l t r a t i o n through
the thimble f o l l o w e d by Soxhlet e x t r a c t i o n with n-pentane. The
asphaltene f r a c t i o n was obtained by Soxhlet e x t r a c t i o n o f the
residue with benzene. In the f o l l o w i n g t e x t , the three asphal-
tenes w i l l be abbreviated as B i t u , R and R ^ Q Q r e p r e s e n t i n g
4 2 5
bitumen asphaltene and asphaltenes d e r i v e d from shale o i l s r e -

t o r t e d at 425 and 500°C r e s p e c t i v e l y .
P h y s i c a l and Chemical A n a l y s i s . Elemental analyses were done

by Elek M i c r o a n a l y t i c a l L a b o r a t o r i e s , Torrance, C a l i f o r n i a . Mo-
l e c u l a r weights were determined on a Mechrolab Model 301A Vapor
Pressure Osmometer using THF as the s o l v e n t at 40°C. IR s p e c t r a
were recorded at a c o n c e n t r a t i o n o f 25 mg/ml i n CH C1 u s i n g 0.5
2
mm NaCl c e l l s on a Beckman Acculab 6 instrument. Proton and

carbon-13 NMR s p e c t r a were obtained on a V a r i a n XL-100 spectro-
meter o p e r a t i n g at 100.1 MHz f o r proton o r 25.2 MHz f o r carbon.
Proton NMR was measured i n C D C 1 ( c e n t r a l residue peak at 5.3
2 2
ppm). Carbon-13 NMR was measured i n CDCl^ ( c e n t r a l peak at 77.1

ppm). A sample o f asphaltene (0.5 g) was d i s s o l v e d i n 2.5 ml o f
CDC1_ with 35 mg o f C r ( a c a c ) added to i t .
3 To o b t a i n r e l i a b l e
q u a n t i t a t i v e r e s u l t s , a delay time o f 4 sec a f t e r each 35° p u l s e
and 0.68 sec a c q u i s i t i o n time was used i n the gated decoupling
sequence. A l l chemical s h i f t s were reported i n ppm downfield
from TMS.
F r a c t i o n a t i o n o f the three samples a f f o r d e d the asphaltene

f r a c t i o n s c o n s t i t u t i n g 7.3%, 0.39% and 0.74% by weight f o r the
shale bitumen, shale o i l s r e t o r t e d at 425 and 500°C r e s p e c t i v e l y .

9. SHUE A N D Y E N A Comparison of Asphaltenes 131
Elemental Composition. Elemental a n a l y s i s data f o r the three

asphaltene samples are presented i n Table I.
Table I . Elemental Compositions of Green R i v e r Asphaltenes
Bitu R
R
425 500
Wt. % C 74.53 76.50 78.22
wt. % H 8.86 7.97 7.02

wt. % N 2.71 4.49 5.03
wt. % S 1.80 1.37 1.08
wt. % o a
10.32 8.01 7.71
wt. % Ash 1.78 1.59 0.94
H/C 1.42 1.25 1.08
N/C 0.031 0.050 0.055
s/c 0.009 0.0067 0.0052
0/C 0.104 0.079 0.074
3
Molecular
1100 660 620
a by d i f f e r e n c e
b by VPO i n THF
The r e s u l t s o f the elemental a n a l y s i s show that asphaltenes

d e r i v e d from r e t o r t e d shale o i l s have s m a l l e r values o f H/C r a t i o
and s m a l l e r oxygen and s u l f u r contents, but g r e a t e r n i t r o g e n con-
tent than that d e r i v e d from shale bitumen.
I n f r a r e d Data. I n f r a r e d s p e c t r a o f the three asphaltene sam-

p l e s are presented i n F i g u r e 1. A number o f w e l l d e f i n e d ban^s
were used f o r comparison: 0-H s t r e c h i n g o f phenols (3600 cm" ) ,
N-H s t r e c h i n g o f p y r r o l e s (3460 cm" ) , C-H s t r e c h i n g o f a l i p h a t i c
1
a l k y l groups (2925 and 2860 cm" ) , C=0 s t r e c h i n g o f carbonyl com^

pounds (1800 - 1650 cm" ) , C-C s t r e c h i n g o f aromatics («1600 cm" )
and C-0 s t r e c h i n g o f aromatic ethers and phenols (1320 - 1200

4000 5000 2000 1800 1600 1400 1200 1000

- 1
Wavenumber, c m
4000 3000 2000 1800 1600 1400 1200 1000

Wavenumber, cm"**
4000 2000 1800 1600 1400 1200 1000
Wavenumber, cnr*
Figure 1. IR spectra of shale oil asphaltene

R a n c R a v es t r
cm" ) . A2S * 500 ^ ° n g e r absorption i n t e n s i t i e s f o r
p h e n o l i c 0-H and p y r r o l i c N-H groups and C-0 s t r e c h i n g o f aromatic
ethers and phenols. As the p r o c e s s i n g temperature i n c r e a s e s , the
a l i p h a t i c C-H absorptions decrease and the aromatic C-C a b s o r p t i o n
i n c r e a s e s . Band shapes f o r the carbonyl s t r e c h i n g r e g i o n o f the
three samples a l s o show remarkable d i f f e r e n c e s . B i t u has very
strong carbanyl absorption at 1700 cm" . F o r a
d 5QQ>
n R
C
"
A R
bonyl absorptions were s h i f t e d toward lower f r e q u e n c i e s . Since

i t i s w e l l known that e i t h e r hydrogen bonding o r conjugation with
an o l e f i n i c o r phenyl group causes a s h i f t o f the carbonyl ab-
s o r p t i o n a t lower f r e q u e n c i e s , the r e s u l t seems t o i n d i c a t e a r e -
l a t i v e l y g r e a t e r p r o p o r t i o n o f hydorgen-bonded and/or conjugated
carbonyl groups f o r R and R Q Q than f o r B i t u .
4 2 5 5
a r e
*H NMR Data. Proton NMR s p e c t r a o f B i t u , R425 and R500
shown i n Figures 2-4. I f c o n t r i b u t i o n s from a c i d i c protons ( i . e .
0-H and N-H, such protons show very broad chemical s h i f t ranges
(15)) are neglected, the s p e c t r a can be d i v i d e d i n t o d i f f e r e n t
proton groups based upon chemical s h i f t ranges. Proton type
d i s t r i b u t i o n s are d e f i n e d as f o l l o w s : H^(9.0-6.0 ppm), protons on
aromatic r i n g s ; H (4.5-1.9 ppm), alpha a l k y l protons; Hg(1.9-1.0
a
ppm), beta a l k y l protons p l u s methine and methylene protons i n the

gamma p o s i t i o n s o r f u r t h e r from aromatic r i n g s ; Hy(1.0-0.4 ppm),
methyl protons i n the gamma p o s i t i o n s o r f u r t h e r from aromatic
r i n g s . The i n t e g r a t e d proton i n t e n s i t i e s f o r each s p e c i f i c group
were obtained d i r e c t l y from i n t e g r a t i o n curves. Normalized proton
type d i s t r i b u t i o n s are given i n Table I I . A s p e c i f i c group o f
protons with chemical s h i f t s i n the range o f 4.5-3.3 ppm, assigned
as protons on carbons alpha t o two aromatic r i n g s , were observed
i n the NMR s p e c t r a o f B i t u and R425- The r e s u l t seems t o i n d i c a t e
that diphenyl methane type o f s t r u c t u r e remains s t a b l e at 425°C
but i s cleaved a t 500°C.
Carbon-13 NMR Data. Carbon-13 NMR data were f r a c t i o n a t e d i n t o

groups based upon chemical s h i f t ranges: carbonyl carbons (220-
168 ppm); aromatic carbons j o i n e d t o oxygens, i . e . , aromatic eth-
ers and phenols (168-148 ppm); aromatic carbons not j o i n e d t o
oxygens (148-100 ppm) and a l i p h a t i c carbons (60-9 ppm). Aromati-
c i t y was c a l c u l a t e d as f r a c t i o n o f aromatic carbons (168-100 ppm)
over t o t a l carbons. For s i m p l i c i t y , carbons a s s o c i a t e d with
nitrogens were discounted i n the above scheme due t o the r e l a t i -
v e l y small percentage o f n i t r o g e n present i n the samples. Carbon
group d i s t r i b u t i o n s and a r o m a t i c i t i e s o f three asphaltene samples
are compared i n Table I I I . We have observed very poor agreement
between the oxygen contents determined by u l t i m a t e a n a l y s i s (see
1 3
Table I) and by C NMR (see Table III) f o r a l l three samples.
For B i t u , 0/C = 0.104 by elemental a n a l y s i s but 0/C =0.024-0.037
by 13Q NMR. We think q u a n t i t a t i v e a n a l y s i s o f carbonyl carbons
by !3c ^MR ^ d i f f i c u l t f o r two reasons: 1) carbonyl carbons gene-
s
r a l l y have very long r e l a x a t i o n times (16) and are q u a n t i t a t i v e l y

underestimated even under current c o n d i t i o n s ; 2) the disappearance
of a large number o f carbonyl absorptions i n the n o i s e i s accen-

9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
Chemical Shift,ppm
Figure 2. H-l NMR spectrum of asphaltene from shale bitumen
9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
Chemical Shift,ppm
Figure 3. H-l NMR spectrum of asphaltene from shale oil retorted at 425°C
9.0 8.0 6.0 5.0 4.0 3.0 2.0 0.0

Chemical Shift,pp:s
Figure 4. H-l NMR spectrum of asphaltene from shale oil retorted at 500°C
( % and 13c NMR are being used only to c h a r a c t e r i z e the

hydrocarbon p o r t i o n and, thus, the c o n t r i b u t i o n from
heteroatom p o r t i o n s of the molecule have been minimized.)

SHUE AND Y E N A Comparison of Asphaltenes
Table I I . F r a c t i o n a l Proton D i s t r i b u t i o n s o f Green R i v e r

Asphaltenes by *H NMR
Proton Type Bitu R

425
R
500
H A (9.0-6.0 ppm) 0.046 0.145 0.179
H a (4.5-1.9 ppm) 0.204 0.337 0.402
Hg (1.9-1.0 ppm) 0.525 0.389 0.330
Hy (1.0-0.4 ppm) 0.225 0.129 0.089
Table I I I . Percentage Carbon Group D i s t r i b u t i o n s o f

Green R i v e r Asphaltenes by l^C NMR
Carbon Type Bitu R 4 2 5 R 5 Q 0
carbonyl carbons(220-168 ppm) 1.3
aromatic carbons j o i n e d t o
oxygens(168-148 ppm) 1.1 2.4 2.8
aromatic carbons not j o i n e d
to oxygens(148-100 ppm) 23.0 48.7 56.8
a l i p h a t i c carbons(60-9 ppm) 74.6 49.9 40.4
Aromaticity 0.24 0.51 0.60

tuated due to the i n e f f i c i e n t number o f scans and the broader

range o f carbonyl resonance f o r a sample c o n t a i n i n g many compo-
nents. A conversion o f C=0 f u n c t i o n s i n t o CHOH o r CH groups by 2
r e d u c t i o n would b e n e f i t t h e i r d e t e c t i o n by l^C NMR. Indeed we

have observed new absorption i n the a l i p h a t i c e t h e r and a l c o h o l
region (75-60 ppm) and i n c r e a s e d a b s o r p t i o n i n the a l i p h a t i c
1 3
amine region (60-50 ppm) i n the C NMR spectrum o f Green R i v e r
Bitumen asphaltene reduced by LiAlH4(17). Reductions o f carbo-
x y l i c acids and ketones to a l c o h o l s , e s t e r s to ethers and amides
to amines by L i A l H are w e l l known r e a c t i o n s (18). Further e v i -
4
dence f o r the presence o f carbonyl f u n c t i o n s i"n~"these samples was

discussed e a r l i e r from i n f r a r e d data.
S t r u c t u r a l Parameters. Average s t r u c t u r a l parameters i n c l u d e :

a r o m a t i c i t y ( f ) , degree o f s u b s t i t u t i o n o f the aromatic s h e e t ( a ) ,

a
number o f carbon atoms per a l k y l s u b s t i t u e n t (n), r a t i o o f p e r i -

pheral carbons p e r aromatic sheet to t o t a l aromatic carbons
(Haru/Car) and a l i p h a t i c H/C r a t i o can be c a l c u l a t e d according to
Eq. ( D - ( 5 )
C/H-QWX + Ho/Y + H /3)

y
Hyx
a
a = — ( 2 )
H. + H /X
A ct
n- Hq/X + H /Y 6 + Hy/3 m
H /X
a
+H /X H A
Haru A a ^
C a r
C/H - (H /X + H /Y a 3 + H /3)
y
1 _ H
H H A
aliphatic — g — ratio = -g- x ^ F (5)
a
where X and Y are the assumed atomic H/C r a t i o s f o r H and Hg a
f r a c t i o n s . Assuming X=Y, these values were chosen to give f a
(aromaticity) values c o n s i s t e n t with those measured d i r e c t l y by

C NMR.
l 3
The c a l c u l a t e d values o f X o r Y were 1 . 6 0 f o r B i t u ,
2.08 f o r R 4 2 5 and 2 . 1 5 f o r R Q Q r e s p e c t i v e l y . C a l c u l a t e d average
5
s t r u c t u r a l parameters are presented i n Table IV. These s t r u c t u r a l

parameters h i g h l i g h t the d i f f e r e n c e s among the three asphaltene
samples. As the temperature o f treatment i n c r e a s e s , the aromati-
c i t y a l s o increases but average a l k y l chain length, degree o f sub-
s t i t u t i o n and degree o f condensation o f the aromatic system de-
crease. The o v e r a l l a l i p h a t i c H/C r a t i o f o r B i t u was 1 . 8 , imply-
i n g a s i g n i f i c a n t amount of condensed naphthenic r i n g s t r u c t u r e .
The a l i p h a t i c H/C r a t i o f o r R 4 2 5 o r R Q Q was above 2 , implying 5
the growing number o f methyl groups upon h e a t i n g . Although

assumptions were made i n c a l c u l a t i o n s o f these s t r u c t u r a l parame-
t e r s , the trend o f changes i n s t r u c t u r e with temperature was
clearly indicated.

Table IV. Average S t r u c t u r a l Parameters o f

Green R i v e r Asphaltenes
S t r u t u r a l Parameter Bitu R
R
425 500
f 0,.24 0,.51 0.60

a
o 0..73 0,.53 0.51
n 4..16 2,.42 1.98
Haru/Car 0,.99 0 .75 0.66

a l i p h a t i c H/C r a t i o 1,.80 2 .18 2.22
Summary
A s t r u c t u r a l comparison o f asphaltenes d e r i v e d from shale

bitumen and r e t o r t e d shale o i l has been undertaken i n order t o
i n v e s t i g a t e s t r u c t u r a l changes during thermal c r a c k i n g . The
r e s u l t s o f elemental a n a l y s i s i n d i c a t e that asphaltene d e r i v e d
from r e t o r t e d s h a l e o i l has lower H/C r a t i o and l e s s oxygen and
s u l f u r contents, but more n i t r o g e n content than that d e r i v e d
from shale bitumen. Heteroatom f u n c t i o n a l groups have a l s o been
i n v e s t i g a t e d f o r these asphaltenes. The r e t o r t e d shale o i l
asphaltene has more 0-H and N-H f u n c t i o n a l groups as i n d i c a t e d
i n the IR s p e c t r a . R e t o r t i n g processes a l s o i n c r e a s e the aromati-
c i t y , decrease the degrees o f s u b s t i t u t i o n and condensation o f
the aromatic sheet and shorten the chain length o f the a l k y l sub-
stituent.
Acknowledgement
This work has supported by U.S. Department o f Energy, O f f i c e

o f Environment under Contract No. 79EV10017,000.
Literature Cited
1. Allred, V.D., Quart. Colorado School of Mines, 1967, 62 (3),
91.
2. Hubbard, A.B. and Robinson, W.E., "A Thermal Decomposition
Study of Colorado Oil Shale," U.S. Bureau of Mines, 1950, R.I.
4744.
3. Wen, C.S. and Yen, T.F., Chem. Eng. Sci., 1977, 32, 346.

4. Yen, T.F., "The Role of Asphaltene in Heavy Crudes and Tar

Sands," Proceeding of the First International Conference on
the Future of Heavy Crude and Tar Sands, paper 54, UNITAR,
1979.
5. Weller, S., Pelipetz, M.G. and Friedman, S., Ind. Eng. Chem.
1951, 43, 1572.
6. Williams, R.B., Sym. on Composition of Petroleum Oils, Deter-
mination and evaluation, ASTM Spec. Tech. Publ., 1958, 224,
168.
7. Brown, J.K. and Ladner, W.R., Fuel, 1960, 39, 87.
8. Bartle, K. D., Martin, T.G. and Williams, D. F., Fuel 1975,

54, 226.
9. Cantor, D. M., Anal. Chem., 1978, 50, 1185.
10. Wooton, D. L., Coleman, W. M., Taylor, L. T. and Dom, H. C.,
Fuel, 1978, 57, 17.
11. Dereppe, J. M., Moreaux, C. and Castex, H. Fuel, 1978, 57,
435.
12. Bartle, K. D., Ladner, W. R., Martin, T. G., Snape, C. E. and
Williams, D. F., Fuel, 1979, 58, 413.
13. Ladner, W. R., Martin, T. F. and Snape, C. E., ACS Div. Fuel
Chem. Preprints, 1980, 25(4), 67.
14. Dickinson, E. M., Fuel, 1980, 59, 290.
15. Jackman, L. M. and Sternhell, S., "Applications of Nuclear
Magnetic Resonance Spectroscopy in Organic Chemistry,"
Pergamon Press, 1969, p.215.
16. Levy, G. C. and Nelson, G. L., "Carbon-13 Nuclear Magnetic
Resonance for Organic Chemists", Wiley-Interscience, 1972.
17. Shue, F. F. and Yen, T. F., unpublished work.
18. House, H. O., "Mordern Synthetic Reactions", W. A. Benjamin,
Inc., 1972.

10
Beneficiation of Green River O i l Shale by
Density Methods
OLAF A. LARSON
Gulf Research & Development Company, Pittsburgh, PA 15230
C. W. SCHULTZ and ELLERY L. MICHAELS
Institute of Mineral Research, Michigan Technological University, Houghton, MI 49931
Green River oil shale, found in Colorado, Utah, and Wyoming

is an extremely complex and challenging resource. The C-a tract
in Colorado has been Gulf's main interest in oil shale since
about 1974. Initial plans called for the use of an open pit
mine with conventional surface retorting.
From a process point of view, the most important property
of much of the oil shale throughout the Green River formation is
its low organic content. For example, the integral average of
shale on the C-a tract, measured from the top of the Mahogany
Zone through the Blue Marker (over a 1,000-foot interval) is
about 23 GPT. This corresponds to an organic concentration of
14.7% by weight.
Retorting of shale is the most commonly considered method
for oil recovery from the rock. Despite the apparent simplicity
of retorting, it is a complex process. This complexity is due
to the lean nature of the ore, the requirement to add heat at
high temperature, and the chemical and physical changes which
take place in retorting.
There are two principal reasons for the beneficiation of
oil shale. First, a reduction in solids handling intensity of
lean shale movement and retorting may be possible. Secondly,
beneficiation to higher concentration levels might allow the
substitution of alternate technology for retorting. Overall,
the incentive is to reduce costs and improve thermal efficiency
of the conventional mining and process routes.
A survey of the l i t e r a t u r e indicated that little
information had been published on o i l shale b e n e f i c i a t i o n .
Dismant (1) reviewed the p o t e n t i a l f o r various b e n e f i c i a t i o n
methods. A density method has been used i n the i n d u s t r y , mainly
as an a n a l y t i c a l t o o l , to prepare o r g a n i c - r i c h concentrates
(2). Most r e c e n t l y , Fahlstrom (3) has described f i n e - g r i n d i n g
and f r o t h f l o t a t i o n on Green River and Kvarntorp (Sweden) o i l
shales. A f t e r reviewing the problem, we decided to focus on
0097-6156/81/0163-0139$05.00/0

what kinds of separation are possible using coarse size

fractions. Avoidance of f i n e g r i n d i n g and h y d r o - m e t a l l u r g i c a l
c i r c u i t s seemed most d e s i r a b l e to reduce complexity and c o s t .
Access to shale at the C-a t r a c t was not p o s s i b l e when t h i s
study was s t a r t e d . The Mahogany Zone shale from the A n v i l
Points Mine was used i n t h i s study.
Experimental
Shale Sampling. O i l shale used i n t h i s work was from the

Mahogany Zone of the Green R i v e r formation. The Bureau of Mines
room-and-pillar mine at A n v i l Points has access to the Mahogany
Zone shale i n the U.S. Naval O i l Shale Reserve. Figure 1 shows
a (72-foot) i n t e r v a l of shale which i s mined at A n v i l P o i n t s .
The histogram p l o t of a t y p i c a l core i s adapted from the Bureau

of Mines report ( 4 ) . The average F i s c h e r Assays of the various
beds of shale have been noted i n Figure 1. A d d i t i o n a l reference
can be made to the Bureau of Mines' reports f o r c h a r a c t e r i s t i c s
of the mine ( 5 ) . The mineable beds l a b e l l e d A through J
correspond to the o r i g i n a l designations of the Bureau of Mines.
During our sampling p e r i o d , shale was being mined mainly
from beds A through F as a part of the Paraho demonstration
program. The normal f l o o r l e v e l i n the mine i s at -20 f e e t
below the Mahogany marker. The r e l a t i v e l y lean shale i n Beds A,
C, and D r e s u l t s i n a low grade of shale as run-of-mine
material. The Mahogany marker itself is a thin bed
approximately 4 to 6 inches i n thickness, which contains l i t t l e
organic matter. The i n t e g r a t i o n of a l l of the zones from A
through F give a shale averaging about 26 GPT. As w i l l be shown
l a t e r , our assay r e s u l t s were c o n s i s t e n t with t h i s value, which
v e r i f i e d that the mine b l a s t i n g and blending procedure was i n
good c o n t r o l .
A second o b j e c t i v e of sampling at the A n v i l Points mine was
to o b t a i n a r e p r e s e n t a t i v e sample of a f u l l 60-foot i n t e r v a l .
The zone s e l e c t e d was from 20 feet above the Mahogany marker to
40 feet below. This procedure gave us samples of shale from
beds G and H, which show a h i g h l y c y I l e a l grade change with
depth i n the core a n a l y s i s histograms.
Every e f f o r t was taken to assure uniform and accurate
sampling i n the mine. C a r e f u l measuring was done by d r i v i n g a
s t e e l p i n i n t o the face at the upper edge of the Mahogany
marker. V e r t i c a l i n t e r v a l s were measured from the reference
p o i n t s and marked with spray p a i n t . Samples were broken from
the face using a hammer and rock c h i s e l . Ten to twelve pounds
of sample were taken from each one-foot i n t e r v a l .
Samples f o r the i n t e r v a l from 2 feet below the Mahogany
marker to 20 feet above the marker were taken from the face of G
(George) d r i f t , approximately 20 feet south of number 11 c r o s s -
cut. The s t r a t a from 2 feet to 20 feet below the Mahogany
marker were taken at the i n t e r s e c t i o n of A (Able) d r i f t and

LARSON E TAL. Green River Oil Shale 141
Figure 1. Core intervals and mineable beds at Anvil Points mine, Rifle, CO

number 11 c r o s s c u t . The only l o c a t i o n i n the mine where the

s t r a t a from 20 feet to 40 feet below the marker i s exposed i s at
the north end of the A d r i f t . At number 11 c r o s s c u t , A d r i f t
d e c l i n e s to -40 feet at the number 13 c r o s s c u t . The samples f o r
the lower zone were taken from t h i s l o c a t i o n .
Sample P r e p a r a t i o n . The mine-run sample was received i n a
nominal crushed form of 3 inch by 1/4 i n c h . An a l i q u o t p o r t i o n
of a 470 pound l o t was screened again over a 1/4-inch screen.
Only about 0.5% was recovered as f i n e s , which i n d i c a t e d good
screening at the mine s i t e . The +1/4 inch m a t e r i a l was d i v i d e d
i n t o two p o r t i o n s . The f i r s t p o r t i o n was reserved f o r heavy
media t e s t s . The other h a l f of the 3 inch by 1/4 inch m a t e r i a l
was crushed to pass a 3/4-inch screen. This sample was then
screened through a 1/4-inch screen and 19% of the sample was
recovered as f i n e s . The remaining 3/4 inch by 1/4 inch m a t e r i a l

was reserved f o r heavy media t e s t s .
Each i n d i v i d u a l hand-picked sample was stage crushed to
pass a 2-inch screen and was screened at 1/4 inch to remove
fines. Three composites were made from the 60 interval
samples. The f i r s t composite was from 0 to +20 feet above the
Mahogany marker. The other two samples were from 0 to -20 feet
below the marker and from -20 to -40 feet below the marker.
Each composite c o n s i s t e d of an equal weight of each one-foot
interval.
Heavy Media Tests. The general t e s t procedure i s
i l l u s t r a t e d s c h e m a t i c a l l y i n Figure 2. Heavy media suspensions
were made by adding magnetite (-65 mesh) to water i n a s t i r r e d
separating v e s s e l . The f i r s t separating g r a v i t y was 1.8. The
pre-wetted shale sample was introduced i n t o the v e s s e l with
constant s t i r r i n g . A f t e r removal of the f l o a t product, the sink
m a t e r i a l was removed and r i n s e d of a l l adhering media. The
process was repeated at s p e c i f i c g r a v i t i e s of 1.95, 2.10, 2.25,
and 2.40. A mixture of 75% by weight magnetite and 25% by
weight f e r r o s i l i c o n was used to prepare the 2.40 specific
g r a v i t y suspension.
A l l products from the l a b o r a t o r y heavy media separation
were thoroughly r i n s e d to remove adhering medium and were a i r
d r i e d at 90°C. Representative samples were crushed to -10
mesh. S p e c i f i c g r a v i t i e s were obtained with an a i r pycnometer
and standard F i s c h e r Assays were run.
Results
The heavy media separation procedure r e s u l t e d in six

separate f r a c t i o n s f o r each composite. Table I shows the y i e l d
r e s u l t s , s p e c i f i c g r a v i t y , and F i s c h e r Assay r e s u l t s f o r the
mined composite of 3 Inch to 1/4 inch m a t e r i a l . Similarly,
Table I I gives the r e s u l t s f o r the 3/4 inch by 1/4 inch crushed
material.

10. LARSON E T A L . Green River Oil Shale 143
Table I
R i f l e Mine
(Mined Composite, -3 inch + 1/4 inch)
Specific Weight % F i s c h e r Assay,

Product Gravity Yield GPT
F l o a t (1.80) 1.76 3.07 70.1
Sink (1.80), F l o a t (1.95) 1.98 7.67 49.4
Sink (1.95), F l o a t (2.10) 2.14 22.53 35.2
Sink (2.10), F l o a t (2.25) 2.28 34.45 22.7
Sink (2.25), F l o a t (2.40) 2.44 30.06 13.6
Sink (2.49) 2.62 2.22 (-5.0) e s t .
Total 2.265 100.00 25.8
Table I I
R i f l e Mine
(Mined Composite, -3/4 inch to +1/4 inch)

F l o a t (1.80) 1.74 2.74 70.4
Sink (1.80), F l o a t (1 .95) 2.04 13.96 36.0
Sink (1.95), F l o a t (2 .10) 2.18 31.33 29.0
Sink (2.10), F l o a t (2 •25) 2.38 45.33 17.4
Sink (2.25), F l o a t (2 .40) 2.50 6.25 10.7
Sink (2.40) 2.72 0.39 (0.0) e s t .
Total 2.261 100.00 24.6
Some s h i f t i n the y i e l d s of each d e n s i t y f r a c t i o n can be

noted i n comparing r e s u l t s i n Tables I and I I . For example,
n e a r l y 65% of the m a t e r i a l i s c o l l e c t e d i n the two f r a c t i o n s
averaging about 18 GPT f o r the coarse sample. A f t e r crushing to
3/4 i n c h , only about 50% of the t o t a l i s found i n these
f r a c t i o n s , and the average grade was decreased s l i g h t l y from
18 GPT. However, very l i t t l e r i c h m a t e r i a l has been l i b e r a t e d
through the crushing to f i n e r s i z e .
The e f f e c t of crushing can be seen i n F i g u r e 3. The cumu-
l a t i v e weight f r a c t i o n of shale, when p l o t t e d versus d e n s i t y ,
shows a s h i f t to lower s p e c i f i c g r a v i t y upon c r u s h i n g . However,
the steep slope of the curve between s p e c i f i c g r a v i t y of 1.95
and 2.10 shows that most of the m a t e r i a l i s found between these
two extremes. When i t i s noted that 19% of the coarse shale was
removed as -1/4 i n c h f i n e s , i t i s apparent that crushing the
shale to the f i n e r s i z e had very l i t t l e e f f e c t i n l i b e r a t i o n of
rich material. Crushing appears to have s h i f t e d the curve
without changing i t s shape significantly in the richer
fractions.
The r e s u l t s f o r each of the hand-picked composites are
given i n Tables I I I , IV, and V. The i n t e r v a l f o r 20 feet above
the Mahogany marker, shown i n Table I I I , has a behavior s i m i l a r

Sample
T
Heavy Madia Separation (1.80)
Sink
Float
Haavy Madia Separation (1.95)
I 1
Float ^Slnk
J "1
Float Sink
Haavy (2.25)
"1
Float Sink

r "1
Float Sink
Figure 2. Heavy-media test flowsheet
100
90 f-
80
70
60 -3/4 x 1 / 4 inch /
/ 0)
#
50 -
JZ
9
e
40
30 -
20 - E
o
10
J i I l I i. I I I 1 L. 100
1.80 1.90 2 . 0 0 2 . 1 0 2 . 2 0 2 . 3 0 2 . 4 0
Specific Gravity of Madia
Figure 3. Weight recovery vs. specific gravity for mine-run composites

to the run-of-mine m a t e r i a l . For example, about 61% of the

material falls i n two fractions, averaging about 18 GPT.
Moreover, only a l i t t l e m a t e r i a l i s found i n the r i c h f r a c t i o n s
above 40 GPT.
Table I I I
R i f l e Mine
Hand Picked Composite, 0 to +20 Feet

F l o a t (1.80) 1.85 2.9 53.1
Sink (1.80), F l o a t (1.96) 2.02 7.8 38.5
Sink (1.96), F l o a t (2.12) 2.22 21.3 27.0
Sink (2.12), F l o a t (2.26) 2.32 33.2 21.6

Sink (2.26), F l o a t (2.41) 2.43 28.0 14.4
Sink (2.41) 2.58 6.8 8.6
Total 2.31 100.00 22.1
Table IV
Hand Picked Composite, 0 to -20 Feet
Specific Weight % Fia scher Assay,

Float (1.79) 1.76 21.3 65.6
Sink (1.79), F l o a t (1.95) 1.93 16.2 43.6
Sink (1.95), F l o a t (2.11) 2.12 19.2 33.1
Sink (2.11), F l o a t (2.25) 2.31 22.3 22.9
Sink (2.25), F l o a t (2.40) 2.48 18.8 12.0
Sink (2.40) 2.54 2.2 5.8
Total 2.132 100.00 34.9
Table V
Hand Picked Composite, -20 to -40 Feet

Float (1.78) 1.81 13.8 58.9
Sink (1.78), F l o a t (1.95) 1.93 12.5 46.7
Sink (1.95), F l o a t (2.11) 2.13 15.6 32.3
Sink (2.11), F l o a t (2.25) 2.29 31.6 23.4
Sink (2.25), F l o a t (2.39) 2.43 25.4 16.2
Sink (2.39) 2.53 1.1 9.2
Total 2.192 100.00 30.6
The richest material sampled i s that i n the 20-foot

interval below the Mahogany marker. These r e s u l t s are
summarized i n Table IV. About 38% of the m a t e r i a l averages
about 55 GPT. A l s o , only about 20% of the t o t a l m a t e r i a l i s i n
the leanest f r a c t i o n s .

The lowest i n t e r v a l sampled, from 20 feet to 40 feet below

the Mahogany marker, i s summarized i n Table V. In one respect,
this interval i s similar to the i n t e r v a l above i t . For
instance, a s i g n i f i c a n t f r a c t i o n of the samples i s contained i n
the r i c h e r f r a c t i o n s . However, the degree of enrichment i s not
q u i t e as good as i n the upper zone. This can be noted i n that
the r i c h e s t f r a c t i o n was 58.9 GPT. In c o n t r a s t , a l a r g e r
f r a c t i o n of r i c h e r m a t e r i a l (65.6 GPT) was obtained i n the upper
interval.
Discussion
L i b e r a t i o n by Fine G r i n d i n g . Two samples shown i n Table I

(49.4 GPT, s p e c i f i c g r a v i t y of 1.98) and (13.6 GPT, specific
g r a v i t y of 2.44) were examined f u r t h e r f o r l i b e r a t i o n of organic

matter by f i n e g r i n d i n g to a p a r t i c l e s i z e of l e s s than
45 microns. The samples were sent to H. T i n s l e y and Company i n
London f o r a Micro V i b r a t o r y S l u i c e s e p a r a t i o n .
A f t e r separation at l e s s than 45 microns, the r i c h sample
(49.4 GPT) contained most of the f i n e p a r t i c l e s below 2.00
gravity. Moreover, l e s s than 10% of the m a t e r i a l was contained
between 2.0 and 2.20 and less than 5% over 2.2 specific
gravity. The lean sample (13.6 GPT) had a main band at 2.33
g r a v i t y and other bands at 2.40 and 2.46 g r a v i t y . In the lean
sample, about 90% of the m a t e r i a l was between 2.20 and 2.47,
with about 40% below 2.30 s p e c i f i c g r a v i t y .
These finely ground samples represent narrow specific
gravity distributions. I t i s apparent that l i t t l e a d d i t i o n a l
organic and mineral separation i s p o s s i b l e by f i n e g r i n d i n g down
to about 45 microns.
Geochemlcal B a s i s . The existence i n Green River shale of
the minute seasonal p a i r s of lamina c a l l e d varves i s important
to the understanding of b e n e f i c i a t i o n p o t e n t i a l . The most
c l a s s i c work i n the areas of geology and geochemistry i s by
Bradley (6^ 7).
Bradley estimated that r i c h shale of about 35 GPT required
8,200 years per foot of accumulation. Lean shale of 10-14 GPT
required about 2,000 years per foot with other shale
intermediate to these extremes. Accordingly, the annual
thickness of the l a y e r p a i r s range from about 150 microns f o r
lean shale to about 25-35 microns f o r r i c h s h a l e . Moreover,
Bradley found that the thickness of the r i c h shale (designated
o i l shale) and the thickness of the lean shale (designated
raarlstone) followed q u i t e p r e c i s e rhythmical changes. The
length of the c y c l e over the e n t i r e depth averaged about 22,000
years. Bradley pointed out that the average of the precession
c y c l e and e c c e n t r i c i t y c y c l e i n the earth's o r b i t would give a
resultant c y c l e of about 21,000 years. Most of the lean
marlstone beds are about 6 feet t h i c k , though the range was from
3.8 to 8.8 f e e t . The r i c h e r o i l shale beds range from 0.6 to

3 . 0 feet. These rhythmic c y c l e s can e a s i l y be v i s u a l i z e d by

examining Figure 1 . Bradley's observations of more than 5 0
years ago are remarkable. Recent modeling of c l i m a t i c responses
to o r b i t a l v a r i a t i o n s seems to suggest a general r e l a t i o n s h i p i n
a l l organic sediments ( 8 ) . A c c o r d i n g l y , the c y c l i c a l ups and
downs of shale grade i n the Green R i v e r are due to changes i n
weather c y c l e s which, i n t u r n , were due to changes i n the
earth's o r b i t .
C o r r e l a t i o n of Grade with S p e c i f i c G r a v i t y . Correlation
between d e n s i t y of o i l - s h a l e rock and the rock's organic content
have been known f o r some time. For example, F r o s t and
S t a n f i e l d ( 2 ) , and Smith and co-workers ( 9 , 10, 1 1 ) have
published data s p e c i f i c a l l y f o r Green River s h a l e . An e m p i r i c a l
expression has been developed between o i l - s h a l e d e n s i t y and o i l
yield:
(1) O i l Yield (GPT) = 31.563 D R

2
- 205.998 1^ + 326.624
where D i s the rock d e n s i t y i n gm/cm .

R
3
This i s a p a r a b o l i c
f u n c t i o n , which i s s t r o n g l y curved, p a r t i c u l a r l y i n r i c h shale
above 3 5 GPT. I t has been g e n e r a l l y recognized that the F i s c h e r
Assay i s a r e l a t i v e l y poor measure of the grade or q u a l i t y of
shale. The q u a l i t y and q u a n t i t y of l i q u i d can vary, h i g h l y
dependent on the elemental and minerals a n a l y s i s and how the
r e t o r t i n g Is c a r r i e d out.
The F i s c h e r Assay r e s u l t s and s p e c i f i c g r a v i t y obtained i n
t h i s study have been p l o t t e d i n Figure 4 . The c o r r e l a t i o n shown
above has been p l o t t e d i n Figure 4 to see how i t compares.
Between a s p e c i f i c g r a v i t y of 1 . 9 5 and 2 . 0 5 , the agreement i s
q u i t e good. However, the heavy media samples of lean shale
between s p e c i f i c g r a v i t i e s of 2 . 2 0 and 2 . 5 0 seem to c o n t a i n more
organic matter than the Smith c o r r e l a t i o n would i n d i c a t e . This
difference i s not s u r p r i s i n g . The Smith c o r r e l a t i o n was
developed by averaging core data of long i n t e r v a l s f o r the
e n t i r e Green R i v e r formation, while the data i n Figure 4 a r e
s p e c i f i c , small p a r t i c l e r e s u l t s f o r extremely narrow s p e c i f i c
gravity fractions.
Volume percent of organic matter i s a l i n e a r f u n c t i o n of
rock d e n s i t y . Smith ( 6 ) has a l s o shown that
(2) V Q - 100 ( 1 ^ - \)/(\ ~ D ) Q
where V i s volume percent of o r g a n i c .

Q
Using an average d e n s i t y of mineral matter, of 2 . 7 2 and

1 . 0 7 f o r organic d e n s i t y , D Q , the equation reduces t o :
(3) V Q » 164.85 - 60.61
where D R i s the d e n s i t y of the s h a l e .
American Chemical
Society Library
1155 16th St. N. W.
Washington, 0 . C. 20038

0 1.80 1.90 2.00 2.10 2.20 2.30 2.40 2.50

Specific Gravity, gm/cm*
Figure 4. Fischer assay results for separated fractions: correlation based on specific gravity
(-•-)(10).
Equation (3) i s the standard form recommended f o r Mahogany

Zone s h a l e . However, s e v e r a l l i n e a r p l o t s are shown i n
Figure 5. The s p e c i f i c g r a v i t y f o r the mineral matter has been
v a r i e d from 2.66 to 2.78. A l s o , the organic g r a v i t y has been
v a r i e d from 1.02 to 1.12 gm/cm . I t i s c l e a r that the lean
shale p a r t i c l e s show an extreme s e n s i t i v i t y to v a r i a t i o n s i n the
mineral density and organic d e n s i t y . For example, a p a r t i c l e of
2.60 s p e c i f i c g r a v i t y shows a range from 4.0 volume % organic to
10.0% f o r the d i f f e r e n t d e n s i t i e s chosen. Moreover, the
c a l c u l a t e d organic content of r i c h shale p a r t i c l e s show much
lower s e n s i t i v i t y to the d e n s i t i e s of the mineral and organic
components. A c c o r d i n g l y , the d e n s i t y c o r r e l a t i o n developed by
Smith must be used with c a u t i o n f o r lean shale p a r t i c l e s . For
lean shale p a r t i c l e s , the d e n s i t y of the organic phase i s lower
than average while the mineral phase i s higher than average. In

comparison, i n the r i c h shale p a r t i c l e s , the organic phase i s
higher than average while the mineral phase i s lower than
average. These e f f e c t s are masked by the average values of
Smith (10, 11).
Bi-Modal Nature of Shale Deposits
Our r e s u l t s i n d i c a t e that the organic concentration and

s t r a t i g r a p h y of shales f a l l i n t o two d i s t i n c t c l a s s e s . These
c l a s s e s are shown by the data i n Tables I I I , IV, and V. The
shale i n t e r v a l above the Mahogany marker contains very l i t t l e
r i c h shale which can be freed by crushing to about 1 inch i n
size. In c o n t r a s t , the two i n t e r v a l s below the marker c o n t a i n
much r i c h m a t e r i a l which i s separable at coarse s i z e f r a c t i o n s .
The bi-modal nature of the shale over the f u l l 60-foot zone
is shown more c l e a r l y i n Figures 6, 7, and 8. The weight
percent of organic m a t e r i a l present i n each f r a c t i o n has been
calculated from Fischer Assay using the Smith (11)
correlations. The d i s t r i b u t i o n of organic m a t e r i a l i n each
f r a c t i o n i s p l o t t e d as histograms f o r each of the three sub-
zones. The upper and lower zones of shale shows a r e l a t i v e l y
sharp maximum at about 25 GPT. The middle zone, immediately
below the marker, does not show t h i s maximum (Figure 7 ) . The
two zones below the marker show a trend toward a second maximum
i n the range of 60-70 GPT. Our lowest separation g r a v i t y was at
1.80, so there i s no way of d e f i n i n g the second maximum
precisely. Since the i n t e r v a l s of organic l e v e l i n the r i c h e r
zones above 30 GPT are somewhat broader, t h i s adds to the
i m p r e c i s i o n i n d e f i n i n g the second maximum.
This bi-modal nature of Mahogany Zone shale i s c o n s i s t e n t
with the observations of Bradley (6). In t h i s c l a s s i c work
Bradley noted the d i s t i n c t c y c l i c behavior of accumulations of a
lean marls tone and a r i c h o i l s h a l e . As p r e v i o u s l y noted, the
c y c l i c accumulations were c o r r e l a t e d with the earth's o r b i t and
subsequent weather c y c l e s . Since the c y c l e s were detected at

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F/gwre 5. Dependence of calculated organic volume on organic and mineral specific gravity 2>
r
oo
LARSON E T A L . Green River Oil Shale 15
UPPER ZONE
+20 t o 0 ft.
JZL —I—
60
—i
10 20 30 40 50 70
Fischer A»iay,GPT
Figure 6. Distribution of organic matter in Mahogany zine shale, Anvil Points

mine, upper zone, -j- 20 ft to Mahogany marker
40 r
MIDDLE ZONE
0 to-20 ft.
—i—
10 20 30 40 50 60 70
Fischer Assay, GPT
Figure 7. Distribution of organic matter in Mahogany zone shale, Anvil Points

mine, middle zone, Mahogany marker to — 20 ft

LOWER ZONE
- - 2 0 to - 4 0 ft.
10 20 3 0 4 0 50 60 70
Fischer Assay, G P T
Figure 8. Distribution of organic matter in Mahogany zone shale, Anvil Points

mine, lower zone, —20 to —40 ft
25 r
20 C-A Tract
•u 5 10 15 20 25 30 35
Ua
40 45 50 55
NOSR Tract
5 -
0 •
10 15 20 25 30 35 40 45 50 55 60 65
Fischer Assay, GPT
Figure 9. Relative distribution of shale grade on C-a tract and Mahogany zone,
Anvil Points:/upper figure,) based on CE-205 core, 2-ft increments, 1050-ft interval;
flowerfigure)based on A-core, 1-ft increments, 73-ft interval.

i n t e r v a l s of about 1-9 f e e t , c o n s i s t e n t with the frequency of

21,000 years, there i s every reason to b e l i e v e t h i s c y c l e would
be detected at our dimensions of 1/4 to 3 inches. As noted by
Bradley, the c l a s t i c s - r i c h (lean marlstone) p o r t i o n s have varve
thicknesses of about 150 microns. A c c o r d i n g l y , a lean p a r t i c l e
averaging 1.18 inches (3 cm) i n dimension perpendicular to the
varves would represent a 20-year i n t e r v a l . In c o n t r a s t , an
extremely r i c h p a r t i c l e of about 65 GPT with s i m i l a r dimensions
would represent an i n t e r v a l of at l e a s t 100 years. Finally, i t
can be noted that the f i n e crushing of shale down to about
45 microns f a i l e d to change the d e n s i t y d i s t r i b u t i o n of the
particles significantly. A c c o r d i n g l y , i t can be concluded that
the histograms shown i n Figure 6 would not change s i g n i f i c a n t l y
i f the m a t e r i a l were separated at these smaller s i z e s .
A p p l i c a t i o n to Other Shale Zones
The r e s u l t s described i n t h i s study were on shale from the

Mahogany Zone i n the southern Perimeter of the Piceance B a s i n .
Given the r e l a t i v e l y constant s t r a t i g r a p h y , i t may be assumed
that the r e s u l t s are at l e a s t q u a l i t a t i v e l y a p p l i c a b l e to the
Mahogany Zone. For example, Curry (12) demonstrated the p r e c i s e
match of i n d i v i d u a l t i n y annual varves i n two core s e c t i o n s
taken 8-1/2 miles apart. Smith and Robb (13) have a l s o remarked
on the s i m i l a r i t y i n mineral character and organic character
throughout the shale measures i n the Green River formation.
Yet, c a u t i o n should be e x e r c i s e d i n e x t r a p o l a t i n g these r e s u l t s
to the deeper shale. For example, n a h c o l i t e and dawsonite are
found i n the S a l i n e Zone, while dawsonite i s much more common i n
the Leached Zone. A l s o , the s p e c i f i c g r a v i t y of the organic
matter i s known to change with depth.
We were g e n e r a l l y i n t e r e s t e d i n comparing the d i s t r i b u t i o n
of r i c h and lean zones of shale throughout the C-a tract
relative to the Mahogany Zone on the southern perimeter.
A c c o r d i n g l y , the F i s c h e r Assay r e s u l t s f o r one core i n the
c e n t r a l p o r t i o n of t r a c t C-a have been compared with the r e s u l t s
from a core i n the southern Mahogany Zone. This comparison i s
shown i n Figure 9. The data are based on a 2-foot i n t e r v a l
sampling on C-a t r a c t versus a 1-foot i n t e r v a l i n the southern
perimeter shale. Several i n t e r e s t i n g comparisons are noted.
The C-a t r a c t shale shows a peak at 15 GPT i n s t e a d of 20 GPT.
A l s o , the C-a shale i n t e r v a l shows more of the m a t e r i a l i n the
medium-grade i n t e r v a l of 25-35 GPT. I t i s a l s o apparent that
i n t e r v a l s of 40 GPT and r i c h e r shale blocks are a much lower
percentage on the C-a t r a c t .
Nevertheless, i t seems apparent that the paleo-limnology
and paleo-climatology of the Green R i v e r Lakes, which was so
beautifully analyzed by Bradley, has a dominant e f f e c t i n
predicting results.

Acknowledgements
The authors are indebted to J- F. Patzer and P. S. Sundar

for t h e i r a s s i s t a n c e , d i s c u s s i o n s , and t h e i r reviews.
Literature Cited
1. Dismant, John H. The Mines Magazine March, 1961, pages 15-

22.
2. Frost, I.C. and Stanfield, K. E. Anal. Chem. March, 1950,
22, pages 491-492.
3. Fahlstrom, P. H., Proceedings of 12th Oil Shale Symposium,

Colorado School of Mines, 1979.
4. Stanfield, K. E.; Frost I. C.; McAuley, W. S.; Smith, H. N.,
Bureau of Mines, RI 4825, November, 1951.
5. East, J. H., Jr. and Gardner, E. D., Bureau of Mines,
Bull 611, 1964.
6. Bradley, Wilraot H., U.S. Geological Survey, Professional
Paper 158-E, 1929.
7. Bradley, W. H. Geological Society of America Bulletin 1948,
59, pages 635-648.
8. Imbrie, John, and Imbrie, John Z. Science February 29, 1980,
207, pages 943-953.
9. Smith, John Ward Chem. Eng. Data Series 1958, 3, No. 2,
pages 306-310.
10. Smith, John Ward, Bureau of Mines RI-7248, 1969, 14 pages.
11. Smith, John Ward, LERC/RI-76/6, September, 1976.
12. Curry, H. D., Intermountain Assoc. Petrol. Geol., 13th Ann.
Field Conf. Guidebook, 1964, pages 169-171.
13. Smith, John Ward and Robb, William A., Bureau of Mines
RI-7727, 1973.
RECEIVED February 18, 1981.

11
Beneficiation of Green River Oil Shale by
Pelletization
J. REISBERG
Shell Development Company, P.O. Box 481, Houston, TX 77001
Green River shale i s a sedimentary, h i g h l y laminated, f i n e

textured rock composed mainly of the minerals dolomite, c a l c i t e ,
quartz, f e l d s p a r , c l a y and f r e q u e n t l y , p y r i t e . A minor p o r t i o n ,
l e s s than 50 percent by weight and averaging about 10 percent,
c o n s i s t s of kerogen, a s o l i d organic, h i g h l y c r o s s - l i n k e d poly-
meric substance, p o l y c y c l i c i n nature, with an appreciable
hetero-atom content. O i l shale, u n l i k e t a r sands and g i l s o n i t e ,
i s l a r g e l y i n s o l u b l e i n organic s o l v e n t s . However, i t e x h i b i t s
a s t r i k i n g tendency to imbibe and swell i n the presence of organic
liquids. Kerogen can be converted by p y r o l y s i s to l i q u i d and
gaseous f u e l s and to a carbonaceous r e s i d u e .
The high mineral content of o i l shale imposes a huge heat
demand upon a thermal upgrading process and c a l l s for very l a r g e
processing f a c i l i t i e s . A r e d u c t i o n i n the mineral content of
the feed by an ore b e n e f i c i a t i o n step can s t r o n g l y i n f l u e n c e the
process economics and may a l s o a f f o r d the a n c i l l a r y advantage of
a decreased volume of contaminated, p o s s i b l y b i o l o g i c a l l y harmful
retort tailings. A process for the b e n e f i c i a t i o n of Green River
shale was i n v e s t i g a t e d which y i e l d s kerogen-enriched o l e o p h i l i c
p e l l e t s and a d i s p e r s i o n i n water of most of the mineral matter.
BACKGROUND
There e x i s t a number of f a m i l i a r procedures for e f f e c t i n g

mineral separations, i n c l u d i n g s i n k - f l o a t methods based on d e n s i t y
d i f f e r e n c e s and f r o t h f l o t a t i o n based on w e t t a b i l i t y . Because
of the tendency of kerogen to swell and s o f t e n i n the presence
of organic l i q u i d s and thus p o s s i b l y to m o b i l i z e trapped mineral
p a r t i c l e s , and because most minerals are water-wetted and thus
e x t r a c t a b l e with water, we i n v e s t i g a t e d a l i q u i d - l i q u i d ( o i l -
water) p e l l e t i z a t i o n method.
Several r e l a t e d procedures for upgrading shales have been
described i n the l i t e r a t u r e . G e n e r a l l y these were developed as
an adjunct to the chemical a n a l y s i s of kerogen, the purpose
being to reduce i n t e r f e r e n c e by minerals and to avoid the r i s k
of o x i d a t i o n of the organic matter by severe chemical deashing.
0097-6156/81/0163-0155$05.00/0

A South A f r i c a n shale, Torbanite,(_L^ was ground with water

in a porcelain b a l l m i l l . O i l ( u n s p e c i f i e d ) was added i n s u f f i -
c i e n t quantity to form a paste with the o r g a n i c - r i c h f r a c t i o n
and g r i n d i n g was continued. Mineral matter became suspended i n
the aqueous phase and t h i s was discarded. The o i l y paste was
solvent washed, d r i e d and analyzed. The ash content was reduced
from an o r i g i n a l value of l e s s than 40 percent to a value of
about 10 percent.
A new Brunswick o i l shale c o n t a i n i n g 58 percent mineral
m a t t e r ^ ) was processed i n a s i m i l a r way except that i t was
preground i n a heavy g a s - o i l p r i o r to the i n t r o d u c t i o n of water.
Following a 16-hour g r i n d i n g p e r i o d , the d r i e d , enriched m a t e r i a l
had a mineral content of 34 percent.
Green River o i l shale^.?/ was treated with 5 percent a c e t i c
acid to remove carbonate minerals p r i o r to g r i n d i n g i n a water,

n-octane system. The aqueous mineral suspension was removed and
replaced repeatedly with fresh water u n t i l no mineral matter was
observable i n the water. A n a l y s i s of the residue i n d i c a t e d that
the mineral content was reduced from an i n i t i a l 75 percent to 16
percent.
These procedures resemble the process for c o a l p u r i f i c a t i o n
described i n 1922 by W. E. T r e n t . I t comprised g r i n d i n g of
coal to a 100/200 mesh s i z e , s u f f i c i e n t to detach the mineral
p a r t i c l e s from the c o a l , then a g i t a t i n g with an organic, water
i n s o l u b l e l i q u i d possessing a " s e l e c t i v e a f f i n i t y " f o r the c o a l .
The process produced an "amalgam" of c o a l and organic l i q u i d and
r e j e c t e d the i n o r g a n i c gangue as aqueous s l u r r y .
Recently, s i m i l a r methods have been a p p l i e d to the separa-
t i o n of t a r from A l b e r t a t a r sands.
EXPERIMENTAL
Procedure. The l a b o r a t o r y work described here was performed

with two shale samples; one c o n s i s t e d of m a t e r i a l from cores
taken at a depth of 1830-1860 feet from the Marathon lease and
the second i n the form of rock fragments from the Colony mine
(Dow p r o p e r t y ) .
For the b e n e f i c i a t i o n we used a 5.5 g a l l o n p o r c e l a i n b a l l
m i l l , and 1.5-inch g r i n d i n g medium (Burundum, of c y l i n d r i c a l
form). The m i l l was charged with 10 pounds of g r i n d i n g medium,
400-800 ml of water, 100-200 grams of shale ( p u l v e r i z e d e a r l i e r
to pass through a 100 mesh screen) and 50-100 ml of organic
l i q u i d binding agent (heptane). The m i l l was r o t a t e d f o r an
hour. T y p i c a l l y , a f t e r about 10 minutes of operation, a kerogen-
enriched f r a c t i o n i n the form of d i s c r e t e flakes or p e l l e t s
began to separate. A f t e r a one-hour m i l l i n g c y c l e , the aqueous
gangue d i s p e r s i o n was removed and replaced with fresh water. A
small sample, 0.2-0.3 grams, of the enriched p e l l e t s was recover-
ed f o r a n a l y s i s and the m i l l i n g o p e r a t i o n repeated f o r as many

11. REISBERG Pelletization 157
c y c l e s as deemed necessary. Both gangue and kerogen-enriched

p e l l e t s were d r i e d under vacuum at 70°C-80°C (see P l a t e I ) . The
kerogen content was determined as weight l o s s by plasma ashing.
(We used two plasma ashing d e v i c e s : I n t e r n a t i o n a l Plasma Corpora-
t i o n , Model 1003B-248AN and LFE Corporation, Low Temperatures
Asher, No. LTA-600.) Since the plasma combustion temperature
does not exceed 50°C we avoid the p o s s i b i l i t y of mineral decom-
p o s i t i o n ( e s p e c i a l l y of carbonates) encountered during high
temperature combustion.
Results. The s i z e of the enriched p e l l e t s i s a f u n c t i o n of

the q u a n t i t y of added organic binding agent. An i n s u f f i c i e n t
quantity of b i n d i n g agent y i e l d s p e l l e t s too small f o r easy
separation from the gangue suspension by means of coarse s i e v e s .
An excess of binder r e s u l t s i n the formation of a voluminous,

s o f t kerogen paste which e n t r a i n s gangue. The optimum c o n d i t i o n
described above y i e l d s p e l l e t s about 1 cm i n diameter. The
r e s u l t of a t y p i c a l b e n e f i c i a t i o n experiment with Marathon lease
m a t e r i a l i s shown i n Figure 1. This e n t a i l e d four one-hour
m i l l i n g c y c l e s , the aqueous mineral d i s p e r s i o n being removed and
replaced with fresh water a f t e r each c y c l e . Kerogen contents
for both the o r g a n i c - r i c h p e l l e t s ( o l e o p h i l i c ) and the water
d i s p e r s i b l e mineral gangue ( h y d r o p h i l i c ) are shown. The f i g u r e
a l s o shows the r e s u l t s of two s i n g l e c y c l e experiments.
The Marathon sample was obtained from a depth of more than
1800 f e e t . Since an ore b e n e f i c i a t i o n step would be more appro-
p r i a t e f o r a minable, shallow formation, we a l s o tested samples
from the Dow-Colony (Parachute Creek) mine. S t a r t i n g with p a r t i -
c l e s i n the 8 to 10 sieve s i z e range, t h i s m a t e r i a l was m i l l e d
i n water u n t i l 90 percent passed through a 100 mesh screen.
Organic binder was added to the aqueous s l u r r y and the process
was continued as described above. Results of d u p l i c a t e e x p e r i -
ments are shown i n Figure 2. The b e n e f i c i a t i o n obtained with
t h i s Dow-Colony shale i s l e s s favorable than that with Marathon
lease m a t e r i a l .
A n a l y s i s of o i l shale surfaces by the scanning e l e c t r o n
microscope p r i o r to and f o l l o w i n g low temperature ashing r e v e a l s
that the mineral matter occurs i n the form of f i n e , d i s c r e t e
p a r t i c l e s w i t h i n a continuous kerogen matrix.
Figure 3 shows the s i z e d i s t r i b u t i o n s of inorganic mineral
p a r t i c l e s obtained by low temperature ashing of unprocessed o i l
shales. These minerals have mean p a r t i c l e diameters (50 percent
frequency l e v e l ) of 5-6 microns.
X-ray d i f f r a c t i o n a n a l y s i s of the products of the b e n e f i c i -
a t i o n of Dow-Colony shale i s shown i n Table I. I t i s c l e a r that
the o l e o p h i l i c e x t r a c t ( p e l l e t s ) r e t a i n s or concentrates the
calcium and magnesium carbonates (dolomite, c a l c i t e , a r a g o n i t e ) ,
p a r t i c u l a r l y the dolomite. The h y d r o p h i l i c gangue c o n s i s t s
mainly of f e l d s p a r and quartz. Since s i l i c a , s i l i c a t e s and
Ca/Ca-Mg carbonates, i n a c l e a n c o n d i t i o n , are water wettable

Plate I. Beneficiation products of Green River oil shale

90
NUMBER OF PROCESS CYCLES
Figure 1. Recovery of Marathon Lease kerogen as a function of the number of

beneficiation cycles. (Kerogen determined by weight loss on low-temperature ash-
ing.)

Figure 2. Beneficiation of Dow-Colony shale

REISBERG Pelletization 161
1.0 10 100
PARTICLE SIZE ( M I C R O N S )
Figure 3. Cumulative particle-size distribution of the mineral constituents of oil

shales (by low-temperature ashing). Particle size by Coulter counter.

the above r e s u l t s would i n d i c a t e that the b e n e f i c i a t i o n procedure

renders at l e a s t a p o r t i o n of the carbonates o i l - w e t t a b l e . The
mechanism for the w e t t a b i l i t y r e v e r s a l of the carbonates may
r e s i d e i n the adsorption of c e r t a i n c a r b o x y l i c c o n s t i t u e n t s of
the shale, v i z . , the bitumens. Bitumens, the s o l v e n t - e x t r a c t a b l e
organic components of o i l shale are r i c h i n c a r b o x y l i c f u n c t i o n a l
groups; they contain about 35 percent f a t t y a c i d s , resinous
a c i d s , polymer acids and benzenoid a c i d s ^ ^ / (see below). Their
d i s s o l u t i o n i n the added organic binder would make them a c c e s s i b l e
to adsorption by the carbonates. Carboxylic acids are a commonly
u t i l i z e d " c o l l e c t o r " for carbonate minerals i n f r o t h f l o t a t i o n
processes.^Z^ They adsorb s t r o n g l y and decrease the water wetta-
b i l i t y of calcium carbonate thus f a c i l i t a t i n g i t s separation
from a h y d r o p h i l i c gangue with the gas phase. S i m i l a r l y , i n
t h i s p e l l e t i z a t i o n process, the a c t i o n of the adsorbed bitumen

c o n s t i t u e n t s on the Ca/Ca-Mg carbonate mineral p a r t i c l e s renders
them l a r g e l y inseparable from the o l e o p h i l i c , o i l swollen kerogen.
Where p y r i t e i s present, one would expect that, due to i t s
inherent o i l w e t t a b i l i t y , i t too would accumulate i n the o l e o -
philic pellets.
TABLE I. MINERAL DISTRIBUTION FOLLOWING BENEFICIATION STEPS

DOW-COLONY SAMPLE
(Estimated Weight Percent i n C r y s t a l l i n e
P o r t i o n by X-ray D i f f r a c t i o n )
Kerogen E x t r a c t Gangue
Untreated
(Oleophilic Pellets) (Hydrophilic)
Calcite 10 10 5
Dolomite 65 83 20
Aragonite 5 5 -
Quartz 10 1 20
Feldspar 10 1 52
Dawsonite — — 3
Samples of p u l v e r i z e d Dow-Colony o i l shale were extracted

both at room temperature and by Soxhlet re f l u x i n g with n-heptane
and with toluene. Solvent was s t r i p p e d from the e x t r a c t under
vacuum and the a c i d numbers of the t a r - l i k e r e s i d u a l bitumens
were determined. Results for d u p l i c a t e samples are shown i n
Table I I . We note that s i g n i f i c a n t q u a n t i t i e s of c a r b o x y l i c
acids are indeed extracted.
In view of the above, one would a n t i c i p a t e d i f f i c u l t y i n
upgrading by t h i s method, shales containing large q u a n t i t i e s of
carbonate mineral (dolomite, c a l c i t e , aragonite) and/or p y r i t e
(FeS2). In Table I I I we show the mineral d i s t r i b u t i o n s , d e t e r -
mined by X-ray d i f f r a c t i o n , of samples from the Marathon and

TABLE I I . EXTRACTION OF BITUMEN FROM DOW-COLONY SHALE
Bitumen Recovered Acid Number,

% of Shale MgKOH/gram
Toluene, Room Temp. 0..7 9. 2, 9,.5

Heptane, Room Temp. 0.,9 3. 6, 2..6
Toluene, Soxhlet 1..5 12..7, 18..8
Heptane, Soxhlet 1..6 19. 2, 13..1
Dow-Colony l e a s e s . The sums of the weight percent of the Ca/Ca-

Mg carbonates and p y r i t e s i n the Marathon samples l i e between 30
and 35 percent whereas i n the Dow-Colony samples, they l i e between

47 and 80 percent. This o b s e r v a t i o n supports the f i n d i n g that
the superior upgrading of the Marathon lease shale i s due to i t s
lower carbonate/pyrite content.
TABLE I I I . MINERAL CONSTITUENTS OF MARATHON LEASE

AND DOW-COLONY MINE SHALE SAMPLES
(Estimated Weight Percent i n C r y s t a l l i n e P o r t i o n )
Marathon Lease Dow-Colony
Calcite 10 10 10
Dolomite 35 30 27 40 65
Aragonite - - - - 5
Pyrite - - 10 10 -
Quartz 15 20 12 10 10
Feldspar 15 20 25 15 10
Analcite - - 3 10 -
Dawsonite 20 15 5 - -
Nahcolite 10 10 - - -
Clay - - 5 - -
Unidentified 5 5 3 5 -
In an e f f o r t to improve the ore upgrading process by i n c r e a s -

ing the l e v e l of carbonate minerals r e j e c t i o n , we studied the
e f f e c t of the chemical a d d i t i v e s shown below.
1. F l o t a t i o n depressants: It was i n d i c a t e d e a r l i e r that
the r e l e a s e of o i l s o l u b l e carboxyl i c acids may be r e s p o n s i b l e
for the r e t e n t i o ni of Ca/Ca--Mg carbonates by the kerogen-organic
binder p e l l e t s . Chemical f l o t a t i o n depressants are sometimes
a p p l i e d to overcome the c o l l e c t i n g tendency of f a t t y acids and
thus to increase the water w e t t a b i l i t y of the carbonate p a r t i c l e s
i n the presence of c a r b o x y l i n acids.(j) The i n t r o d u c t i o n of
such f l o t a t i o n depressants, i n c l u d i n g sodium o x a l a t e , chromium
n i t r a t e , copper n i t r a t e , f e r r i c s u l f a t e and aluminum n i t r a t e
f a i l e d to improve the b e n e f i c i a t i o n process d e s c r i b e d here.

2. Sodium bicarbonate: Marathon lease samples which e x h i b i t

high l e v e l s of b e n e f i c i a t i o n a l s o c o n t a i n n a h c o l i t e (NaHC03).
The b e n e f i c i a t i o n process thus operates at an elevated pH.
To i n v e s t i g a t e the e f f e c t of high pH on Dow-Colony shale, e x p e r i -
ments were performed with added sodium bicarbonate and sodium
hydroxide. No improvement i n kerogen enrichment was obtained.
3. S u r f a c t a n t s : A s e l e c t i o n o f t y p i c a l commercial surface
a c t i v e agents, both a n i o n i c and nonionic, were tested to determine
whether b e n e f i c i a l i n t e r f a c i a l or wetting c o n d i t i o n s could be
obtained. These agents i n c l u d e d :
T r i t o n X-100 (nonionic, ethoxylated o c t y l phenol)
P l u r o n i c F68 (nonionic, ethylene oxide - propylene
oxide condensation product)
NEODOL® 25-7, 25-9, 25-30, 25-45 (nonionic, l i n e a r
primary a l c o h o l ethoxylates)
NEODOL 25-3S ( a n i o n i c , s u l f a t e d form o f NEODOL 25-3).
The e f f e c t s o f several d i s p e r s a n t s were a l s o examined; they
included:
Marasperse N22 and CB ( l i g n o s u l f o n a t e s )
Guartec ( i n d u s t r i a l grade guar gum)
These approaches were a l s o unrewarding.
Product Assay. F i s c h e r Assays were performed with samples

of Marathon lease m a t e r i a l , with both raw shale and with the
beneficiated pellets. Spent shale (char) from the assay was
subjected to heat value (Btu content) a n a l y s i s . Results are
shown i n Table IV.
TABLE IV. FISCHER ASSAYS, MARATHON LEASE SHALE
Beneficiated
Raw Shale
Product
O i l , gal/ton 44.3 154.2

O i l , % by weight 16.6 57.4
Water, g a l / t o n 6.4 2.5
Water, % by weight 2.7 1.0
Spent Shale ( c h a r ) , 74.4 33.0
% by weight
Gas + Loss, 6.3 8.6
% by weight
Btu/lb o f char 693.0 5,352.0
DISCUSSION
Kerogen, as noted e a r l i e r , i s a polymeric substance that can

imbibe large q u a n t i t i e s o f organic l i q u i d s . This i s accompanied

by s w e l l i n g and a s l i g h t s o f t e n i n g o f the matrix. Such gross

s w e l l i n g , as w e l l as e x f o l i a t i o n , under the i n f l u e n c e o f v a r i o u s
organic l i q u i d s can be observed v i s u a l l y with raw o i l shale. We
suggest that t h i s s w e l l i n g and s o f t e n i n g o f the kerogen i s a key
element i n the b e n e f i c i a t i o n scheme described here. During the
m i l l i n g process the inorganic mineral p a r t i c l e s are not e j e c t e d
v i a comminution of a b r i t t l e matrix (chopped out o f the kerogen,
so to speak) but are instead worked out o f the softened kerogen
mass by a deforming and kneading process. The kerogen p a r t i c l e s
become fused r a t h e r than bridged by pendular r i n g s o f binding
agent as i n coal p e l l e t i z a t i o n . A f t e r d r y i n g , the gangue d i s -
i n t e g r a t e s i n t o i t s component small p a r t i c l e s but the kerogen
p e l l e t s dry to a hard b r i t t l e mass e x h i b i t i n g no evidence of the
presence o f d i s c r e t e small p a r t i c l e s .
Two shale samples were studied; one from the Marathon lease
(cores) and the other from the Dow-Colony mine. C l e a r l y , the
l a t t e r i s the more r e l e v a n t to an ore b e n e f i c i a t i o n process.
The r e s u l t s obtained with t h i s m a t e r i a l are l e s s favorable than
those achieved with the Marathon cores. S t i l l the increase i n
kerogen content from a value o f 21 percent f o r the raw m a t e r i a l
to 62 percent for the upgraded p e l l e t s represents a r e j e c t i o n of
83 percent o f the mineral matter ( n e g l e c t i n g a small loss of
kerogen to the gangue). This upgrading can represent a s i z a b l e
decrease i n the heat demand of a r e t o r t i n g process. There may
also be an a n c i l l a r y environmental b e n e f i t . The r e j e c t e d inorgan-
i c gangue contains only a small residue o f kerogen, i n unmodified
form. This i s no more damaging than the kerogen i n the o r i g i n a l
o i l shale. The r e s i d u a l char from the r e t o r t i n g o f the enriched
p e l l e t s has a s u f f i c i e n t l y high Btu content (Table IV) and low
minerals content to be i t s e l f u s e f u l as a process f u e l . I t s ash
would be free o f organic matter and low i n s i l i c a dust. Thus
the m a t e r i a l returned to the environment from a process i n v o l v i n g
ore b e n e f i c i a t i o n , r e t o r t i n g of the kerogen-enriched p e l l e t s and
char burning would be free o f organic p y r o l y s i s products.
The l a b o r a t o r y experiments were performed batchwise i n small
ball mills. A l a r g e r scale operation would c a l l f o r continuous
processing, probably i n a rod m i l l . At present the procedure
does not appear to be economically f e a s i b l e . A major cost i s
that o f the i n i t i a l comminution of the shale. Because the
m a t e r i a l possesses a very unfavorable g r i n d a b i i l t y work index,
t h i s step r e q u i r e s an excessive power o u t l a y . Furthermore, the
process c a l l s for a large quantity o f organic binding agent, the
recovery of which i s a l s o very c o s t l y . Whether or not means can
be devised for improving the economics must await f u r t h e r i n v e s t i -
gation .
ABSTRACT
A procedure is described for the beneficiation of Green
River oil shale, based on the wettability contrast between the

organic kerogen and its inorganic minerals. It entails the

milling of the shale in a mixture of water and a liquid hydro-
carbon binding agent followed by the separation of kerogen-
-enriched pellets and the rejection of an aqueous dispersion of
hydrophilic mineral particles. A portion of the calcite and
dolomite is rendered oleophilic and inseparable from the
hydrocarbon-swollen kerogen pellets. This is brought about by
the adsorption of oil soluble carboxylic constituents contained
in the bitumens. Certain shale samples were upgraded from an
initial kerogen content of 15 percent to a kerogen content in
excess of 80 percent.
LITERATURE CITED
1. Quass, F. W., The Analysis of the Kerogen of Oil Shales,

Inst. Pet. J., 1939, 25, 813.
2. Himus, G. W. and Basak, G. C., Analysis of Coals and
Carbonaceous Materials Containing High Percentages of
Inherent Mineral Matter, Fuel, 1949, 28, 57.
3. Smith, J. W. and Higby, L. W., Preparation of Organic
Concentrate from Green River Oil Shale, Anal. Chem., 1960,
32, 1718.
4. Trent, W. E., Process of Purifying Materials, U. S. Patent
No. 1,420,164, 1922.
5. Puddington, I. E. and Farnard, J. R., Oil Phase Separation,
U. S. Patent No. 3,999,765, 1968.
6. Investigation of Colorado Oil Shale, First Annual Report,
Denver Research Institute, 1966, pp. 19-20.
7. Sutherland, K. L. and Wark, I. W., Principles of Flotation,
Australasian Institute of Mining and Metallurgy, 1955, pp.
317-321.

12
Shell Pellet Heat Exchange Retorting:
The S P H E R Energy-Efficient Process for
Retorting O i l Shale
J. E. GWYN, S. C. ROBERTS, D. E. HARDESTY,

G. L. JOHNSON, and G. P. HINDS, JR.
Shell Development Company, P.O. Box 1380, Houston, TX 77001
Oil shales o f primary interest f o r surface processing occur

mainly i n the Piceance Basin o f western Colorado. These shales
c o n t a i n , t y p i c a l l y , 10 t o 20 p e r c e n t w e i g h t o f h y d r o c a r b o n s r e -
coverable by simple p y r o l y s i s .
Process r e s e a r c h and development i n s h a l e o i l p r o d u c t i o n has
gone o n f o r d e c a d e s , b u t t h e once p l e n t i f u l s u p p l y o f low c o s t
p e t r o l e u m c r u d e s made t h e e c o n o m i c s o f s u c h p r o c e s s e s v e r y u n -
f a v o r a b l e . T h e r e c e n t s h o r t a g e s and c o s t e s c a l a t i o n o f p e t r o l e u m
c r u d e s have renewed i n t e r e s t s i n " u n c o n v e n t i o n a l " raw m a t e r i a l
s o u r c e s s u c h a s c o a l and o i l s h a l e .
S e v e r a l p r o c e s s e s f o r above ground r e t o r t i n g o f o i l s h a l e , w h i c h
have been under d e v e l o p m e n t f o r some t i m e , i n c l u d e t h e T 0 S C 0 - I I ,
1
PARAH0, and U n i o n t e c h n o l o g i e s . ' S h e l l had p a r t i c u l a r i n t e r e s t s i n
t h e f i r s t two. The TOSCO (The O i l S h a l e Company) p r o c e s s u s e s h o t
b a l l s t o h e a t p r e h e a t e d s h a l e i n a r o t a r y k i l n t o r e t o r t i n g tempera-
t u r e s . The s h a l e i s preheated d u r i n g staged, pneumatic t r a n s p o r t
u s i n g f l u e gas f r o m t h e r e t o r t b a l l h e a t e r . The PARAH0 r e t o r t i s a
v e r t i c a l k i l n e m p l o y i n g a downward moving r o c k bed w i t h u p f l o w i n g
r e c y c l e gas and c o m b u s t i o n p r o d u c t s w h i c h sweep r e t o r t e d h y d r o c a r b o n s
f r o m t h e v e s s e l . The U n i o n p r o c e s s i s s i m i l a r b u t u t i l i z e s an upward
f l o w o f c r u s h e d s h a l e . S h a l e i s i n t r o d u c e d a t t h e bottom o f t h e
r e t o r t and pushed upward b y a m e c h a n i c a l " r o c k pump". F l u i d i z e d bed
r e t o r t i n g o f o i l s h a l e was p r o p o s e d i n t h e e a r l y f i f t i e s but was n e v e r
developed t o a commercial s t a t e .
The T 0 S C 0 - I I p r o c e s s i s c a p i t a l i n t e n s i v e b e c a u s e i t r e q u i r e s a
l a r g e volume o f h e a t i n g g a s e s and m e c h a n i c a l l y complex e q u i p m e n t ; t h e
PARAH0 and Union p r o c e s s e s a r e a l s o c a p i t a l i n t e n s i v e b e c a u s e t h e y
have l o n g r e s i d e n c e t i m e r e q u i r e m e n t s t h a t e n t a i l m a s s i v e h a r d w a r e .
The PARAH0 and Union p r o c e s s e s a r e , however, h e a t e f f i c i e n t a s a
r e s u l t o f c o u n t e r c u r r e n t s h a l e and gas f l o w . But t h e TOSCO p r o c e s s ,
a l t h o u g h h a v i n g some d e g r e e o f h e a t r e c o v e r y , uses h e a t r e l a t i v e l y
inefficiently.
The p u r p o s e o f t h i s work was t o d e v e l o p a new r e t o r t i n g p r o c e s s
o f r e l a t i v e l y low c a p i t a l c o s t t h a t i s m e c h a n i c a l l y s i m p l e , h i g h l y
2
r e l i a b l e , and u s e s h e a t e f f i c i e n t l y . The p r o c e s s , ' t e r m SPHER f o r
0097-6156/81/0163-0167$05.00/0

S h e l l P e l l e t Heat Exchange R e t o r t i n g , i s a f l u i d i z a t i o n bed p r o c e s s

conceived f o r the r e t o r t i n g o f o i l shale. T h e f l u i d i z a t i o n mode
r e f e r r e d t o i n t h i s d i s c u s s i o n a p p l i e s t o a range o f s u p e r f i c i a l gas
v e l o c i t i e s between t h o s e used f o r r i s e r t r a n s p o r t and d e n s e b e d
o p e r a t i o n i n p r o c e s s e s such a s c a t a l y t i c c r a c k i n g . By t h i s mode,
s h a l e can be made t o f l o w upward, c o u n t e r c u r r e n t l y t o l a r g e r h e a t -
c a r r i e r p e l l e t s that f a l l through t h e f l u i d i z e d mixture. This
c o u n t e r f l o w o f h e a t - c a r r i e r p e l l e t s and r e l a t i v e l y c o a r s e s h a l e
p a r t i c l e s i s the b a s i c idea around which n o v e l , small s i z e d , t h e r -
m a l l y e f f i c i e n t and e c o n o m i c a l l y v i a b l e p r o c e s s e s have been c o n -
c e i v e d . O t h e r f e e d s t o c k s t o w h i c h SPHER may have p o t e n t i a l a p p l i -
c a b i l i t y i n c l u d e numerous c o a l s , l i g n i t e , wood and bark w a s t e ,
a g r i c u l t u r a l r e s i d u e s , b i o t r e a t e r s l u d g e s , and i n d u s t r i a l and m u n i -
c i p a l s o l i d w a s t e s . Some s p e c i f i c p r o c e s s d e s c r i p t i o n s , w i t h some
v a r i a t i o n s , are d i s c u s s e d below.
B r i e f D e s c r i p t i o n o f Process Applied t o O i l Shale
The SPHER p r o c e s s as o r i g i n a l l y c o n c e i v e d i s shown s c h e m a t i c a l l y

i n F i g u r e 1. T h i s c o n c e p t u a l d e s i g n p r o d u c e s 55,000 b b l / d a y (7575
t / d ) * o f raw s h a l e o i l f r o m 66,000 t o n / d a y (60,000 t / d ) o f 35 g a l / t o n
(13.6%w) o i l s h a l e . I t c a n be seen t h a t t h e r e a r e two l o o p s f o r
c i r c u l a t i o n o f h e a t c a r r y i n g b a l l s . The c o o l b a l l l o o p c a r r i e s heat
f r o m t h e heat r e c o v e r y column t o t h e p r e h e a t e r . T h e hot b a l l l o o p
c a r r i e s heat from the b a l l heater t o the r e t o r t .
Shale i s crushed o r ground t o a f l u i d i z a b l e s i z e ; p r e f e r a b l y as
l a r g e as i s compatible with heat t r a n s f e r requirements and ready
s e p a r a t i o n from h e a t - c a r r y i n g b a l l s . I n i t i a l work i n d i c a t e s t h a t
1 / 1 6 - i n c h (1.6 mm) minus s h a l e and 1/4 (6 mm) o r 5/16 (8 mm) i n c h b a l l s
are d e s i r a b l e .
The s h a l e i s p r e h e a t e d i n a f a s t - f l u i d i z e d ( e n t r a i n i n g ) b e d b y
outer loop, h e a t - c a r r y i n g b a l l s t h a t r a i n through the bed i n coun-
t e r c u r r e n t f a s h i o n ( F i g u r e 2 ) . W i t h a i r a s t h e f l u i d i z i n g medium,
p r e h e a t i n g i s l i m i t e d t o a b o u t 600°F ( 3 1 5 ° C ) b e c a u s e t h e r e i s d a n g e r
from a u t o - i g n i t i o n , w h i c h i s t i m e , t e m p e r a t u r e , and o x y g e n d e -
3
p e n d e n t . ) With other n o n o x i d i z i n g gases, p r e h e a t i n g i s l i m i t e d t o
about 650°F (343°C) b y t h e o n s e t o f k e r o g e n p y r o l y s i s .
In a d e n s e - b e d f l u i d i z e d b e d t h e p r e h e a t e d s h a l e i s f u r t h e r
h e a t e d t o and h e l d a t t h e r e t o r t i n g t e m p e r a t u r e f o r s u f f i c i e n t t i m e t o
c o m p l e t e t h e p y r o l y s i s r e a c t i o n s ( F i g u r e 3 ) . The t o t a l i n v e n t o r y o f
shale i n the r e t o r t i n g v e s s e l i s determined by the r e q u i r e d r e s i d e n c e
t i m e f o r c o m p l e t e k e r o g e n c o n v e r s i o n and t h e s h a l e t h r o u g h p u t . T h e
r e t o r t h e a t r e q u i r e m e n t s a r e s u p p l i e d by c e r a m i c b a l l s w h i c h c i r -
c u l a t e i n t h e i n n e r l o o p . T h e y are r e h e a t e d i n a s e p a r a t e v e s s e l
w h i c h may o p e r a t e a s a moving bed, r a i n i n g p e l l e t bed, o r e n t r a i n e d
flow heater.
The s p e n t s h a l e i s c o o l e d i n a f a s t - f l u i d i z e d b e d b y t h e r e -
c i r c u l a t e d cool p e l l e t s from the p r e h e a t e r . In t h i s manner, c o u n -
t e r c u r r e n t f l o w o f heat c a r r i e r s and t h e s h a l e a s s u r e s efficient
* t o n = 2000 pounds, t = m e t r i c t o n = 1000 k g .

Os
i?
S3
S'
>
>s
W
Ο
ri
H
a
Figure 1. SPHER oil shale process

65°C
Figure 2. SPHER preheater

12. GWYN ET A L . Shell Pellet Heat Exchange Retorting 171
Figure 3. SPHER retort

energy u t i l i z a t i o n . T h i s c h a r a c t e r i s t i c i s a prime advantage o f the

process.
Most c o n d i t i o n s a n d f e a t u r e s o f t h e c o n c e p t u a l p r o c e s s a r e
c h o s e n t o a s s u r e h i g h t h r o u g h p u t s ( s m a l l e q u i p m e n t ) and hence r e l a -
t i v e l y low c a p i t a l and f i x e d c o s t s . T h e s e i n c l u d e t h e c h o i c e o f f l o w
r e g i m e s , h e a t c a r r i e r s ( d e n s i t y and h e a t c a p a c i t y ) and t h e s o l i d s - t o -
gas w e i g h t r a t i o s . A t t e n d a n t f e a t u r e s o f t h e p r o c e s s , such a s b a f f l e
d e s i g n and gas r o u t i n g , a r e c h o s e n t o a c h i e v e o p e r a b i l i t y and optimum
operation.
S e g r e g a t i o n o f t h e two b a l l l o o p s p e r m i t s t h e t a i l o r i n g o f t h e
b a l l m a t e r i a l , shape and s i z e t o e a c h s p e c i f i c t a s k . C i r c u l a t i o n o f
b a l l s i n t h e o u t e r l o o p i s a r e l a t i v e l y low t e m p e r a t u r e o p e r a t i o n and
i s d e d i c a t e d t o heat t r a n s f e r . T h e r e f o r e , d e s i r e d b a l l p r o p e r t i e s
i n c l u d e high heat c a p a c i t y , small s i z e o r l a r g e heat t r a n s f e r
s u r f a c e , e r o s i o n r e s i s t a n c e , and low c o s t . Hence, a pea g r a v e l may be

s u i t a b l e . C o r r o s i o n r e s i s t a n c e may n o t be needed u n l e s s c o n d e n s a t i o n
o c c u r s i n t h e h e a t r e c o v e r y s e c t i o n . T h e use o f t h e s m a l l e s t b a l l s
s e p a r a b l e f r o m t h e s h a l e i n c r e a s e s h e a t t r a n s f e r and r e d u c e s t h e s i z e
o f the exchange v e s s e l r e q u i r e d .
In c o n t r a s t , c i r c u l a t i o n o f b a l l s i n t h e i n n e r l o o p i n v o l v e s t h e
b a l l h e a t e r and r e t o r t where h i g h t e m p e r a t u r e s a n d l o n g e r r e s i d e n c e
times a r e r e q u i r e d . Reaction r a t e r a t h e r than heat t r a n s f e r i s
e x p e c t e d t o be t h e c o n t r o l l i n g f a c t o r i n t h e r e t o r t d e s i g n . I n o r d e r
t o a c h i e v e t h e r e s i d e n c e t i m e needed f o r h i g h c o n v e r s i o n a p s e u d o
p l u g - f l o w d e v i c e such a s a r o t a r y k i l n o r a s t a g e d , d e n s e - p h a s e
f l u i d i z e d b e d may be d e s i r a b l e . Since heat t r a n s f e r i s n o t
c o n t r o l l i n g , t h e b a l l s can be l a r g e r f o r e a s i e r s e p a r a t i o n f r o m s h a l e
but t h e y must s t i l l be s m a l l enough t o p e r m i t p n e u m a t i c t r a n s p o r t .
T h e s e i n n e r l o o p b a l l s must a l s o be r e s i s t a n t t o t h e r m a l s h o c k ,
c h e m i c a l a t t a c k b y t h e hot g a s e s and s p e n t s h a l e and e x p o s u r e t o h i g h
temperatures. Thus, the c h o i c e of the inner loop b a l l s i s l i m i t e d t o
m a t e r i a l s such a s c e r a m i c s .
Detailed Process D e s c r i p t i o n
A more p r o c e s s o r i e n t e d s c h e m a t i c o f the process i s shown i n

F i g u r e 4.
S h a l e Feed P r e p a r a t i o n . S h a l e p r e p a r a t i o n f o r SPHER r e q u i r e s
more e n e r g y t h a n i t d o e s f o r p r o c e s s e s such a s T 0 S C 0 - I I i n t h a t t h e
l a r g e r c r u s h e d s h a l e used i n T 0 S C 0 - I I , e.g., 1 / 2 - i n c h (13 mm) m i n u s ,
must be r e d u c e d t o a r e a d i l y f l u i d i z a b l e s i z e , e.g., 1 / 1 6 - i n c h (1.6
mm) m i n u s , f o r use i n SPHER. G r i n d i n g b y s e p a r a t i n g and r e c y c l i n g
coarse shale i s expected t o produce a b e t t e r s i z e range with l e s s
f i n e s t h a n o n c e - t h r o u g h g r i n d i n g i s f o r t h e same maximum p a r t i c l e
size. S e p a r a t i o n o f s h a l e with t h e d e s i r e d s i z e from o v e r s i z e d
m a t e r i a l may be a c c o m p l i s h e d b y e l u t r i a t i o n w i t h gas o r b y s c r e e n i n g .
The r e c o v e r e d c o a r s e s h a l e i s c o n v e y e d back t o t h e g r i n d e r . Shale
w i t h t h e d e s i r e d t o p s i z e may t h e n be p n e u m a t i c a l l y t r a n s p o r t e d t o a
feed hopper o r standpipe.

Product Vapor
Superheater Flue Gas Steam 900F
1000F 482C
538C
11 OOF o
593C • 0 -
500 F
260C
Air to fteheat w
Air + Fuel Gas
-67 .— _ Water
H
50F >
10C
625F
329C
• Flue Gas
-8 550F "a
288C
Preheat Retort
I
900 F
482C
a
Moisturizer =^> Spent Shale
Raw Shale 0 Ball Mill
175F
50F 79C
10C
100F
38C
5

900F 560F
482C 293C

Air Xir —g
Steam
Aii from Heat Recovery

<1
Figure 4. Raining ball oil shale pyrolysis scheme
Preheater. Figure 2 i s a schematic o f the preheat s e c t i o n .

Ground raw s h a l e i s a l l o w e d t o s l i d e i n t o o r i s p n e u m a t i c a l l y t r a n s -
p o r t e d ( a m i n i m a l volume f l o w ) i n t o t h e lower p a r t o f t h e p r e h e a t e r .
A s t a n d p i p e o f s h a l e s e r v e s a s a r e s i s t a n c e s e a l t o p u r g i n g gas and
a l l o w s t h e p r e h e a t e r t o be p r e s s u r i z e d b y t r a n s p o r t i n g g a s . A l t h o u g h
a s l i d e v a l v e near the bottom of the s t a n d p i p e should p r o v i d e adequate
f l o w c o n t r o l f o r t h e s h a l e , a f l a p p e r v a l v e , screw f e e d e r , o r r o t a r y
l o c k may be c o n s i d e r e d a s o p t i o n s .
The s h a l e i s c a r r i e d up, c o u n t e r c u r r e n t t o t h e r a i n i n g p e l l e t s ,
as a f a s t - f l u i d i z e d bed b y compressed gas ( a i r o r m i x t u r e s o f a i r and
f l u e gas o r r e c y c l e process gas). The preheated shale i s then
recovered a t the top o f the preheater i n h i g h - e f f i c i e n c y , h i g h - l o a d
c y c l o n e s . E x t r e m e l y f i n e d u s t may be c a r r i e d b y e l u t r i a t i o n t o t h e
b a l l h e a t e r when a i r o r a i r c o n t a i n i n g m i x t u r e s a r e used f o r
c o n v e y i n g . T h u s , t h e e n e r g y c o n t e n t o f even t h e f i n e s t s h a l e d u s t can
be r e c o v e r e d w i t h o u t r e q u i r i n g e x p e n s i v e d u s t - c o n t r o l e q u i p m e n t
d u r i n g t h e p r e p a r a t i o n o f s h a l e f o r r e t o r t i n g . A s c o n c e i v e d , t h e use
of s t a n d p i p e s and p r o p e r r o u t i n g gas s t r e a m s r e d u c e s t h e n e c e s s a r y
number o f a i r and gas c o m p r e s s o r s and a l s o a i d s i n h e a t r e c o v e r y . In
t h i s f a s h i o n , p r e s s u r e b a l a n c e a c r o s s t h e whole s y s t e m i s a c h i e v e d
with s u f f i c i e n t extra pressure d i f f e r e n t i a l a v a i l a b l e f o r process
control.
Warm (~625°F, ~33CK)C) b a l l s , p n e u m a t i c a l l y t r a n s p o r t e d f r o m t h e
heat r e c o v e r y s e c t i o n , are recovered at the top of the p r e h e a t e r by a
c y c l o n i c s e p a r a t o r i n t o a surge hopper. From t h e hopper t h e y a r e
a d m i t t e d i n c o n t r o l l e d f l o w t o t h e upper p a r t o f t h e p r e h e a t e r t h r o u g h
an a p p r o p r i a t e c o n t r o l v a l v e a n d steam purge s y s t e m . A c o n i c a l ( o r
o t h e r shaped) d e f l e c t o r i s d e s i r a b l e t o d i s p e r s e t h e b a l l stream
u n i f o r m l y . B a l l s f a l l under t h e i n f l u e n c e o f g r a v i t y a g a i n s t t h e
r i s i n g steam o f f a s t - f l u i d i z e d s h a l e . The r a n g e o f c o n d i t i o n s under
which c o u n t e r c u r r e n t f l o w w i l l e x i s t i s being s t u d i e d . The s m a l l e s t
b a l l s , i . e . , those with the h i g h e s t surface-to-volume r a t i o , t h a t
w i l l f a l l s u f f i c i e n t l y f a s t t h r o u g h t h e p r e h e a t e r a t an e c o n o m i c a l
s h a l e mass f l u x a r e d e s i r a b l e f o r e f f e c t i v e h e a t e x c h a n g e .
B a l l s c o l l e c t i n g a t t h e bottom o f t h e p r e h e a t e r i n an a p p r o -
p r i a t e l y dimensioned boot are s t r i p p e d o f s h a l e p a r t i c l e s by e l u -
t r i a t i n g g a s . Under i d e a l c o n d i t i o n s , t h e l a r g e s t s h a l e p a r t i c l e s
t h a t can be r e a d i l y e l u t r i a t e d f r o m between t h e p e l l e t s a r e a b o u t h a l f
t h e s i z e o f t h e p e l l e t s . In p r a c t i c e t h e s e p a r a t i o n i s more e f f i c i e n t
when t h e b a l l / s h a l e s i z e r a t i o i s 4-5. B a l l s d r o p b y c o n t r o l l e d f l o w
i n t o a t r a n s p o r t l i n e where t h e y a r e p n e u m a t i c a l l y c o n v e y e d t o t h e
shale heat r e c o v e r y s e c t i o n .
The c o u n t e r c u r r e n t r a i n i n g - b a l 1 / f a s t - f l u i d i z e d f l o w r e q i m e must
be o p e r a t e d s o t h a t s t a g i n g i s e f f e c t e d , i . e . , b a c k m i x i n g must be
T
e f f e c t i v e l y r e t a r d e d . e m p e r a t u r e a p p r o a c h e s were i n i t i a l l y assumed
to be 75°F ( 4 2 ° C ) a t t h e t o p and 50°F (28°C) a t t h e bottom o f t h e
preheat v e s s e l . A n y i n c r e a s e i n holdup o f the b a l l s i n c o n t a c t with
shale w i l l reduce the height o f v e s s e l r e q u i r e d . Increased s t a g i n g
and h o l d u p o f b a l l s a r e b o t h a c c o m p l i s h e d b y a s y s t e m o f b a f f l e s
and/or g r i d p l a t e s . With such d e s i g n s i t i s i m p o r t a n t t o a v o i d dead

hot s p o t s where s h a l e m i g h t a c c u m u l a t e b e c a u s e s p o n t a n e o u s i g n i t i o n
of s h a l e m i g h t o c c u r i f a i r i s used as t h e t r a n s p o r t i n g g a s .
Due t o v a p o r i z a t i o n o f w a t e r i n t h e p r e h e a t e r i t may be d e s i r a b l e
to i n c r e a s e t h e diameter o f t h e p r e h e a t e r with i n c r e a s i n g h e i g h t t o
maintain r e l a t i v e l y constant flow c o n d i t i o n s . At proposed preheater
temperatures, the short r e s i d e n c e time i n the preheater should allow
a i r t o be used as a t r a n s p o r t i n g gas w i t h o u t s p o n t a n e o u s i g n i t i o n and
w i t h l i t t l e s h a l e d e g r a d a t i o n and y i e l d l o s s . D i l u t i o n o f t r a n s p o r t
a i r w i t h f l u e g a s may be used t o p e r m i t a h i g h e r p r e h e a t i n g
t e m p e r a t u r e w i t h o u t i g n i t i o n . The u s e o f a i r as t h e e n t r a i n i n g gas i n
t h e p r e h e a t e r p e r m i t s t h e f i n e s t o i l s h a l e d u s t and any p r e m a t u r e l y
e v o l v e d h y d r o c a r b o n s t o be e c o n o m i c a l l y burned i n t h e b a l l h e a t e r .
T h u s , c o m b u s t i o n a i r i s a l s o p r e h e a t e d i n t h e s h a l e p r e h e a t e r . By
o p e r a t i n g the p r e h e a t e r i n c o u n t e r f l o w with a temperature approach
o f £ 1 0 0 ° F (55°C), overheating o f small p a r t i c l e s i s avoided.
Retort. Figure 3 depicts the retort section of the r a i n i n g

pellet process.
S h a l e e n t r a i n e d f r o m t h e p r e h e a t e r i s f e d t o t h e lower p o r t i o n o f
t h e r e t o r t t h r o u g h a h i g h - l o a d , h i g h - e f f i c i e n c y s e p a r a t e r and s u r g e
hopper ( w i t h a e r a t i o n ) . The s h a l e f e e d r a t e t o t h e r e t o r t i s
c o n t r o l l e d i n t h e same way as i t i s t o t h e p r e h e a t e r .
Steam o r gas i n j e c t i o n i s r e q u i r e d a t t h e bottom o f t h e r e t o r t t o
s t a r t t h e f l u i d i z a t i o n . However, some o r a l l o f t h i s gas may be f i r s t
used i n t h e b a l l s t r i p p i n g s e c t i o n . V a p o r e m i t t e d by r e t o r t i n g adds
g r e a t l y t o t h e v o l u m e t r i c f l o w o f f l u i d i z i n g gas a s i t r i s e s up
through the r e t o r t . The v e s s e l c r o s s - s e c t i o n i s i n c r e a s e d a c -
c o r d i n g l y t o m a i n t a i n c o n s t a n t c o n d i t i o n s f o r the dense f l u i d i z e d
bed.
Hot h e a t c a r r y i n g b a l l s ( a t about 1400°F, 7 6 0 ° C ) a r e added t o t h e
t o p o f t h e r e t o r t i n t h e same manner as t h e y a r e t o t h e p r e h e a t e r , b u t
in s e p a r a t e r streams t o d i f f e r e n t l e v e l s i n t h e r e t o r t . T h i s avoids
o v e r h e a t i n g (and c r a c k i n g ) at t h e t o p o f t h e r e t o r t . The b a l l
d i a m e t e r s s h o u l d be about 1 / 4 - i n c h (6 mm) t o a s s u r e a r e a s o n a b l e f a l l
v e l o c i t y (0.25 f p s , 0.087 m/s) t h r o u g h t h e d e n s e - p h a s e f l u i d i z e d bed
of s h a l e .
The b a l l s c o l l e c t i n a b o o t a t t h e bottom o f t h e r e t o r t and a r e
s t r i p p e d o f s h a l e f i n e s i n an e l u t r i a t i n g s e c t i o n . S u p e r h e a t e d steam
(1200°F, 6 5 0 ° C ) p r o v i d e s b o t h t h e s t r i p p i n g a c t i o n and t h e f e e d s h a l e
fluidizing action. T h e c o o l e d b a l l s (900°F, 4 8 0 ° C ) a r e t h e n
r e c i r c u l a t e d pneumatically to the b a l l heater f o r reheating. A i r f o r
t h e b a l l l i f t i s combined w i t h a i r f r o m t h e p r e h e a t e r c y c l o n e s and
with a t h i r d a i r / f u e l - g a s stream t o provide the d e s i r e d f u e l mixture
for the ball heater.
P r o c e s s e d s h a l e i s removed a t t h e t o p o f t h e r e t o r t . A c i r -
c u m f e r e n t i a l w e i r i s p r o v i d e d t o m a i n t a i n a c o n s t a n t bed h e i g h t i n t h e
upper s t a g e . E n t r a i n e d s h a l e p a r t i c l e s a r e removed f r o m t h e p r o d u c t
v a p o r by h i g h - e f f i c i e n c y c y l o n e s l o c a t e d i n t h e v a p o r d i s e n g a g e m e n t
s e c t i o n . The d i m e n s i o n s o f t h i s t o p s e c t i o n a r e a , i n f a c t , d e t e r m i n e d
by t h e c y c l o n e c o n f i q u r a t i o n . S u p e r h e a t e d steam ( 1 2 0 0 ° F , 6 5 0 ° C ) i s

i n j e c t e d i n an e f f o r t t o e l i m i n a t e c o n d e n s a t i o n c o k i n g i n t h e v a p o r
section.
A d s o r b e d and e n t r a i n e d v a p o r s a r e removed f r o m t h e r e t o r t e d
s h a l e b y steam i n t h e s p e n t s h a l e s t r i p p e r . S t r i p p e d s h a l e i s s e n t t o
t h e h e a t r e c o v e r y s e c t i o n . The o v e r h e a d p r o d u c t s f r o m t h e s p e n t s h a l e
s t r i p p e r a r e combined w i t h t h e r e t o r t v a p o r s a n d a r e f u r t h e r
s u p e r h e a t e d w i t h steam t o r e d u c e c o n d e n s a t i o n c o k i n g and quenched
w i t h f r a c t i o n a t o r bottoms i n a q u e n c h t o w e r .
Staging o f t h e r e t o r t c a n reduce t h e average r e s i d e n c e time
required f o r a given hydrocarbon y i e l d . T h i s s t a g i n g c o u l d be
achieved by adding r e s t r i c t i v e h o r i z o n t a l g r i d s spaced, f o r example,
a t t e n - f o o t i n t e r v a l s o f h e i g h t . However, s i n c e s t a g i n g may a l s o
i n t r o d u c e an unwanted t e m p e r a t u r e g r a d i e n t a c r o s s t h e r e t o r t , a
s i n g l e - s t a g e d e s i g n may be f a v o r e d .
P y r o l y s i s data i n d i c a t e that a r e l a t i v e l y long ( s e v e r a l minutes)

1
r e s i d e n c e t i m e i s r e q u i r e d f o r t h e r e t o r t i n g r e a c t i o n . * ) Hence, h e a t
t r a n s f e r i s n o t l i m i t i n g i n t h e r e t o r t and l a r g e r b a l l s w i t h a lower
s u r f a c e - t o - v o l u m e r a t i o may be u s e d . Larger b a l l s a r e d e s i r a b l e
b e c a u s e , i n t e r a l i a , t h e i r m a n u f a c t u r i n g c o s t i s l e s s . The maximum
b a l l d i a m e t e r i s l i m i t e d b y t h e a b i l i t y t o t r a n s p o r t them pneu-
m a t i c a l l y and b y t h e i r s e t t l i n g v e l o c i t y t h r o u g h t h e f l u i d i z e d bed o f
s h a l e . Thermal shock c o u l d a l s o be a f a c t o r t h a t l i m i t s b a l l s i z e .
About 1 / 4 - i n c h (6 mm) d i a m e t e r b a l l s may be a good compromise on s i z e ,
as m e n t i o n e d above.
B a l l H e a t e r . T h e b a l l h e a t e r c a n be a m o v i n g bed, a r a i n i n g
p e l l e t o r an e n t r a i n e d f l o w d e s i g n . P r e h e a t e d a i r f r o m t h e b a l l l i f t
p i p e p l u s a i r f r o m t h e p r e h e a t e r and s u p p l e m e n t a l a i r and f u e l f o r m
t h e c o m b u s t i o n m i x t u r e used t o h e a t t h e b a l l s . B a l l h e a t e r f l u e gas
i s r o u t e d p a r t l y t o a waste heat b o i l e r t o r e c o v e r energy i n the form
o f h i g h - p r e s s u r e steam and p a r t l y t o o t h e r v e s s e l s i n t h e p r o c e s s t o
s e r v e a s a t r a n s p o r t g a s . C o o l e d g a s e s a r e t h e n s c r u b b e d t o remove
b o t h p a r t i c u l a t e s and any s u l f u r o x i d e s . The p a r t i c u l a t e s h a l e d u s t
n a t u r a l l y a b s o r b s s u l f u r o x i d e s i n t h e wet s c r u b b e r . E x i t i n g h o t
b a l l s r e t u r n t o the r e t o r t through s e v e r a l feed standpipes.
Heat R e c o v e r y . The heat r e c o v e r y s e c t i o n i s s i m i l a r t o t h e

preheat s e c t i o n s .
F a s t - f l u i d i z e d r e t o r t e d s h a l e i s c o o l e d f r o m 990°F (482°C) t o
about 175°F (79°C) b y c o n t a c t i n g i t c o u n t e r c u r r e n t l y w i t h b a l l s f r o m
t h e p r e h e a t s e c t i o n . S i n c e t h e c o n v e y i n g ( f l u e ) g a s i s c o o l e d and
c o n t r a c t s a s i t r i s e s , i t may be d e s i r a b l e t o r e d u c e t h e v e s s e l s i z e
a c c o r d i n g l y i n t h e upper p o r t i o n t o m a i n t a i n t h e d e s i r e d f l o w r a t e o f
gas.
E l u t r i a t e d cooled shale i s separated i n a h i g h - e f f i c i e n c y
s e p a r a t o r and r o u t e d t o a m o i s t u r i z e r i n p r e p a r a t i o n f o r d i s p o s a l .
Gas f r o m t h e h e a t r e c o v e r y u n i t i s w a t e r washed i n a v e n t u r i s c r u b b e r
and e x c e s s w a t e r f r o m t h e s c r u b b e r i s used i n t h e m o i s t u r i z e r . L i t t l e
w a t e r v a p o r i s g e n e r a t e d i n s c r u b b i n g t h e gas and w e t t i n g t h e s p e n t
s h a l e b e c a u s e t h e o u t l e t t e m p e r a t u r e o f t h e h e a t r e c o v e r y u n i t i s low

(175°F, 7 9 ° C ) . Water u s a g e i n t h e SPHER p r o c e s s i s , therefore,

d e s i r a b l y low.
Problem Areas
S i n c e SPHER r e p r e s e n t s t h e a p p l i c a t i o n o f new r e g i m e s o f f l u -
i d i z a t i o n t o s h a l e r e t o r t i n g , t h e r e a r e a number o f q u e s t i o n s t h a t
must be answered and f a c t o r s t h a t must be q u a n t i f i e d . Some have been
answered by s i m p l e e x p e r i m e n t s , t h e r e s u l t s o f w h i c h w o u l d i n d i c a t e
e i t h e r a "go" o r a "no go" o n f u t u r e work, and some f a c t o r s w i l l
e v e n t u a l l y r e q u i r e d e m o n s t r a t i o n p l a n t o p e r a t i o n under d e s i g n c o n d i -
t i o n s t o prove the p r o c e s s . F a c t o r s o f primary concern are d i s c u s s e d
below.
Heat T r a n s f e r R a t e s . P r o c e s s e v a l u a t i o n s have used a r a t e

2
c o e f f i c i e n t o f 9 0 B t u / s q f t / h r °F (0.51 k w / m / ° C ) , b a s e d upon t h e
s u r f a c e a r e a o f t h e b a l l s . L i t e r a t u r e d a t a on t r a n s f e r f r o m f l u i d i z e d
beds t o submerged o b j e c t s i n d i c a t e t h a t even h i g h e r r a t e s have been
a c h i e v e d , b u t t h e s e h i g h r a t e s a r e f u n c t i o n s o f bed d e n s i t y and t h e
s i z e of the f l u i d i z e d p a r t i c l e s . Data d i r e c t l y a p p l i c a b l e t o the
SPHER s y s t e m a r e r e q u i r e d f o r f i n a l e v a l u a t i o n s and d e s i g n s .
F l o w R e g i m e s . The c o u n t e r c u r r e n t f l o w o f p e l l e t s r e l a t i v e t o
t h e f a s t - f l u i d i z e d s h a l e and i t s f l u i d i z i n g gas s u g g e s t s t h e e x i s -
t e n c e o f l i m i t i n g o r f l o o d i n g v e l o c i t i e s . The impingement o f s h a l e
p a r t i c l e s upon p e l l e t s (knockback e f f e c t ) r e t a r d s t h e upward f l o w o f
s h a l e as w e l l as t h e f a l l o f t h e p e l l e t s . The s i z e o f t h e e f f e c t i s
d i f f e r e n t i n dense-bed and f a s t - f l u i d i z e d r e g i m e s . In d e n s e beds,
t h e f a l l i n g v e l o c i t y o f p e l l e t s w i l l be a b o u t 1/4 f p s (0.08 m/s) w h i l e
i n t h e f a s t - f l u i d i z e d bed t h e f a l l i n g v e l o c i t y i s e x p e c t e d t o be
l a r g e r . O p e r a t i o n a l windows and p r e s s u r e d r o p / h o l d u p e q u a t i o n s must
be d e f i n e d . T h e s e phenomena have been i n v e s t i g a t e d on t h e 7 - 1 / 2 - i n c h
2
(19 cm) d i a m e t e r c o l d - f l o w u n i t . S h a l e f l u x r a t e s o f 10 l b / s e c / f t (49
2 2 2
k g / s e c / m ) and b a l l f l u x r a t e o f 15 l b / s e c / f t (73 k g / s e c / m ) were
a c h i e v e d a t s u p e r f i c i a l gas v e l o c i t i e s o f 15 t o 20 f t / s e c (4.6 t o 6.1
m/s).
S t a g i n g . E f f i c i e n t use o f h e a t and, t o a l e s s e r e x t e n t r e t o r t i n g
y i e l d , r e q u i r e some c o u n t e r c u r r e n t s t a g i n g t o a c h i e v e t h e e c o n o m i c
a d v a n t a g e s e x p e c t e d f o r t h e SPHER p r o c e s s . About s i x stages are
d e s i r e d f o r t h e p r e h e a t e r , f o u r i n t h e h e a t r e c o v e r y s e c t i o n and two
o r t h r e e s t a g e s may be d e s i r e d i n t h e r e t o r t .
G a s - f l u i d i z e d beds a r e b a s i c a l l y u n s t a b l e and t h e y t e n d t o have
a h i g h d e g r e e o f b a c k m i x i n g due t o c i r c u l a t i o n p a t t e r n s c a u s e d b y
r i s i n g gas b u b b l e s . Beds w i t h a l a r g e h e i g h t - t o - d i a m e t e r r a t i o (L/D)
tend t o r e s t r i c t t h i s c i r c u l a t i o n and i n c r e a s e the s t a g i n g o f
f l u i d i z e d s o l i d s . F o r e x a m p l e , t h e S h e l l ' s A n a c o r t e s CCU r e g e n e r a t o r
( L / D = 2 . 5 ) performs w i t h about f o u r s o l i d s mixing s t a g e s .

Pneumatic l i f t p i p e s ( r i s e r s ) f o r s o l i d s do not e x h i b i t l a r g e
eddy m i x i n g c u r r e n t s b u t t h e y do have r a d i a l v e l o c i t y p r o f i l e s t h a t
peak t o w a r d t h e c e n t e r o f t h e p i p e . I t i s even p o s s i b l e ( a t l o w e r
v e l o c i t i e s ) f o r s o l i d s i n r i s e r s t o f l o w down a l o n g t h e w a l l . C a t -
a l y t i c c r a c k i n g f e e d r i s e r s (L/D = 20) e x h i b i t f o u r t o s i x s o l i d s
m i x i n g s t a g e s . The v e l o c i t y p r o f i l e f l a t t e n s ( a p p r o a c h e s p l u g f l o w )
w i t h i n c r e a s i n g p i p e d i a m e t e r b u t becomes more peaked w i t h i n c r e a s e d
s o l i d s l o a d i n g and d e c r e a s e d v e l o c i t y .
D e t e r m i n a t i o n o f s t a g i n g and mixing o f s o l i d s i n the r a i n i n g
p e l l e t s y s t e m may r e q u i r e l a r g e t e s t f a c i l i t i e s .
A g g l o m e r a t i o n and D e f l u i d i z a t i o n . Two p o s s i b l e p r o b l e m s a r i s e :
(1) ground s h a l e c o n t a i n i n g a s i z e a b l e f r a c t i o n o f 1 / 1 6 - i n c h - o r - l e s s
(1.6 mm) p a r t i c l e s w i l l s e g r e g a t e i n t o c o a r s e and f i n e l a y e r s , even
under m o d e r a t e f l u i d i z a t i o n c o n d i t i o n s , and ( 2 ) t h e ground s h a l e

m i g h t become t a c k y , d u e t o t h e p r e s e n c e o f l i q u i d s on t h e s h a l e
s u r f a c e under r e t o r t c o n d i t i o n s , and d e f l u i d i z e b y a g g l o m e r a t i o n .
The q u e s t i o n o f a g g l o m e r a t i o n needs f u r t h e r r e s o l u t i o n . S m a l l
scale experiments i n d i c a t e d d i r e c t v a p o r i z a t i o n of shale o i l occurred
d u r i n g r e t o r t i n g a n d no a g g l o m e r a t i o n t e n d e n c i e s were n o t e d . How-
e v e r , a g g l o m e r a t i o n c o u l d t a k e p l a c e i n c o l d s p o t s where h y d r o c a r b o n
c o n d e n s a t i o n m i g h t o c c u r . Two r e q u i r e m e n t s o f r e t o r t d e s i g n a r e t o
a v o i d c o l d s p o t s and t o p r o v i d e s u f f i c i e n t m i x i n g o f f r e s h s h a l e w i t h
i n e r t s ( i . e . , with spent shale) t o prevent agglomeration.
O v e r h e a t i n g and I g n i t i o n . A i r was o r i g i n a l l y c o n c e i v e d a s t h e
p r e h e a t e r gas f o r t r a n s p o r t i n g s h a l e b u t use o f an i n e r t gas may be
p r e f e r r e d . I f s h a l e i s h e a t e d i n a i r t o a t e m p e r a t u r e where r e t o r t i n g
p r o c e e d s , t h e n a c o m b u s t i b l e m i x t u r e i s formed and i g n i t i o n c a n
o c c u r . A t a t m o s p h e r i c p r e s s u r e t h i s o c c u r s a t about 630°F ( 3 3 2 ° C ) .
L o c a l s t a g n a t i o n zones o f s h a l e n e a r t h e b a l l i n l e t s h o u l d be a v o i d e d
because they might l e a d t o such a c o n d i t i o n . D i l u t i o n w i t h an i n e r t
gas o r use o f a n o t h e r gas a s a c a r r i e r may be p r e f e r r e d b e c a u s e b o t h
w i l l permit a broader range o f o p e r a t i o n without the p o s s i b i l i t y o f
shale i g n i t i o n .
Pressure Balance - O p e r a b i l i t y . O v e r a l l o p e r a t i o n , as i n
c a t a l y t i c c r a c k i n g , depends on u s e o f s t a n d p i p e s t o g e n e r a t e t h e
p r e s s u r e d i f f e r e n t i a l s n e c e s s a r y t o cause s h a l e and b a l l s t o f l o w
i n t o the process v e s s e l s . Excess pressures are taken out by s l i d e
v a l v e c o n t r o l w h i c h a l s o dampens t h e t r a n s f e r o f p r e s s u r e s u r g e s
between v e s s e l s .
The h i g h p e r m e a b i l i t y o f t h e s t a n d p i p e m a t e r i a l , e s p e c i a l l y o f
t h e s p h e r e s o r p e l l e t s , w i l l a l l o w a p p r e c i a b l e gas l e a k a g e . A d e q u a t e
p u r g e g a s e s i n t h e s t a n d p i p e w i l l , t h e r e f o r e , be r e q u i r e d .
B a l l S e p a r a t i o n and Recovery. T h e r a i n i n g b a l l s must be

s t r i p p e d f r e e o f s h a l e b e f o r e b e i n g removed f r o m a v e s s e l . T h i s can

be most r e a d i l y done b y use o f a s t r i p p i n g gas a t r e l a t i v e l y h i g h

v e l o c i t y (^10 f p s , 3 m/s) i n a b a l l - c o l l e c t i o n b o o t . T h i s m i g h t be
a l a r g e f r a c t i o n o f t h e f l u i d i z i n g gas i n a v e s s e l and r e d u c e s t h e
q u a n t i t y o f gas a v a i l a b l e f o r t r a n s f e r r i n g s h a l e i n t o t h e v e s s e l
above t h e b o o t .
G e n e r a t i o n o f F i n e s and E n t r a i n m e n t o f S h a l e . Although r e -
tort irTg~of~shaTe~doe^ i t does weaken
t h e p a r t i c l e s so t h a t t h e y a r e more r e a d i l y a t t r i t a b l e . P a r t i c l e s i z e
d i s t r i b u t i o n r e p o r t e d f o r a f l u i d i z e d bed p r o c e s s i s l i s t e d i n T a b l e
1. T h i s p o t e n t i a l g e n e r a t i o n o f f i n e s may not be s e r i o u s f o r SPHER
s i n c e o p e r a t i o n w i l l be o n c e t h r o u g h f o r t h e s h a l e and r e s i d e n c e t i m e
i n v e s s e l s w i t h f l u i d i z e d beds i s o n l y a few m i n u t e s .
E n t r a i n m e n t o f s h a l e i n gas i n t h e p r e h e a t and h e a t r e c o v e r y
s e c t i o n s i s t h e b a s i c mode o f t r a n s p o r t f o r s h a l e . In t h e r e t o r t ,
e x c e s s i v e e n t r a i n m e n t r e d u c e t h e r e s i d e n c e t i m e below t h a t needed f o r
r e t o r t i n g and e x t r a s t e p s may be r e q u i r e d f o r r e t u r n i n g s h a l e f i n e s t o
the r e t o r t .
In a l l c a s e s , h i g h - l o a d and h i g h - e f f i c i e n c y ( c y c l o n e ) s e p a r a t o r s
w i l l be r e q u i r e d t o p r e v e n t e x c e s s i v e c a r r y o v e r o f s h a l e i n gas
s t r e a m s t o o t h e r p o r t i o n s o f t h e p r o c e s s . T h e s e r e c o v e r e d f i n e s may
need t o be r e c y c l e d t o t h e a p p r o p r i a t e v e s s e l s i n o r d e r t o i n s u r e t h e
p r o p e r c o n c e n t r a t i o n o f f i n e s f o r smooth f l u i d i z a t i o n .
C h o i c e o f B a l l M a t e r i a l . The p u r p o s e o f t h e b a l l s i s t o p r o v i d e
a means o f c o n v e y i n g and e x c h a n g i n g h i g h l y c o n c e n t r a t e d h e a t e n e r g y .
T h u s , t h e y s h o u l d have a h i g h e x t e r n a l s u r f a c e a r e a ( i . e . , a s m a l l
d i a m e t e r ) and a h i g h h e a t c a p a c i t y . However, t h e y must b e l a r g e
enough t o be r e a d i l y s e p a r a b l e f r o m t h e s h a l e . F o r e a s e o f s e p a r a t i o n
t h e y s h o u l d have a h i g h d e n s i t y . T a b l e 2 l i s t s some p r o p e r t i e s o f
candidate materials. O t h e r f a c t o r s t o c o n s i d e r i n c l u d e c o s t and
r e s i s t a n c e t o c o r r o s i o n , a b r a s i o n and t h e r m a l s h o c k . The q u a l i t y o f
a m a t e r i a l such as a l u m i n a i s h i g h l y d e p e n d e n t upon i t s method o f
m a n u f a c t u r e and t h e s u i t a b i l i t y o f s p e c i f i c a l u m i n a s must be d e f i n e d .
E r o s i o n / A t t r i t i o n / T h e r m a l S h o c k . The h i g h v e l o c i t i e s o f b a l l s
i n l i f t p i p e s and t h e t u r b u l e n t n a t u r e o f t h e f l u i d i z e d beds l e a d t o
the p o s s i b i l i t y o f e r o s i o n o f the equipment and a t t r i t i o n o r
f r a c t u r i n g o f t h e b a l l s . E r o s i o n can be r e d u c e d by u s i n g a b r a s i o n
r e s i s t a n t r e f r a c t o r y l i n i n g s i n p i p e s . A t t r i t i o n and f r a c t u r i n g o f
b a l l s can b e r e d u c e d by p r o p e r d e s i g n t o r e d u c e t h e e f f e c t o f im-
p a c t i o n a t e l b o w s and on d e f l e c t i o n p l a t e s .
B r e a k a g e b y t h e r m a l shock i s r e d u c e d by c o u n t e r c u r r e n t o p e r a -
t i o n , w h i c h a l l o w s r e d u c e d t e m p e r a t u r e g r a d i e n t s , and by a s m a l l b a l l
s i z e , which reduces thermal s t r e s s e s .
Conclusions
As w i t h most n e w l y c o n c e i v e d p r o c e s s e s t h e r e i s c o n s i d e r a b l e
d e v e l o p m e n t work t o be done b e f o r e SPHER i s a m a t u r e p r o c e s s . This

TABLE 1. PARTICLE SIZE DISTRIBUTIONS OF SHALE RETORTED BY

FLUIDIZED BED TECHNIQUES.
3
F l u i d i z e d Spent S h a l e )
S i z e Range,u Percent
0-20 <25
20-60 5-15
60-200 20-50
200-400 20-30
<400 < 5
a] See R e f e r e n c e No. 5
TABLE 2. PROPERTIES AND CIRCULATION RATES OF CANDIDATE MATERIALS

FOR OUTER BALL LOOP.
Density Heat C a p a c i t y
3 a 3 i 0
Material lb/ft t/m Btu/Lb °F B t u / F t F Kcal/m
High D e n s i t y Alumina 231 3.70 0.22 50.8 814

(ceramic b a l l s used
by T o s c o )
Aluminum 168 2.69 0.23 38.8 622
Steel 487 7.80 0.12 58.4 935
Lead 686 10.99 0.03 20.6 330
Gravel 156 2.50 0.2 31.2 500

12. GWYN ET AL. Shell Pellet Heat Exchange Retorting 181
r e p o r t s e r v e s t o p r e s e n t t h e b a s i c f e a t u r e s o f SPHER and t o p o i n t up
some a r e a s r e q u i r i n g d e v e l o p m e n t work.
Abstract
The concept of a novel retorting process for the recovery of
hydrocarbonaceous fluids from particulate solids, especially o i l
shale, is described. In this process, heat is transferred between
fluidized shale and heat-carrier pellets, raining in countercurrent
flow in a preheater, a retort, and a heat recovery vessel.
The desirability of this process results from a high heat flux
and efficient countercurrent heat recovery from the spent shale.
This, in turn, results in a thermally efficient plant of relatively
small size and low capital expense.
The process is also adaptable to similar uses with other feed

materials; for example, the devolatilization of coal and lignites.
New regions of fluidization technology and rapid pyrolysis are
envisioned and some developments of these regions are covered. This
report further discusses the basic features of the conceptual process
and potential problem area.
References
1. Hendrickson, T. A . , Quarterly of Colorado School of Mines
69(2):45 (1974).
2. U.S. Patent No. 4,110,193, dated August 29, 1978.
3. Allred, V. B., Quarterly of Colorado School of Mines 59(3):56
(1964).
4. Hinds, G. P. Jr., AIChE Annual Mtg., Miami, Nov. 1978.
5. U.S. Patent No. 2,717,869, dated September 13, 1955.

13
Retorted O i l Shale Disposal Research
R. N. HEISTAND
Paraho Development Corporation, Box A, Anvil Points, Rifle, CO 81650
In the quest for alternate energy sources, oil shale

appears particularly attractive because of the large domestic
deposits and because the retorting process produces liquid and
gaseous fuels directly. However, the retorting process also
produces large quantities of retorted shale which could pose a
potentially adverse environmental impact if not disposed of
properly. A mature, million-barrel-per-day oil shale industry
would produce over one-and-one quarter million tonnes of
retorted shale during each day of operation.
Although the retorted, or processed, shale represents the
largest by-product from oil shale retorting operations, results
from detailed studies indicate that it can be managed in an
environmentally acceptable manner. Laboratory and field tests
have demonstrated the following properties: compaction to 1600
3
kg/m, using normal vehicular traffic; cementation strength to
1480 kPa, using only retorted shale and optimum water; perme-
-7
abilities as low as 1 x 10 cm/s, using proper handling
techniques. In addition, tests have shown that dusting, auto-
-ignition, and leaching pose no special problems. These research
results indicate that properly managed retorted shale exhibits
the properties of a low-grade cement.
Although the nature o f r e t o r t e d shale c e r t a i n l y depends
upon the nature o f the g e o l o g i c a l d e p o s i t from which the raw o i l
shale was mined, i t depends, t o a l a r g e extent, a l s o upon the
r e t o r t i n g technology used t o process the raw o i l s h a l e . The
i n f o r m a t i o n presented i n t h i s paper i s obtained from the Paraho
O i l Shale Demonstration c a r r i e d out from 1973 t o 1976(1^).
The Paraho semi-works r e t o r t i s a c y l i n d r i c a l v e s s e l ,
having a 2.5 m i n t e r n a l diameter and i s capable o f p r o c e s s i n g
about 250-300 tonnes o f raw o i l shale p e r day. A schematic o f
the Paraho d i r e c t mode operations i s shown i n F i g u r e 1. Raw
shale, crushed and screened t o +1.0 cm t o -10.0 cm, enters the
top o f the r e t o r t , passes through the r e t o r t under the i n f l u e n c e
0097-6156/81/0163-0183$05.00/0

RAW SHALE
GAS
Preheat
Retort
Combust
Cool
GAS
RETORTED
SHALE
Figure 1. Paraho direct mode operation

13. HEISTAND Retorted 0;1
Shale Disposal Research 185
of g r a v i t y and c o n t r o l l e d by the grate mechanism a t the bottom.

The r e t o r t e d shale s t i l l contains many of the l a r g e r , +5.0 cm to
-10.0 cm, p i e c e s . T h i s range i n p a r t i c l e s i z e found i n the
r e t o r t e d shale enhances i t s s t r e n g t h p r o p e r t i e s and minimizes
d u s t i n g while h a n d l i n g . The Paraho process uses counter-current
flows — s o l i d s moving downward and gases moving upward. As the
shale moves downward through the r e t o r t , i t passes through four
d i s t i n c t zones as shown i n F i g u r e 1. The uppermost i s the m i s t
formation zone where the shale i s preheated by the r i s i n g gases
to r e t o r t i n g zone. In the next zone, the r e t o r t i n g zone, the
shale i s heated so t h a t i t s s o l i d organic component, kerogen,
breaks down to form gas, o i l and r e s i d u a l carbon, or coke. The
o i l and gas are swept upward out of the r e t o r t to the o i l - g a s
s e p a r a t i o n equipment.
The shale enters the combustion zone where most of the coke
i s burned to supply process heat. T h i s reduces the organic
carbon i n the r e t o r t e d shale to approximately 2 wt%. Air,
d i l u t e d with r e c y c l e gas, assures even d i s t r i b u t i o n of oxygen
across the shale bed and d i l u t e s the oxygen to c o n t r o l the flame
temperature. One important f e a t u r e of t h i s combustion zone i n
the Paraho process i s the t w o - l e v e l d i s t r i b u t i o n system. T h i s
system assures s u f f i c i e n t heat f o r r e t o r t i n g while keeping the
combustion temperatures low enough to a v o i d excessive carbonate
decomposition. T h i s carbonate decomposition wastes v a l u a b l e
heat and energy through endothermic r e a c t i o n s and produces a
r e t o r t e d shale higher i n water-soluble oxides which would
i n c r e a s e l e a c h i n g tendencies and cause a leachate higher i n pH
and s a l t content. The shale f i n a l l y enters the c o o l i n g zone
where i t i s cooled with r e c y c l e gas before i t i s discharged
from the r e t o r t . Within t h i s zone the r e t o r t e d shale r e a c t s
with most of the hydrogen s u l f i d e i n the r e c y c l e gas. This
reduces s u l f u r emissions when a p o r t i o n of t h i s gas i s u t i l i z e d
and forms a v a r i e t y of s u l f u r compounds i n the r e t o r t e d s h a l e .
These s u l f u r compounds reduce the oxide content and promote
s t r e n g t h through cementation r e a c t i o n s . More thorough d e s c r i p -
t i o n s of the Paraho technology and the composition of the
r e t o r t products have been p u b l i s h e d p r e v i o u s l y ( 2 _ / .
Most of the m a t e r i a l used i n the r e t o r t e d shale d i s p o s a l
r e s e a r c h was produced by the Paraho semi-works r e t o r t o p e r a t i n g
i n the d i r e c t mode o p e r a t i o n . Another mode of o p e r a t i o n , an
i n d i r e c t mode, was a l s o s t u d i e d . In the i n d i r e c t mode, a i r i s
not introduced i n t o the r e t o r t . I n t e r n a l combustion does not
occur; none of the organic carbon remaining on the r e t o r t e d
shale i s u t i l i z e d . Process heat f o r the i n d i r e c t mode o p e r a t i o n
i s s u p p l i e d by heating the r e c y c l e gas i n an e x t e r n a l heater.
During the recent Paraho o p e r a t i o n s , the p o t e n t i a l problem
of r e t o r t e d shale d i s p o s a l was recognized. A seven-stage
r e t o r t e d shale r e s e a r c h program, j o i n t l y supported by the U. S.
Bureau of Mines, was c a r r i e d out using both l a b o r a t o r y and f i e l d
s t u d i e s (4_) . H i g h l i g h t s of t h i s r e t o r t e d shale r e s e a r c h program

showed t h a t r e t o r t e d o i l shale, produced by the Paraho process,

can be e f f e c t i v e l y compacted and handled to produce strong and
water impervious s t r u c t u r e s (_5) . These d e s i r a b l e p r o p e r t i e s of
Paraho r e t o r t e d shale are b e l i e v e d due to the formation of a
low-grade cement by chemical r e a c t i o n s which occur d u r i n g
retorting.
In t h i s paper the chemistry of Paraho r e t o r t e d shale, the
nature of the thermo-chemical r e a c t i o n s t h a t can c o n t r i b u t e t o
i t s cement-like p r o p e r t i e s , and the chemistry of the leachates
obtained from p e r m e a b i l i t y s t u d i e s w i l l be presented. Although
c i v i l engineering i n f o r m a t i o n now e x i s t s which permits the
d i s p o s a l of r e t o r t e d shale i n an environmentally acceptable
manner, a b e t t e r understanding of the thermal r e a c t i o n s of
r e t o r t i n g and the chemical composition of r e t o r t e d shale may
suggest changes i n r e t o r t i n g operations which would f u r t h e r

l e s s e n any p o s s i b l y adverse environmental impact.
Experiment Design
Because the d i s p o s a l of r e t o r t e d shale i s , u l t i m a t e l y , a

f i e l d e x e r c i s e , t h i s paper w i l l d i s c u s s the experimental design
and data from f i e l d s t u d i e s which have been c a r r i e d out.
Laboratory experimentation and data w i l l be used to complement
the r e s u l t s of f i e l d s t u d i e s . Two f i e l d s t u d i e s , compaction and
p e r m e a b i l i t y , were c a r r i e d out during the Paraho r e s e a r c h
operations.
The f i e l d compaction s t u d i e s were c a r r i e d out i n a r e l a -
t i v e l y f l a t area, 2-3 km from the r e t o r t i n g operations (see
F i g u r e 2 ) . The compaction s i t e , measuring 55 m wide by 120 m
long, was d i v i d e d i n t o two s e c t i o n s . In one s e c t i o n the r e t o r t -
ed shale was p l a c e d dry; i n the other, optimum water was added
before placement. The m a t e r i a l was hauled d i r e c t l y from the
r e t o r t e d shale d i s p o s a l system and spread as soon as p o s s i b l e .
No problems with d u s t i n g or a u t o - i g n i t i o n were noted. The
m a t e r i a l was spread i n 20-30 cm l a y e r s and subjected to v a r i o u s
compactive e f f o r t s . Approximately 1200 m^ (15000 tonnes) of
r e t o r t e d shale was used i n these f i e l d compaction s t u d i e s .
The f i e l d i n f i l t r a t i o n s t u d i e s were c a r r i e d out near the
r e t o r t i n g o p e r a t i o n s . Two shallow ponds, 25 m diameter, were
constructed using techniques developed during the e a r l i e r f i e l d
compaction s t u d i e s (see F i g u r e 3). Both ponds were constructed
out of Paraho r e t o r t e d shale p l a c e d i n l a y e r s to an o v e r a l l
t h i c k n e s s about 1 m. Both ponds had s l o p i n g s i d e w a l l s to
obviate w a l l e f f e c t s and to e l i m i n a t e any wall-bottom i n t e r f a c e .
One pond was c o n s t r u c t e d with dry r e t o r t e d shale using l i g h t
compaction. The other pond was constructed of r e t o r t e d s h a l e ,
mixed with optimum water, and p l a c e d using heavy compaction.
A f t e r c o n s t r u c t i o n , both ponds were f i l l e d with water and the
i n f i l t r a t i o n r a t e s were measured u s i n g s t a f f gauges and flows
through the d r a i n l i n e s .

13. HEISTAND Retorted Oil Shale Disposal Research 187
Figure 2. Field compaction area
Figure 3. Field infiltration area

R e s u l t s and Discussion
Compaction. The f i e l d compaction s t u d i e s confirmed e a r l i e r

l a b o r a t o r y s t u d i e s r e g a r d i n g the e f f e c t of compactive e f f o r t ,
moisture a d d i t i o n , and aging on d e n s i t y and s t r e n g t h . Shown i n
F i g u r e 4 i s the r e l a t i o n s h i p of compactive e f f o r t on the d e n s i -
t i e s of r e t o r t e d s h a l e . At l e a s t three i n - p l a c e d e n s i t y
measurements were made i n each l a y e r . Results show t h a t d e n s i -
3
t i e s averaging 1400 kg/m (about 95 l b / c u . f t . ) can be achieved.
Optimum water i s needed to achieve optimum s t r e n g t h . The
a d d i t i o n of water does not improve c o m p a c t a b i l i t y . The s t r e n g t h
of the compacted r e t o r t e d shale was measured u s i n g unconfined
compression(6). The r e l a t i o n s h i p between t h i s s t r e n g t h data and
added moisture a t v a r i o u s seasoning times i s shown i n F i g u r e 5.

The remarkable s t r e n g t h i n c r e a s e obtained with the a d d i t i o n of
optimum water i n d i c a t e s the occurrence of some s o r t of cementing
r e a c t i o n . Further evidence of t h i s cementing r e a c t i o n i s
apparent where the compressive s t r e n g t h gains with aging. Aging
60 days a f t e r the a d d i t i o n of optimum water produced compressive
strengths of n e a r l y 1500 kPa (205 p s i ) . The r e t o r t e d shale
produced by i n d i r e c t heat operations shows no s t r e n g t h .
Infiltration. I n f i l t r a t i o n data f o r the two ponds are
l i s t e d i n Table I . A l s o l i s t e d are i n - p l a c e and core d e n s i t i e s ,
TABLE I
FIELD INFILTRATION ANALYSIS
Pond I Pond I I
Initial Cores Initial
Moisture, wt% 22.1 18.5 0.0
3
Density, Bottom kg/m 1602 1697 1474
3 1394
1602
Sides kg/m
1482
Strength, kPa -6
0.3 0.6 2000
P e r m e a b i l i t y , cm/sec x 10
moisture contents, and compressive s t r e n g t h s . These data show
t h a t Pond I (high compaction, optimum water) was w e l l -
constructed. D e n s i t i e s matched those achieved i n e a r l i e r l a b o r -
a t o r y and f i e l d compaction t e s t s . The s t r e n g t h , measured i n a
core sample (1480 kPa), exceeded those achieved d u r i n g those
e a r l i e r t e s t s . The f i e l d p e r m e a b i l i t y , as measured by s t a f f
gauge, when c o r r e c t e d f o r i n i t i a l a b s o r p t i o n and normal evapora-
t i o n , approaches the value obtained from a n a l y s i s of the core
7
(6 x 10" cm/s). A c t u a l i n f i l t r a t i o n from the h i g h l y compacted
7
pond shows the permeation r a t e to be 3 x 10~ cm/s.
Pond I I , r e c e i v i n g only l i g h t compaction and no added water,
shows a p e r m e a b i l i t y r a t e o f 2 x 10~4 cm/s. Although the

COMPACTION
- HEAVY
o -STANDARD
i 1 r T
30
10 15 20
MOISTURE CONTENT ADDED (% by dry weight)
U.S. Bureau of Mines
Figure 4. Compaction test results. Paraho retorted shale, semiworks plant-

direct heat; 1.5-in. maximum size fraction.
-HEAVY COMPACTION
DENSITY = 98.7 pcf
x(205)
200 -
150 - DIRECT HEAT
-STANDARD COMPACTION
> DENSITY = 92.5 pcf
% too
50 - INDIRECT HEAT
L
STANDARQ COMPACTION
DENSITY = 92.5 pcf
-(10)
-i 1 1 1 1 r -
20 40 60 80 100 120
OAYS CURING AT 125° F
Figure 5. Compression test results. Paraho retorted shale, semiworks plant;

.75-in. maximum size jraction.

p e r m e a b i l i t y of t h i s m a t e r i a l i s q u i t e high, e f f l u e n t s c o u l d be
contained i n a d i s p o s a l area u s i n g p r o p e r l y - p l a c e d , w e l l -
c o n s t r u c t e d m a t e r i a l such as used i n Pond I . Even though the
l o o s e l y compacted Pond I e x h i b i t e d a high p e r m e a b i l i t y r a t e , an
a d d i t i o n a l f i e l d experiment i n d i c a t e d t h a t p e r m e a b i l i t y may not
pose a s e r i o u s problem. A f t e r Pond I I ( l i g h t compaction) had
d r i e d thoroughly f o r s e v e r a l months f o l l o w i n g the f i e l d i n f i l -
t r a t i o n t e s t , a s p e c i a l t e s t was conducted. The surface was
sprayed with 17,400 & of water to represent a r a i n f a l l of 5 cm
i n 30 minutes. No e f f l u e n t occurred f o r n e a r l y one f u l l day. A
small seepage began the second day and continued f o r two days.
Only 7 £ were c o l l e c t e d from the d r a i n p i p e . E s s e n t i a l l y a l l of
the simulated r a i n f a l l was l o s t to a b s o r p t i o n and subsequent
evaporation. T h i s i n d i c a t e s t h a t l e a c h i n g and p e r m e a b i l i t y may
not be a problem f o r Paraho r e t o r t e d shale, even when l i g h t l y

compacted, because even heavy r a i n f a l l w i l l not penetrate the
p i l e to s i g n i f i c a n t depths.
Chemical and P h y s i c a l P r o p e r t i e s . Paraho r e t o r t e d shale i s
d e s c r i b e d according to standard s o i l s c l a s s i f i c a t i o n as a
silty-gravelly material{4). A s i z e d i s t r i b u t i o n diagram i s
presented i n F i g u r e 6. Some of the f a v o r a b l e p r o p e r t i e s of the
r e t o r t e d shale i s a t t r i b u t e d to t h i s s i z e d i s t r i b u t i o n - l i k e a
good aggregate mix, t h i s m a t e r i a l has the proper r a t i o of f i n e s
to l a r g e r s i z e d p i e c e s so t h a t v o i d s between the l a r g e r
p i e c e s are f i l l e d with f i n e s . This r e l a t i o n s h i p increases
d e n s i t y , promotes s t r e n g t h , and reduces d u s t i n g and e r o s i o n .
The chemical composition of r e t o r t e d shale depends on the
composition of the raw shale and the r e t o r t i n g p r o c e s s . The
m i n e r a l composition of the Green R i v e r shale used i n the Paraho
operations c o n s i s t s of a complex mixture o f m i n e r a l s . These
i n c l u d e : carbonates (50%), c l a y s (40%), quartz (8%), and s u l -
f i d e s and others (2%). The p r i n c i p a l carbonate m i n e r a l
undergoing thermal r e a c t i o n s during the normal r e t o r t c o n d i t i o n s
i s dolomite (CaC03*MgC03), or more p r o p e r l y f e r r o a n (CaC03«Fe , x
M c o
9 l - x 3 ) where a p o r t i o n of the magnesium i s r e p l a c e d by i r o n .
I t i s b e l i e v e d t h a t f e r r o a n undergoes the f o l l o w i n g chemical
r e a c t i o n during normal r e t o r t i n g c o n d i t i o n s :
(1) Ferroan + Heat — • Calcite (CaC03) + Magnesia (MgO)

+ FeO + CO2
Many s t u d i e s have been made concerning the mean chemical

a n a l y s i s o f Paraho r e t o r t e d s h a l e ( 7 ) . Although i t i s important
to know t h i s chemical composition, i t i s not h e l p f u l i n a s s e s s -
ing the components r e s p o n s i b l e f o r the cement-like p r o p e r t i e s .
Much emphasis has been p l a c e d upon the formation o f r e a c t i v e
oxides, such as f r e e lime and magnesia, from carbonate decompo-
s i t i o n . Although f r e e lime can be formed under l a b o r a t o r y
c o n d i t i o n s ( 8 ) , i t has not been detected i n the r e t o r t e d shale
used i n the f i e l d s t u d i e s . Although f r e e lime was not detected,

SILT-CLAY SIZE
^ SAND SIZE • a GRAVEL SIZE

(STANDARD SIEVE SERIES) (INCHES)
#200 #100 #50 #30 #16 #8 #4 | | l£
I I 100
Figure 6. Gradation data. Paraho retorted shale, semiworks plant—direct heat;

1.5-in. maximum size fraction.

192 OIL SHALE, TAR SANDS, AND R E L A T E D MATERIALS
magnesia has been found i n Paraho r e t o r t e d s h a l e . S u l f u r

minerals, known to e x h i b i t cement-like p r o p e r t i e s , have been
found i n Paraho r e t o r t e d shale (<4) . These i n c l u d e : anhydrite
(CaS0 ), bassanite (CaS04-0.5H20), gypsum (CaS04-2H 0). These
4 2
s u l f u r minerals present i n the r e t o r t e d shale may be there as a

r e s u l t of the raw shale composition or as a r e s u l t of absorption
of hydrogen s u l f i d e by the r e t o r t e d s h a l e . I t i s b e l i e v e d t h a t
the magnesia and s u l f u r minerals are r e s p o n s i b l e f o r the cement-
l i k e p r o p e r t i e s of the Paraho r e t o r t e d s h a l e .
Many s t u d i e s have been c a r r i e d out concerning the a n a l y s i s
of leachates from r e t o r t e d s h a l e . R e s u l t s from these s t u d i e s
are h i g h l y dependent upon the procedure t h a t i s employed. L i s t e d
i n Table I I are some of the leachate data obtained during the
TABLE I I
INITIAL LEACHATE COMPOSITION
Loose F i l l Compacted
6
Permeation Rate, cm/sec 3.0xl0" 5
3.2xl0~
pH, pH Units 7.5 7.8
TDS, ppt 6.9 9.2
Calcium 407 157
Magnesium 47 37
Iron 0.05 0.07
Aluminum < 0.05 < 0.05
Silicon 5 10
Sodium 1300 3200
Potassium 325 500
Chloride 580 790
Sulfate 3330 4320
Carbonate 19 66
A l l data i n mg/£ except as noted.
r e t o r t e d shale s t u d i e s ( 4 ) . As the compaction i s i n c r e a s e d , the

column experiments show t h a t the leachate c o n c e n t r a t i o n i s
i n c r e a s e d , but the t o t a l amount leached i s decreased. Another
experiment showed t h a t l e a c h i n g diminishes as the leachate i s
r e c i r c u l a t e d . T h i s i n d i c a t e s t h a t l e a c h i n g should not proceed
to great depths i n a r e t o r t e d shale d i s p o s a l area. Batch exper-
iments i n d i c a t e t h a t about 1 wt% of m a t e r i a l i s e x t r a c t e d from
the r e t o r t e d s h a l e . T h i s meets e s t a b l i s h e d engineering
standards (_4) .

Data shown i n Table I I c o n s i s t s o f m a t e r i a l s which can

c o n t r i b u t e t o s a l i n i t y , t o x i c elements had not been considered.
More r e c e n t l y , the U. S. Environmental P r o t e c t i o n Agency has
proposed an e x t r a c t i o n procedure t o determine hazardous wastes.
Results obtained using the proposed EPA e x t r a c t i o n procedure are
shown i n Table I I I f o r Paraho r e t o r t e d s h a l e . The low
TABLE I I I
LEACHATE DATA
EPA EXTRACTION
Arsenic < 0.1 ppm
Barium < 10 ppm
Cadmium < 0.05 ppm

Chromium < 1 ppm
Mercury 14 ppb
Lead 220 ppb
Selenium 23 ppb
Silver 30 ppb
concentrations shown i n Table I I I i n d i c a t e t h a t t h i s m a t e r i a l

i s not a hazardous waste as i n d i c a t e d by the U. S. EPA. These
low concentrations o f t o x i c m a t e r i a l s found i n leachates from
Paraho r e t o r t e d shale using the proposed U. S. EPA e x t r a c t i o n
procedure would not be i n c r e a s e d t o hazardous l e v e l s i f a l l o f
these m a t e r i a l s normally present i n the r e t o r t e d shale were
solubilized.
Conclusions
D e t a i l e d l a b o r a t o r y and f i e l d s t u d i e s have shown t h a t

Paraho r e t o r t e d shale can be compacted e a s i l y ; i s not subject t o
d u s t i n g , e r o s i o n , or a u t o - i g n i t i o n ; and can be handled t o create
s t r u c t u r e s o f very low p e r m e a b i l i t y . A b a s i s f o r these b e n e f i -
c i a l p r o p e r t i e s can be found, i n p a r t , by an examination o f the
chemical and p h y s i c a l p r o p e r t i e s o f the r e t o r t e d s h a l e . F o r
example, i t i s b e l i e v e d t h a t the strengths achieved are caused
by the h y d r a t i o n o f magnesia, r e a c t i o n s o f the gypsum m i n e r a l s ,
and the compaction o f the s i l t y - g r a v e l mix.
However, more s t u d i e s are needed t o f u r t h e r d e f i n e these
chemical and p h y s i c a l p r o p e r t i e s . Results from these a d d i t i o n a l
s t u d i e s can f u r t h e r reduce the p o s s i b i l i t y o f any p o t e n t i a l l y
adverse impact from r e t o r t e d shale d i s p o s a l .

194 OIL SHALE, T A R SANDS, A N D R E L A T E D MATERIALS
Acknowledgement
The r e t o r t e d shale r e s e a r c h s t u d i e s d i s c u s s e d i n t h i s paper

were c a r r i e d out a t the U. S. Department o f Energy A n v i l P o i n t s
Research F a c i l i t y l o c a t e d on the Naval O i l Shale Reserves Nos. 1
and 3 near R i f l e , Colorado.
Literature Cited
1. Pforzheimer, H., Jr., "The Paraho Oil Shale Demonstration -
A 1975 Progress Report," Oil Shale - Tar Sand Symposium,
American Institute of Chemical Engineers, National Meeting,
Los Angeles, CA, November 1976.
2. Jones, J. B., Jr., "The Paraho Oil Shale Retort," 9th Oil
Shale Symposium, Colorado School of Mines, Golden, CO, 1976.

3. Jones, J. B., Jr. and Heistand, R. N., "Recent Paraho
Operations," 12th Oil Shale Symposium, Colorado School of
Mines, Golden, CO, 1979.
4. Holtz, W. G., "Disposal of Retorted Shale from the Paraho
Oil Shale Project," U.S. Department of Interior, Bureau of
Mines, J0255004, 1976.
5. Heistand, R. N. and Holtz, W. G., "Retorted Shale Research,"
13th Oil Shale Symposium, Colorado School of Mines, Golden,
CO, 1980.
6. American Society for Testing and Materials, "ASTM Standards,"
Parts 10 and 19, ASTM, Philadelphia, PA, 1974.
7. Heistand, R. N., Atwood, R. A., and Richardson, K. L.,
"Paraho Environmental Data; Part I, Process Characterization;
Part II, Air Quality; Part III, Water Quality," U. S.
Department of Energy, DOE/EV 0086, UC-66e & 91, 1980.
8. Heistand, R. N., Jones, D. B. and Morriss, L. M., "Free Lime
in Retorted Shale," Energy Sources, 4, 195-202, 1978.
9. U.S. Environmental Protection Agency, "Hazardous Waste
Management System," Federal Register, 45, (98), 33063-
33285, May 19, 1980.

14
An Investigation into the Potential Economics of
Large-Scale Shale Oil Production (1)
BEN C. BALL, JR.
Adjunct Professor of Management and Engineering, Massachusetts Institute of
Technology, Cambridge, MA 02139
If there is any aspect of energy upon which most informed

people agree, it is that our nation's increasing reliance on
foreign petroleum is not good for the United States. The unfavor-
able nature of that dependence may be seen as arising from
national security, foreign policy considerations, and as stemming
from strictly economic effects.
There is less agreement about which alternatives are less
objectionable for the United States than importing so much oil.
One broad alternative is to increase supplies of domestic substi-
tute liquids like coal liquids or/and shale oil.
The debate over the alternatives has been exhaustive and
public. Unhappily, all the alternatives seem to have significant
difficulties associated with them.
Interest in shale oil is motivated largely by the enormous
size of oil shale deposits in the United States. A further reason
for interest in oil shale processing is that processes for the
production of liquid fuels from oil shale appear cheaper than
those that start from coal (2). This is primarily because oil
shale contains a very much higher ratio of hydrogen to carbon, and
process costs tend to correlate directly with the increase in the
net H/C ratio required. This cost advantage is somewhat offset by
increased materials handling required by shale. But, on balance,
it is expected that most liquid synfuels will be produced from
shale (3).
InTustry seemingly does not regard shale oil ventures as
attractive now. Dissatisfaction is most frequently expressed in
terms of "non-economic" barriers - innumerable permits, changing
environmental regulations, tax and pricing uncertainties, lease
limitations, water rights c o n f l i c t s , and legal challenges. The
crucial barrier is the fact that shale oil simply costs more than
imported o i l . If shale oil cost l e s s , we would probably see more
determined and more successful efforts by both industry and
government to surmount the non-economic barriers. ("Non-economic"
is shorthand, of course; there are costs, often large ones,
resulting from those barriers.)
0097-6156/81/0163-0195$06.75/0

Industry's continued interest in shale o i l , despite its

current unattractiveness, is sustained primarily by the belief
that the real cost of imported oil will continue to rise and
ultimately surpass shale oil at some unpredictable future date.
Government assistance is sought by industry before that date on
the grounds that: a) there is a public value, which cannot be
directly captured by a company undertaking a shale oil venture
now, in reducing imported oil and b) there is need for an immedi-
ate start in order to have significant shale oil production in
place when the cost curves do intersect.
A secondary reason for industry's continued interest is the
belief that the real cost of producing shale oil may be reduced
through technological improvement. (There are quite different
views on the prospects for reducing cost through improvement of
current technologies. For example, Merrow ("Constraints on the

Commercialization of Oil Shale", Rand/R-2293-D0E, September, 1978)
is pessimistic, but Hutchins ("Oil Shale 1979", presented at the
Twelfth Annual Oil Shale Symposium, A p r i l , 1979) is optimistic.)
That belief raises the issue of how the process of technological
change occurs, and what the consequences might be for two d i f f e r -
ent paths of the shale oil industry. One set of consequences
would result from the industry following the usual evolutionary
path; a different set of consequences would result from an
"industry-in-place" path.
Shale oil studies in both the private and public sectors have
emphasized what we call here an "evolutionary" approach. Costs
are estimated for a single plant by looking at one installation as
a totality within i t s e l f , not as part of a complex, such as an
industrial park, or as a shale oil industry. It is not clear
whether the "evolutionary" approach is an oversimplification that
tends to result in costs that are too high or too low, on the
average, for a whole industry. In some ways, this approach is the
cheapest. For example, the highest quality shale would be mined
f i r s t , and the lowest-cost water would be used f i r s t ; local en-
vironmental pollution would be lowest with the f i r s t plants;
demand for labor and steel would be limited and would not drive up
price levels.
However, other economies would result from the existence of a
cluster of plants. For example, a separate grass-roots community
need not be built for each plant - one larger (lower unit cost)
community could serve several plants; product transportation costs
would be lower for an industry pipeline than for any mode scaled
for a single plant; unit equipment manufacturing costs would be
lower i f many units were replicated.
This latter set of p o s s i b i l i t i e s encourages us to raise the
question of the economics of an industry, once in place. Might
not a shale oil industry be the beneficiary of economies that
simply would not be applicable to a single plant. Might these
economies by significant? Might an industry be viable whereas a

14. B A L L Large-Scale Shale Oil Production 197
plant or a few plants might not be? Investigating the f r u i t f u l -

ness of this line of thinking is the purpose of this study. The
questions we are raising are of the kind one might ask when re-
flecting on U.S. shipbuilding dynamics early in World War II: the
decision to build several Liberty ships a week resulted in
structural and technical changes that permitted economies that
simply were not possible when shipbuilding was considered a one-
at-a-time process.
The present study attempts to contribute to the consideration
of oil shale as a serious option by identifying technological
opportunities to reduce substantially the costs of producing shale
oil on a large scale, such as 2-5 million barrels/day as opposed
to a small scale of an individual shale oil project of 50-100
MB/D. These opportunities involve the application of existing
technology which has not been seriously considered on a small

scale and the development of new technology which looks reasonably
susceptible to successful development and which would have im-
portant impact on a large scale. To focus on the questions
suggested above, we note but do not consider a number of other
important issues, though we recognize that they may well be con-
t r o l l i n g factors in the development of a shale oil industry in the
United States.
• We do not consider how the industry will be b u i l t , but
rather consider i t already in place at steady state; in
chemical terms, we are concerned with equilibrium rather
than kinetics.
• We consider only the economic consequences of technologi-
cal alternatives; we do not evaluate other alternatives,
such as financial or tax devices for example, to reduce
cost.
• We do not attempt to reevaluate process economics or make
fine comparisons among various competing processes; we
have made an effort to obtain the latest data available
from the most active promoters, accepting their data at
face value.
• We assume that the environmental specifications which
must be met are those presently established.
• We do not take account of unique project features In-
applicable on a large scale, for example, the recovery
for sale of alkaline minerals along with the shale.
• We do not compare shale oil to other alternatives for
reducing oil imports.
• We do not evaluate current or potential government
policies affecting shale.
In other words, in this study we deliberately take a narrow tech-
nologist's view of the potential for reducing costs through
technology in a large, distant-future shale oil industry.

Background
Oil shale processing has been practiced on an industrial

scale since the 1860's. Much "coal o i l " produced in the
United States before the discovery of petroleum was in fact shale
oil. Production of 2,500 B/D was maintained by the Scottish oil
shale industry for long periods of time over its 100-year
history. A Manchurian oil shale industry, begun in 1929, reached
outputs of 35,000 B/D while under Japanese control during World
War II. The Chinese expanded the Manchurian operation, and output
during the Korean War is believed to have been as high as 40,000
B/D (4_).
During the 1960's, shale oil R&D was being carried on by
several of the major oil companies, and by The Oil Shale Company
(TOSCO), newly formed expressly to become a major factor in a new

shale oil industry. With the announcement of the sale of U.S.
Government shale leases in Utah and Colorado in early 1974, the
level of R&D was temporarily increased somewhat.
This lease sale, taking place at the height of the 1973-74
Arab oil embargo, e l i c i t e d over 1/2 b i l l i o n dollars in bids from
several major oil companies plus TOSCO. These companies appear to
have been acting largely on the belief that some combination of
the following conditions would obtain: (1) world oil prices would
continue to r i s e , and the cost of shale oil production would then
be at a level that would make the industry viable at world oil
prices, and/or (2) shale oil would be "needed", and therefore
prices would be paid that would make its production profitable,
regardless of the market prices and costs, and/or (3) the govern-
ment would take whatever steps might be necessary to ensure that
the necessary technology and regulatory environment would be
available, and that Federal subsidies in some form would be avail-
able i f needed for construction of early plants (5), and/or (4)
improvements in technology or reduction of "non-economic" costs
would reduce the real costs of shale o i l .
Since the lease sale, each of the lessees has been conducting
engineering and f e a s i b i l i t y studies, studying environmental
impact, e t c . , but only modest progress has been made in either the
technology or the conceptual development of the shale oil industry
with the possible exception of Occidental's modified in-situ
process.
Techno!ogy
Oil shale processing technology is simple in principle. Oil

shale contains a carbonaceous material called "kerogen". When oil
shale is retorted, i . e . , heated to about 900°F, the kerogen decom-
poses (pyrolyzes) to y i e l d an oil (raw shale o i l ) , gas, and
residual carbon which remains in the shale. The total solid
residue from retorting is known as spent shale. Typical, "rich"
U.S. shales under consideration yield about 20 to 40 gallons of
raw shale oil per ton of rock heated.

Research has been done on other ways of recovering shale oil

from its rock, for example by extraction with solvents or by the
action of microorganisms. No method other than heating has shown
any real potential for commercial application.
The retorting of oil shale may be done in two general ways:
above-ground or i n - s i t u . For above-ground retorting, the shale
rock is mined, crushed to appropriate sizes, and heated in steel
vessels of various configurations located on the surface. For in-
situ retorting, the shale rock is heated while i t remains under-
ground. (Occidental Petroleum's Modified In-Situ process,
however, requires at least 20% of the shale resource to be mined
and brought to the surface where i t can be retorted conventional-
ly.) Many variations of both above-ground and in-situ retorting
have been investigated. Each variation has its advantages and
disadvantages. No variation has been tested on a commercial scale

in the United States although both above-ground and in-situ
processes have been operated commercially in Scotland. No do-
mestic shale oil project has ever exceeded 700-800 B/D - a number
which can be compared with our current oil imports of 7-8,000,000
B/D.
Regardless of the retorting method used, the resulting raw
shale oil is ordinarily "upgraded" to reduce contaminants -
nitrogen, sulfur, and metals - so that i t may then be processed
further by the same techniques used to process crude petroleum.
The relatively small amount of oil recovered - roughly 10-15%
by weight of the shale rock heated - means that there are sub-
stantial technical problems resulting from the sheer volume of
rock that must be mined and transported to a commercial-scale
processing plant which uses above-ground retorting. Furthermore,
since the shale expands by as much as 50% during crushing, the
volume of spent shale to be disposed of is greater than the volume
of shale that was mined. Spent shale also often has a high
content of alkaline minerals, a factor that must be considered in
the disposal process. Interest in in-situ retorting stems largely
from the fact that i t can avoid handling much or all of the shale
rock and spent shale handled in above-ground processes.
Oil shale processing currently requires about one to four
barrels of water per barrel of shale oil produced. This water is
used in the shale processing i t s e l f as well as for dust control,
but the largest single amount, up to half or more of the t o t a l , is
usually for environmentally acceptable disposal and revegetation
of the spent shale. Water availability is a problem in the arid
shale regions of the West, and opinions about its importance as a
constraint on production are often expressed with intense
emotion. As a result, one typical conclusion is that "...water is
estimated to be the single most limiting restraint (on shale
production)." (6J However, the same source points outs that
Colorado water can be desalinated for about 5$/barrel (7_); at the
extreme l i m i t , fresh water can be brought to the area from 1000
miles away for well under $l/barrel (8j. Also, there are other

trade-offs between cost and level of water consumption. Thus, the

cost of water is significant but need not be an absolute economic
barrier i f institutional regulations are overcome.
Technological Change
It is convenient to think of technological change occurring

in five stages termed: (1) Invention, (2) Development, (3) Intro-
duction, (4) Diffusion, and (5) Maturity. These stages are
described in detail in the Appendix. The normal evolution of
technology - shale oil technology as well as other technologies -
would progress through each of these stages. Thus, a shale oil
industry in a Maturity phase would make use of those mining,
retorting, and upgrading technologies which had proved superior to
competing technologies during extended commercial-scale operation

in the Introduction and early Diffusion phases.
If an industry were put in place in some unspecified way, the
Introduction and early Diffusion phases would be skipped. As the
Appendix points out, the primary purpose of those phases is to
narrow the range of cost uncertainty rather than to reduce the
probable cost, although technical changes which result in reduced
(or increased) cost certainly occur in those phases. Thus, the
later Diffusion and Maturity phases would be entered, although
with less certainty that the best technologies were being used.
A crucial question to be faced is the probability of these
economies of an industry in place being greater than the disecono-
mies of skipping some intermediate stages. In general, the
economies that might result from the industry-in-place approach
f a l l into two categories. One is the economy of scale. An indus-
try can solve problems more economically than individual plants
and can justify the development of technology not otherwise
supportable. Examples of economy-of-scale savings would include
(as i l l u s t r a t i o n s , not proposals):
• Mining. All or much of the Piceance Creek Basin in
Colorado might be open-pit mined, with the resulting oil
shale distributed to individual retorting s i t e s .
• Combinations. An industry basis might better accommodate
an optimum balance between surface and in-situ retorting.
t Infrastructure. An industry might support larger, more
economical c i t i e s .
• Transportation. Pipelining the product out, for example,
to existing refineries, might offer cost savings.
• Spent shale disposal may be more economical on an indus-
try basis.
• Environmental Impact Statement. A simple EIS for the
entire industry may well be more cost-effective than
separate studies and statements for each plant.
• Environmental control . ( e . g . , particulates, N0 , S0 ) may
X 2
be economical for an industry.

• Water supply and disposal could be much more practical

for an industry, through such means as bringing in water
from remote sources.
The other possible source of cost reduction l i e s in the
dimension of mass production economies for the suppliers to the
shale oil industry. If suppliers were to know and could count on
the construction of an industry of, say, 5,000,000 B/D over a
relatively short time frame, say 8 to 15 years, then perhaps
economies could be realized through the planned mass production of
retorts, mining machinery, pipe and valves, etc.
Mining Opportunities
Significant cost savings should be achievable in the mining

operations necessary for producing shale oil on the scale con-
sidered here. However, the enormity of a mining operation moving
3 to 8 million tons per day of rock calls for innovative materials
handling approaches by either identifying old technologies appli-
cable to this new situation or developing new technologies for
it. As an example, i f labor productivity were not increased over
the maximum current level of about 150 tons/man-shift in under-
ground mines, the industry would need 20,000 to 50,000 underground
miners - and supplying just that part of the total labor force
would be an enormous problem.
The most obvious way to increase mining productivity is to
mine on the surface rather than underground. Therefore, proposals
to surface mine all or major portions of the Piceance Creek Basin
should be reevaluated since that may be the most practical way to
produce enough o i l , especially considering the d i f f i c u l t y of
attracting mining labor to the region.
A related proposal would examine the possibility of develop-
ing "surface" mines underground, i . e . , large underground mines
with perhaps 100-foot ceilings excavated as though they were on
the surface.
There appear to be no technological barriers to the develop-
ment or use, or both, of mining equipment on a much larger scale
than now planned. Very large equipment - conspicuously, large-
scale excavators and high-speed conveyors - has been built and
operated economically, for example in surface lignite mining in
Germany. Surface mining there involves stripping 900 feet (soon
to be 1,600 feet) of overburden; that compares with a maximum
Piceance Creek Basin overburden of about 1,800 feet overlying a
maximum shale strata thickness of about 1,300 feet. Although
there are no obvious technical limitations on increasing the size
of mining equipment, there are two caveats: (1) size increases
have to be coordinated among all elements of the mining system,
and (2) continued increases in size do not invariably result in
decreases in cost, i . e . , some mining systems have shown that total
costs (including maintenance, service factor, etc.) may be a
minimum at some size less than the largest sizes tested.

Retorting 1n-s1tu i s , 1n principle, the oil recovery strategy

with potential for reducing the environmental problems and solids-
handling costs of surface retorting. The key to In-situ retorting
is "mining" in the sense of making the rock in place permeable so
that heat can be introduced (or created) pervasively and oil (and
gas) withdrawn e f f i c i e n t l y . In practice, of the various in-situ
methods hypothesized or tested, only modified in-situ (In which
some rock is removed to provide void volume so that the remaining
rock can be fragmented and made permeable) has commercial promise
on a wide scale.
Continuous processes for in-situ or conventional mining to
replace cyclic drill1ng/blasting/muck1ng would Improve labor
productivity and safety. Tunneling or honeycombing machines
capable of handling the hard (relative to coal) shale rock are
needed. Improved mining and controlled rubbling both depend on a

better understanding of rock mechanics Including the special case
of rubbling to a controlled void in a confined volume.
A combination of in-situ and surface retorting may make best
use of the shale resource in place. One can think of surface
retorting the mined-out rock from a primary in-s1tu operation, or
of in-situ retorting the rock l e f t behind after underground mining
for a primary surface operation.
D i f f i c u l t environmental problems are associated with large-
scale mining operations and will require solution. Coping with
large aquifers above, between, and below shale strata 1s a major
problem which may be easier to cope with on an industry scale
(e«9*» by grouting or dewatering on a large scale) than on a
project-by-project basis. Fugitive dust is another problem,
especially with surface mines. The crucial problem of spent shale
disposal may be eased by high-temperature retorting which seems to
reduce both the volume of and the soluble alkalis in the spent
shale.
Several more speculative suggestions can be made for tech-
nologies capable of reducing mining cost significantly. A whole
new in-situ system is possible. Rubbling by new methods -
hydraulic cone fracture, chemical or nuclear techniques, mechani-
cal leverage - can be hypothesized. Underwater mining could be a
way of coping with major aquifer problems.
Retorting Opportunities
In-situ retorting 1s regarded as primarily a mining problem

(see previous section) rather than a retorting problem in the
usual sense. Most, though not a l l , improvements in in-situ
retorting are expected from improved methods of preparing the
retorts (tunneling, rubbling, etc.) rather than from Improved
methods of operating those retorts.
So far, only heating has been demonstrated to have potential
for recovering oil from shale on a commercial scale. Exploratory
R&D on other recovery techniques such as action of microorganisms,

solvent extraction, and RF heating is not regarded as promising.

Beneficiation or enrichment of retort feed by some mechanical or
other means may be worth investigating.
Opportunities for improved technology in heated retorts, both
specific suggestions and identified needs, can be c l a s s i f i e d in
four groups shown below.
1. Economies of scale in retorting seem most likely i f a
major increase in production can be obtained in each retort train
(or module) rather than by replication of small modules. The
retort technology that appears capable of very large single-train
throughputs (based on demonstrated solids-handling capacity in
refining processes) is fluidized bed technology. Fluidized bed
technology for shale retorting was investigated briefly and then
abandoned many years ago and we are not aware of any current major
projects. Nevertheless, advances in that technology, especially

for operations with higher gas velocities and larger particles,
justify another evaluation.
Operating under pressure is another general technique for
increasing throughput in both conventional and fluidized bed
retorts; i t deserves evaluation.
2. Good u t i l i z a t i o n of resources in place means that
retorting processes should be able to handle shales of different
richness, crushed to different sizes, and located at different
places and depths. Retorting of local coal along with shale rock
may be advantageous in special circumstances. Thinking about
retorting in this broader context means that different types of
both surface and in-situ retorts will be employed in an optimum
large industry and that there is value in developing retorting
systems which have inherent feed f l e x i b i l i t y .
3. In addition to having f l e x i b i l i t y to accommodate d i f f e r -
ent feeds, a retorting system could profitably have f l e x i b i l i t y to
make different mixes of products including o i l , gas, and steam (or
electric power). The optimum product mix would differ for differ-
ent technologies, locations, and degrees of integration into the
surrounding industry. Different retorting atmosphere gases (Ho,
02/steam, etc.) offer one means by which product slate can Be
varied. Accessory equipment like f l u i d bed combustors may make i t
possible to convert energy in an economical and environmentally
acceptable manner from one form to another more useful one, say
coal or lean shale to low-Btu gas or carbon on spent shale to
steam or electric power.
4. Costs for controlling or disposing of waste streams in an
environmentally acceptable way are significant 1n shale oil pro-
duction. Improved retorting technologies can help reduce those
costs. Retorting at higher temperatures reduces soluble alkali in
spent shale and thus reduces long-term leaching problems after
spent shale disposal. Investigation of this effect in surface
retorting should be undertaken. Cheaper treatment of contaminated
water streams, from mining or retorting, with the objective of
reuse or discharge, should be possible.

High-temperature retorting can also reduce the volume of

spent shale to about (or perhaps even less than) the volume of the
original rock, thus making i t easier to dispose of all the spent
shale by returning i t to the mine. However, high-temperature
retorting does incur costs because of losses in thermal efficiency
and increased gaseous emissions.
The alkalinity of the spent shale suggests possible use in
gas scrubbers to remove acidic sulfur compounds.
Clean-up and use of low Btu gas from in-situ retorting is a
particularly expensive operation. Cheaper "one-step" technologies
are needed. Improved technology of this type would have a large
impact.
In addition to the specific suggestions and needs identified
above, there are obvious opportunities for cost-saving during
equipment manufacturing by: (a) mass production methods for r e p l i -

cated pieces of equipment, and (b) shop fabrication replacing
f i e l d fabrication wherever practical.
Upgrading Opportunities
There is l i t t l e need to spend much time discussing the tech-

nology of upgrading raw retort shale oil to refinery feedstock.
This opinion is based on several assumptions:
• End products of shale oil will be similar to the current
end products of petroleum in quality characteristics,
even i f not necessarily in volume distribution.
• Conversion of raw shale oil to end products will occur at
existing petroleum refinery s i t e s , or at new refineries
generally similar (in technology) to existing ones, but
tailored to shale oil feed.
• Conversion will be carried out primarily by existing
petroleum refining companies or combinations of existing
companies who already have expertise.
• Large-scale production of shale oil involves very long
lead times and, therefore, refiners will have ample
notice of the need to design for large amounts of raw
shale o i l .
• Petroleum refining technology has shown its a b i l i t y in
the past to cope rapidly and efficiently with new feed-
stocks and changing product slates and qualities.
On the basis of these assumptions, one may conclude that
upgrading technology would occur naturally and effectively in the
petroleum refining industry when i t becomes evident that large
volumes of shale oil would be produced and would have to be
refined. The most important economies of application in a large-
scale industry could result from:
• Pipeline transportation of raw shale oil to existing
refining centers. Movement of raw shale oil ( 1 n heated
pipelines or with additives or other pretreatment) to
existing centers would: (a) make use of existing refining

capacity presumably idled by reduced supplies of imported

petroleum, and (b) shift some demand for human, mechani-
c a l , and natural resources to locations better able to
supply them than Colorado/Utah/Wyoming, which have some
infrastructure limitations.
• Development or modification of refining catalysts and
processes to make them less sensitive to contamination by
the nitrogen present in raw shale o i l .
• Rebalancing of new and existing refinery process capacity
to regard shale oil as a primary feed rather than a
contaminant - analogous to shifting from a sweet crude
refinery to a sour crude refinery - with a corresponding
shift of product slate (consistent with overall market
demand) to best exploit the different optimum product

mixes from shale oil and petroleum.
The "Systems" Approach
It would be unwise to consider cost reductions by looking

only at the individual functional steps by which oil has tra-
ditionally been recovered from shale. The result could be sub-
optimization, and the possibility of a whole new approach or
system might be completely missed. Therefore, one should consider
the systems approach, and from two aspects. The f i r s t concerns
technology, including combinations of some individual functions.
The second concerns implementation of industry development in such
a way as to encourage systemic technological cost reductions.
Obvious examples of "systems" thinking about technology are
referred to in the preceding sections as combinations of various
approaches. Combinations of both in-situ and surface retorts
should be able to best exploit the resource in place in some
locations. The shale mined for modified i n - s i t u , which creates
the void needed for rubbling, would be charged to surface retorts
and the exact balance between modified in-situ and surface re-
torting could be optimized depending on shale quality and depth,
etc. Combinations of different types of retorts should make best
use of mined shale and should make a product mix of maximum
value. Integration of shale oil refining into the total refinery
process should reduce refining costs. Other examples of combi-
nations which serve multiple purposes could also be cited. A more
basic approach is described below.
Imagine an extraction device which travels through the shale,
breaking rock, heating the rubble, separating the oil and gas,
cooling the solid residue and replacing the rock in the mined-out
volume. The products would be shipped to the surface through
pipes which follow the extractor. Air or other gases and/or
liquids are fed to the device through pipes. Possibly, the ex-
tractor could be operated by remote control so that men would not
ordinarily be required underground. A key issue in such a concept
is the ability of the process to reduce the volume of the waste

rock to the original volume. It appears that this may be achieva-

ble by high processing temperatures and compaction.
In order to reduce unit costs through mass production,
perhaps 1000 units should be manufactured. In order to produce
5 million B/D, each unit might have a frontal area of about 10
square meters and would advance about 60 centimeters per minute.
The design of such a device would clearly call for a major
technical effort. A number of important mining, mechanical,
e l e c t r i c a l , and chemical engineering problems must be faced. The
entire unit would likely be more than 30 meters in length, weigh
500 to 1000 metric tons, and cost in production perhaps $30
million each. On the other hand, the revenue from such a unit
even at 50% utilization could amount to $30 million per year, i f
the oil were sold at $20 per barrel.
No such device is now under development or has even been

thought about seriously to our knowledge. And, of course, there
may be l i t t l e probability that such a system can be developed at
acceptable cost, i f at a l l . The example, however, illustrates
that there are other ways of thinking about shale oil recovery
that should at least be studied.
History suggests that the sheer existence of a significant
industry provides the environment necessary for the kinds of
systemic technological innovations that produce significant cost
reductions. Therefore, we present an example of a form which
might make such a significant industry possible. Such a form
would also serve to:
• Stimulate inputs and contributions (of technology, s k i l l ,
experience, perspective, and funds) from all relevant
industries.
• Provide for Federal support at start-up without Federal
control or a continuing Federal role.
• Provide for authentic participation at state, l o c a l , and
public levels.
• Provide a mechanism appropriate to the enormous size of
the task.
The example developed to permit these advantages would be the
creation of a publicly held firm along the lines of COMSAT. Its
purpose would be to produce shale oil and its by-products. The
process firms presently active in the development of shale oil
would be invited to provide process expertise and lease
holdings. Mining companies, equipment manufacturers, engineers,
and construction firms would be invited to provide expertise,
accepting as payment a limited early profit plus an equity posi-
tion. The Federal government would provide leases (land) and
research funds which would be repaid out of earnings. State
governments would provide assistance In meeting the social and
economic impacts of construction and operation. Shale oil would
compete in the marketplace, without price control, with a negoti-
ated royalty to the Federal government. Principal funding would
be through sale of equity to the public, with debt financing as

appropriate. The creation of a strategic planning function capa-

ble of managing the effect of changing technology would be
important.
Through such a vehicle, the rudiments of an "industry in
place" would be created, so that new systemic ideas and concepts
can emerge and so that economies of scale can be identified. R&D
would be centralized at least in part, with the attendant increase
in efficiency and synergy (as well as some accompanying loss of
diversity). The focus would be on optimum exploitation of the
shale oil resource from a total perspective.
Conclusions and Suggestions for Further Work

Production of shale oil on a large scale could provide oppor-

tunities for significant technological economies not otherwise
realizable. Prompt accelerated development of small-scale shale
oil production should be encouraged in the national interest.
Production would f a c i l i t a t e , and may be essential to, the tech-
nology development that should occur both to reduce current
uncertainties and to make informed decisions about any future
large-scale industry. Further work is j u s t i f i e d on more detailed
evaluation of the technological opportunities, of their potential
economic consequences, and of various structural options that
would encourage accelerated development.
The greatest potential for savings in mining for surface
retorts is treatment of part or all of the Piceance Creek Basin as
a single surface mine - even though major aquifer disturbances and
other environmental problems would be encountered and would have
to be solved. Opportunities in mining for in-situ retorting are
less well defined, but they seem to focus on continuous tunneling
and controlled fragmentation, replacing cyclic methods of
d r i l l i ng/blasti ng/muck i ng.
The largest potential for surface retorting appears to l i e in
large fluidized bed retorts. Operations under pressure, or with
retorting atmospheres other than a i r , look interesting for both
f l u i d and non-fluid retorts.
Refiners faced by large quantities of raw shale oil feed are
apt (in their traditional ways) to develop new refining technolo-
gies to handle that feed at significantly lower cost than now
foreseen for brute force hydrogenation, followed by conventional
petroleum refining.
The primary contributions from "systems" technology empha-
sizes the advantages in large-scale production of combinations of
technology to e x l o i t all resources most effectively, e . g . , combi-
r
nations of in-situ and surface retorting to make best total use of

the shale resource in place, combined shale and coal retorting,
and multi-product ( o i l , gas, electric power) retorts.
It is urgent to increase the rate of development of the shale
oil industry in order to accelerate the rate of development of its
technology. This increase would lead to a reduction of technical,

economic, and environmental uncertainties and would put the nation

in a position to exploit oil shale on a large scale rapidly, i f i t
became necessary or desirable to do so. New large-scale struc-
tures involving both the private and public sectors would help and
may be essential to accelerate development and to produce shale
oil on the huge scale potentially desired. COMSAT is a possible
model as a mechanism for the development and implementation of
these suggested technologies. An R&D operation could be linked to
such an organization through a wide range of funding, programming,
and administrative devices.
Two types of further study would be useful for future con-
sideration of new shale oil projects:
t Possible technological alternatives for a large-scale
industry should be hypothesized and the economics for
those alternatives should be estimated. Studies of that

type would not yield costs of absolute accuracy, but the
relative costs could help identify the most promising
technologies for further R&D and the potential gain
relative to current technology.
• Various structural options for a shale oil industry
should be examined. Options should be described in
detail with the advantages and disadvantages of each.
This would contribute to a well-informed choice of an
implementation mechanism that best f i t s policy con-
straints.
Literature Cited
1. Initial research on oil shale was conducted at the MIT Energy
Laboratory by the author, Malcolm A. Weiss and
Rober J. Barbara and was first reported in MIT Energy Labora-
tory Working Papers No. 79-012WP and 79-013WP. This original
work was sponsored by grants from the Edna McConnell Clark,
Ford, and Alfred P. Sloan Foundations. This paper draws on
the initial research and summarizes aspects of a workshop on
shale oil that was sponsored by MIT on June 4-5, 1979. Art
Tybor of Gulf Science and Technology Company provided the
editorial work to produce this paper in its present form.
2. Standford Research Institute, "A Western Regional Energy
Development Study: Economics, Volume 1," SRI Project 4000,
November, 1976, p. 7; Department of Energy, Policy and Evalu-
ation Division, "Inside D.O.E.," May 18, 1979, p. 6.
3. "Recommendations for a Synthetic Fuels Commercialization
Program," Synfuels Interagency Task Force Report to the
President's Energy Resources Council, November, 1975,
Vol. II, p. 18, p. H-27.

14. BALL Large-Scale Shale Oil Production 209
4. Hammond, Ogden H. and Boron, Robert E., "Synthetic Fuels:

Price, Prospects, and Prior Art," American Scientist, July-
August, 1976, pp. 407-417.
5. Whitcombe, J. A., "Shale Oil Production Costs and the Need
for Incentives for Pioneer Plant Construction," TOSCO,
February 1-3, 1976.
6. Ramsey, W. J., "Institutional Constraints and the Potential
for Shale Oil Development," Lawrence Livermore Laboratory,
UCRL-52468, July 6, 1978, p. 24.
7. Ibid., p. 16.
8. Probstein, R. F. and Gold, H., "Water in Synthetic Fuel

Production," M.I.T. Press, Cambridge, MA, 1978, p. 59.
9. Jacoby, H. D. and Lawrence, H. Linden, "Government Support
for the Commercialization of New Energy Technologies -- An
Analysis and Exploration of the Issues," Policy Study Group,
MIT Energy Laboratory Report MIT-EL 76-009, Cambridge, MA,
November, 1976. (Prepared for ERDA under Contract No. E49-18
2295).
10. Allan, Gerald B., "Note on the Use of Experience Curves in
Competitive Decision Making," Intercollegiate Case Clearing
House, #9-175-174, Boston, MA, 1975.
11. Allan, Gerald B., "A Note on the Boston Consulting Group
Concept of Competitive Analysis and Corporate Strategy,
Intercollegiate Case Clearing House #9-175-175, Boston, MA,
1975.
12. Ibid., p. 108.
13. Ball, B. C., Jr., "Energy: Policymaking in a New Reality,"
Technology Review, October/November, 1977.
Appendix - The Process of Technological Change
The Nature of the Process. In order to evaluate properly the

trade-offs in the "evolutionary" versus the "industry in place"
alternatives, i t is helpful to establish a clear view of how new
technologies are, in fact, commercialized.
Commercialization of a new technology occurs, i f i t is avail-
able at a cost allowing the private sector an acceptable return on
the total capital required, given the market prices of inputs,
c a p i t a l , and labor, given the regulatory restrictions, and given
the marketplace.

A way in which this real-world process can be perceived is

through the existence of four rather discrete stages which precede
the establishment of a mature industry:
• Research or invention
• Development or demonstration
• Commercial introduction
• Commercial diffusion
Research or invention is the generation of an idea. A
functioning process or product 1s established. Economic issues
are not dealt with in depth at this stage; technical, market, and
regulatory uncertainties are very high. Costs, prices, and
markets are usually poorly known.
In the Development stage, design is optimized until the
process or product is embodied in an actual model within a working
environment. The principal function of this stage is to eliminate

technological uncertainty and thus determine the expected cost of
mature production ( e . g . , production following the Diffusion
stage). However, the variance of this expected future cost may be
rather high. This stage does not deal at all with market or
regulatory uncertainties.
The Development stage need not, and in fact usually does not,
require the construction of a f u l l - s c a l e production f a c i l i t y .
Pilot plant is the usual approach here. The product may be real-
l i f e ( e . g . , a barrel of real shale o i l ) , so that the product may
be tested, but the production f a c i l i t i e s are expected to be
smaller than full size by virtue of the ability to scale. If they
are readily scalable, then there are no significant technical
uncertainties which require commercial-scale construction for
their resolution. If a crucial sub-unit is not readily scalable,
an alternative to a f u l l - s c a l e demonstration plant is to build a
f a c i l i t y only of the crucial sub-unit, no larger than necessary to
resolve the relevant technical uncertainties.
The purpose of the Development stage i s , thus, twofold:
• To reduce technological uncertainty
• To determine expected mature costs
At the end of this stage, variance of the mature costs will
be rather high. However, the expected value of this cost has been
determined. If this cost is too high to offer adequate hope of
profit ( i . e . , to offer hope that the technology will be com-
mercialized) or i f the cost necessary to commercialize l i e s within
the variance but at an inadequately low probability, then the
technology is not commercial. The project is dropped or perhaps
the Invention stage is reentered.
The Development stage is not primarily intended to reduce
costs. Rather, i t determines them within a broad range, given the
output of the Invention stage. It deals not at all with market or
regulatory uncertainties.
It is the Commercial Introduction stage that deals primarily
with these issues, while further narrowing the range of cost
variance. It is here that f u l l - s c a l e production f a c i l i t i e s are

14. BALL Large-Scale Shale Oil Production 211
put Into operation in order to reduce market uncertainties ( e . g . ,

marketing programs, distribution channels, maintenance organi-
zations, market segmentation and differentiation, character of the
technology and of the industry, and the value of mystique) and
regulatory and legislative uncertainties ( e . g . , environmental,
tax, delays).
It is only after these cost, market, and regulatory un-
certainties have been reduced during the Commercial Introduction
stage that the diffusion stage is considered. The Commercial
Diffusion stage is marked by widespread production in a growing
number of f u l l - s c a l e production f a c i l i t i e s , widespread usage, and
(normally) the entry of competitors. Actual costs begin to
decrease as experience is gained.
What is the driving force for this process? Clearly, i t is
pursuit of economic gain by the individual actors in the private

sector. This scheme might be viewed as a series of investment
decisions, each preceding one of the four stages.
1. The decision to conduct research is a decision to invest
in the possibility of an option to "develop" a new idea,
should one be forthcoming.
2. The decision to "develop" a new idea is a decision to
invest in an option to "introduce" a new product or
process, should the Development stage indicate i t techni-
cally feasible at attractive probable cost.
3. The decision to "introduce" is a decision to invest in an
option to "diffuse", should the market, regulatory, and
cost issues addressed in the Commercial Introduction
stage result in a favorable resolution.
At no point in the process has a "profit" been made or have cash
flows been positive, even undiscounted. Even the Commercial
Introduction stage is not normally expected to be profitable in
i t s own right, though some revenues may obtain. Rather, i t is
another in a series of investments.
4. The decision to diffuse is the decision to invest in
multiple f u l l - s c a l e f a c i l i t i e s and in market share, with
the expectation of "profit", that i s , within the planning
horizon, the discounted cash flows will be positive,
including the investment in the three earlier stages. (A
complicating factor is the fact that, at the point of the
diffusion decision, investments 1n prior stages are sunk
costs.) At the point of the Commercial Diffusion stage,
technical uncertainties are n i l , market and regulatory
uncertainties have been reduced to manageable levels, and
costs are known with a relatively high degree of certain-
ty. The significant uncertainty is competitive action,
which would affect individual actors In the process more
than the progress of the process i t s e l f .
Should the reduction of market, regulatory, and cost un-
certainty, achieved during the Commercial Introduction stage,
indicate a low probability of profitable diffusion, then obviously

the process would be stopped or delayed until a significant change

occurred in one of the key elements. In the latter case, the type
of the change would indicate the stage in which i t occurred, and
therefore, the succeeding stage in which the process would pick
up, for example:
• New idea (new technology) or introduction. Redevelop.
• Lower cost-introduction/development. Reintroduce.
• New market or regulatory climate. Reintroduce or
diffuse.
One would correctly expect the magnitude of the investment to
increase significantly from invention through diffusion to maturi-
ty. The successful invention ( i . e . , one that is eventually
'commercialized') normally has miniscule costs relative to the
investment in the mature, diffused industry. Even the investment
in "introduction" is very small relative to diffusion invest-

ment. In most cases, the cost of each stage (including Commercial
Introduction) is not recovered during that stage. If when
examined at the end of its development, a technology appears to be
commercial in the long run, i t usually will be introduced and
1
'commercialized by the private sector (9_).
The cost of successful invention, development, and intro-
duction are therefore small relative to that of diffusion. One
might say that i t is the unsuccessful ones that are expensive.
Viewed as a whole, the successful ones must more than pay for the
unsuccessful. This is usually viewed in the private sector as
"risk", and is thought of, not as an added cost, but rather as the
expected return necessary to justify "taking the risk", i.e.,
making the investments in invention, development, and intro-
duction.
An additional word needs to be said about the declining costs
in the mature phase following diffusion, as experience is accumu-
lated. It has been found (10) for a wide variety of products and
a wide variety of industries that costs (in constant dollars)
decline through experience as the product matures. This is a
well-known phenomenon for the manufacturing process ("the learning
curve"); the principle applies similarly to the total infra-
structure, i.e., manufacturing, management, distribution,
marketing, etc. (the "experience curve"). This cost reduction is
a function of the number of comparable units produced, and is
expected to amount to a 20-30% reduction for each doubling of
accumulated experience. On a log-log plot, the curve is a
straight l i n e , with a slope of 70-80% (see Figure 1).
Several characteristics of this phenomenon are important to
note here:
t The early points on the plot are scattered, and do not
begin to take form until the system as a whole becomes
organized and routine, well into the Commercial Diffusion
stage.
• Largely, each firm follows its own experience curve. For

Figure 1. Experience curve

example, i f firm X led the Diffusion phase and had

progressed down the experience curve in Figure 1 to
point C at the point in time when firm Y decided to
become a competitor, the latter would enter at, say,
point B.
The implications of these characteristics are significant:
1. In a fragmented industry ( i . e . , many equal competitors)
all competitors would follow the experience curve more or
less together. Prices would be expected to follow the
dotted l i n e , with the ordinal difference between the
solid and dotted lines representing "profit" or return on
total Investment. Under these conditions, a firm is not
likely to diffuse unless this ordinal difference 1s
positive at or very near the beginning of the Diffusion
stage.
2. If one firm were to adopt an aggressive pricing strategy,
i t might become the i n i t i a t o r of diffusion at point B,
but set its price along the dashed line in order to
dominate the market. Only at point A in experience would
i t begin to break even on current production, but at
point C in experience i t could begin reducing prices more
sharply and remain profitable. Of course, the Incentive
for such a strategy would be increased profit ( e . g . ,
higher present value of net cash flows, properly
discounted for the time value of money and for r i s k ) , due
to "investment in market share".
One of the principal strategic reasons for a firm Investing
in Invention, development, and introduction is to give i t "a head
start down the learning curve", i . e . , more accumulated experience
would result in lower unit costs than competitors during dif-
fusion. Strategically, this would lead to a dominant market share
as maturity 1s reached (11). Other strategies are open to compe-
t i t i o n . Either market failure or Inadequate expected profit would
prevent a firm from adopting this particular marketing strategy.
A Summary View. Figure 2 presents a summary view of the
process of technological change as outlined above.
• Invention 1s the generation of a new idea, with l i t t l e
knowledge of costs or of technical, market, or regulatory
uncertainties. An Investment represents an option to
develop.
• Development is the design optimization of the Idea until
i t is embodied 1n an actual model that will perform 1n
the working environment.
Purpose: essentially eliminate technological
uncertainty, and get an idea of the cost. In the
language of the "Commercial1zat1on" paper (12),
mature.cost C(X) 1s estimated, but with high v a r i -
ance GMC(X)).
Market and regulatory uncertainties are not dealt
with.

Invention Development Introduction Diffusion Maturity
Nature Generation Design optimization until Establish initial Widespread usage, Equilibrium
of a new idea. embodied in actual model production facilities, with entry of
in working environment. marketing program, competitors.
distribution channels,
maintenance organiza-
tion, etc.
Function New idea. 1. Eliminate 1. Reduce market and Market, expand, Expand profitably
Technological regulatory uncer- and compete but more slowly.
uncertainty. tainties. profitably. Market and
compete
2. Estimate diffusion 2. Determine intro- profitably.
cost C (X) with high duction cost C *
variance G' C(X). (X*) and thereby
reduce cost variance
1 d
from G to G
(C(X) ).
Criteria of A new idea A product which manage- Not profit, but an Positive net present Net cash flow.
Success with ment can expect to sell expectation to diffuse value (including
practical at a profit. successfully. prior investments).
potential.
Investment in Option to Option to introduce Option to Diffuse Profit Net cash flow.
develop.
Cost Unknown Possibility Estimate of C (X) C(X) C * (X*) determined C(X) C (X) determined C(X) .f (X)
of C (X) determined

Cost - high G' (C (X) ) reduced Gd(C (X) ) low nil
Technology high - nearly eliminated low reduced nil nil nil

Market & - not dealt with high reduced low low low
Uncer tainti
Regulatory
|
Figure 2. Commercialization and the process of technological change
Criteria of success: a product which management can

expect to sell at a profit.
Investment: option to introduce.
• Introduction is the establishment of i n i t i a l f u l l - s c a l e
production f a c i l i t i e s , marketing programs, distribution
channels, maintenance organizations, etc.
Purpose: reduce markej aijd regulatory uncertainty.
Cost: determined as C (X ), reducing the variance of
d
C(X) from G ^ C U ) ) to G (C(X)).
Criteria of success: not p r o f i t , but option to
diffuse profitably.
• Diffusion is widespread production and use, usually
accompanied by the entry of competitors.
Purpose: p r o f i t , sometimes accompanied by a strategy
to dominate the market.

Cost: C(X) is determined, and the slope of the
experience curve C(X) = f(X), is established.
As maturity is approached, each competitor
progresses down his own learning curve.
Thus, each stage performs its own function. For example, i f the
cost of a particular technology emerging from the Commercial
Development stage Is expected to be noncompetitive, the indication
is to invent a new technology, not introduce the noncompetitive
one. Similarly, i f technology emerging from introduction does not
appear profitable, the indication is to invent a new one, not
diffuse the unprofitable one.
At the present time, even those enthusiastic about proceeding
with the construction and operation of f u l l - s c a l e shale oil plants
expect the cost to exceed competitive prices ( i . e . , the world oil
price). Their argument for proceeding is based on the need to
reduce uncertainties (whether technological or regulatory), and to
have the plants ready when competitive prices rise to the level of
their costs. Most of those who make these arguments believe that
a government subsidy of some form ( e . g . , special tax treatment) is
appropriate in order to provide private incentive for the con-
struction of these plants.
The description of the process of technological change is
useful in interpreting these arguments. We are now at the "de-
velopment" stage; the cost uncertainty is high, but is expected to
exceed break-even prices. As displayed in Figure 3, at the De-
velopment stage, probable cost is greater than break-even cost,
C(X) > C(BE).
This analysis indicates the technology is simply not viable.
Effort is indicated at the Invention stage to develop a lower-cost
technology. If technological risk is too high, effort is
indicated at the Development (pilot plant) stage, not at the
Introduction ("demonstration") stage. Effort at the Introduction
stage is possibly appropriate to reduce regulatory uncertainty.
(However, i t needs to be emphasized that there are alternate
methods for reducing regulatory risk which may well be much more

cost-effective.) However, the purpose of doing so Is not clear as

long as the expected cost exceeds break-even, even after reducing
the uncertainty. TTfe argument for government subsidies or incen-
tlves would hinge on a demonstration that the private discount
rate exceeds the public value, or that the social value of shale
oil exceeds the market value (or, perhaps, the existence of some
other form of market f a i l u r e ) . In other words, i f the break-even
price is to rise from C(BE) to C(BE') over some time frame, then
investment in Introduction/Diffusion may well be economically
attractive now, even at C(X), depending on the discount rate. The
question raised by this analysis 1 s , i f the investment is not
attractive to the private sector now, how is i t attractive to the
public?
The process of technological change 1s normally driven by the
expectation that C(X) < C(BE), the difference representing the

possibility of a profit. This is represented in Figure 3 as
C(X) < C(BE'). This relation must hold for each phase in the
process for investment in the next phase to be attractive. If
this relation does not hold at any phase, then the process proper-
ly ceases.
The Shakedown Period. Introduction and Diffusion reduce
uncertainty, not expected cost. One of the ways in which this
occurs is that, by simple t r i a l and error, marginally equivalent
methods, technologies, processes, combinations, and permutations
are tried against each other, and the marginally best is thereby
identified. This begins to occur during the Introduction stage
and continues through the early Diffusion stage. Thus in shale
o i l , the various approaches to retorting would compete against
each other in the real world, as would in-situ and modified in-
s i t u ; by the closing of the Diffusion stage, industry would have
learned the optimum process, the key situational parameters, and
how to obtain maximum p r o f i t , given any particular set of circum-
stances.
An example here may be helpful. During World War II, cataly-
t i c cracking of gas oil was discovered as a practical means of
increasing the yield of high-octane gasoline ( i . e . , avgas) from
crude. At the end of the Development stage, three competing
processes were identified: FCC, TCC, and HCC. (Fluid catalytic
cracking, Thermofor catalytic cracking, and Houdry catalytic
cracking, respectively.) Any of the three was far superior to
none, but i t was not clear which one was best of the three.
Therefore, all three competed in the real world, and by the middle
of the Diffusion stage, the FCC was found to be superior to the
two competing approaches in all applications. That is to say,
against a refinery without catalytic cracking, any of the three
processes was highly attractive. However, against a refinery with
FCC, the other two were very unattractive.
The point here is that the cost advantage of FCC over TCC or
HCC is an order of magnitude less than the cost advantage of any
of the three processes over no catalytic cracking at a l l . Ap-

plying this point to shale o i l , we can see that, as far as the

process of technological change is concerned, the important issue
Is the range of expected costs of any of the competing processes,
relative to expected break-even cost. This is illustrated in
Figure 4, which compares the expected costs of Processes A, B, and
C with the break-even cost C(BE'). The process of technological
change depends on C ( X ) , C o ( X ) , and C ( X ) relative to C(BE'), not
A C
relative to each other. However, during the shakedown period of

the process of technological change, the uncertainties of C ( X ) , A
C ( X ) , and C Q ( X ) relative to each other are reduced significantly,

B
and the appropriate processes are sorted out from the competing
ones.
"Experience" Cost Reduction. It is important to distinguish
this "sorting out" during the shakedown period from the cost
reductions which occur during maturity. The former is the deter-

mination of which process, technique, e t c . , is most cost-
effective. Once this has been determined, then this knowledge
becomes the basis for the rest of the Diffusion stage and for the
Maturity stage. It is only after the established process, techni-
que, e t c . , has become repetitive that the continuing cost
reduction of the "experience curve" (as defined and discussed on
page 17-18) becomes applicable. Thus, the shakedown period 1s one
of cost determination, by selecting the marginally optimum
process, while tfie experience curve effects continuing cost
reduction, resulting from the accumulation of experience in
repeating the same functions.
These two dynamics are not only different in both nature and
in consequences, they are also separated in time. In fact, at any
single point in time, they are by definition mutually exclusive.
Applicability to This Study. Having proposed a model for
understanding the process of technological change, and having
analyzed the present shale oil industry through the framework of
this model, hopefully now we should be able to articulate the
question this study Intends to raise in more precise and succinct
terms.
If an industry were to be put in place, as compared with
evolving through the process of technological change, then we
would, in effect, be jumping from the end of the Development stage
to the end of the Diffusion stage. Since we are focusing here on
technological costs, the major phase bypassed would be the shake-
down period. Thus, a non-optimum process or technique may be the
one selected for the industry in place. To use again our
World War II analogy from the refining industry, we might have
built a refining Industry on the basis of the HCC process. The
question of this study i s , then, what is the probability of the
economies of an industry 1n place being greater than the dis-
economies of skipping the shakedown period?
This question can be seen graphically in Figure 4, if
Processes A, B, and C represent presently competing shale oil
techniques, and C(BE) represents the break-even cost of shale

B A L L Large-Scale Shale Oil Production 219
DEVELOPMENT INTRODUCTION DIFFUSION MATURITY
Probability Probability Probability

! i r
C(BE) C ( X ) C ( B E ' ) C(BE) CUjt^BE*) C(BE) C(X)C(BE') ZX
C(X*)
Figure 3. Cost uncertainties and break-even costs
JO
C ( B E ) C ( X ) CB(X) C ( X ) C ( B E ' )
A C
C(X)
Figure 4. The shakedown

DEVELOPMENT INTRODUCTION DIFFUSION MATURITY
Probability Probabilty
Industry
\
In P l a c e
C(X)
C(BE) C(X)
M
C(X) C(BE) IX
Figure 5. An industry in place

oil. What is the probability of the cost of shale oil from an

industry in place being less than C(BE), even i f Process C is
chosen as the basis for the industry?
Our analytic framework permits asking this same question in
an additional way. Note that in the process of technological
change, cost reductions occur at only the stages at each extreme
of the process: Introduction on the one side and Maturity on the
other. Thus, normally, i f a technology at the end of the Develop-
ment stage has an expected cost greater than C(BE), then the
technology is abandoned. The question here i s , could the econo-
mies of an industry in place reduce the expected cost from greater
than break-even to less than break-even? This is displayed
graphically in Figure 5.
This picture raises quite naturally the question about the
possible role of experience cost reduction (as this term is rather

narrowly defined in this paper). After a l l , this kind of cost
reduction has played a rather spectacular role in other indus-
t r i e s , IC's being the classic example. However, in the shale oil
industry, such reductions are not expected by anyone to be signi-
ficant, principally for two reasons. In the f i r s t place, the
dynamics of limited resources is expected to be overwhelming from
the very beginning. In the second place, none of the components
of the shale oil industry is new ( i . e . , mining, retorting, materi-
als handling); we are already so far down the learning curve on
each of them that additional accumulated experience within the
shale oil industry is expected to result in negligible cost
reductions.
Thus, the picture of shale oil is basically one of continual-
ly increasing, rather than decreasing, costs. Any v i a b i l i t y at
all depends not on increasing economies but on increasing break-
even costs ( i . e . , increasing world oil price). This is a poorly
understood notion and is contrary to most experience. There are
no analytical tools capable of dealing adequately with issues of
marginal costs exceeding average costs (13).
Over against t h i s , the question raised by this study is a
rather fundamental one: When viewed from the perspective of any
industry-in-place, are there possible economies not yet perceived,
which might permit costs to decline (in real terms) rather than to
rise over the long term?
RECEIVED June 19, 1981.

15
Commercial-Scale Refining of Paraho Crude
Shale O i l into Military Specification Fuels
N. J. WASILK
The Standard Oil Company, P.O. Box 696, Toledo, OH 43694
E. T. ROBINSON
The Standard Oil Company, 4440 Warrensville Center Road,
Warrensville Heights, OH 44146
In September, 1977 the Standard Oil Company (Ohio) was con-

tracted by the U.S. Navy to refine up to 100,000 barrels of
crude Paraho Shale Oil into Military Transportation Fuels. The
objective of the program was to demonstrate that shale oil
could be converted into stable, specification military fuels
utilizing conventional refining technology and in sufficient
volumes to support an extensive engine testing program. Yields
of JP-5 (jet fuel) and DFM (diesel fuel marine) were to be
maximized while minimizing the yield of residual fuel.
The crude shale was produced by Paraho Development Corp.
over the three year period from 1976 to 1978. Paraho's Anvil
Point, Colorado works utilizes a vertical direct heat retort to
recover the oil from crushed shale (1).
For contractual reasons the program was divided into three
phases. During Phase I, the proposed shale oil processing
scheme was tested and developed in appropriate pilot plants.
Phase II constituted engineering preparation and the actual re-
finery run. Post run analysis and report writing were comple-
ted in Phase III.
Paraho Shale O i l
The unique nature of crude shale o i l r e q u i r e s s p e c i a l con-

s i d e r a t i o n i n handling and processing. Table I summarizes some
t y p i c a l i n s p e c t i o n s of raw shale o i l and a West Texas crude.
In comparison to conventional petroleum, shale o i l has s e v e r a l
deleterious characteristics:
(1) High n i t r o g e n and oxygen content.
(2) Low hydrogen/carbon r a t i o .
(3) Low y i e l d of 650°F minus m a t e r i a l ( < 30 v o l . % ) .
(4) Moderate a r s e n i c and i r o n content.
(5) Suspended ash and water.
0097-6156/81/0163-0223$05.00/0

Table I
P r o p e r t i e s of Paraho Shale O i l and West Texas Sour Crude
Paraho Shale O i l West Texas Sour
G r a v i t y , °API 20.4 34.1

S p e c i f i c Gr. @ 60°F 0.9315 0.8545
Pour Point, °F +85 F l u i d @ -30
V i s c o s i t y , SSU
@ 60°F Too heavy 57.1

@ 100°F 213 43.1
@ 210°F 44.9
V i s c o s i t y - G r . Constant 0.8899 0.722
Reid Vapor Pressure, PSI 5.1
T o t a l A c i d No., mg KOH/gm 1.988 0.265
Asphaltenes, wt.% 0.889 1.028
Ramsbottom Carbon, wt.% 2.977 2.65
B.S. & W., V o l . % 0.05* 0.30
S a l t , lb/M B b l s . 4.9** 3.3
Elemental A n a l y s i s
C, wt.% 83.68
H, wt.% 11.17
0, wt.% 1.38
N, wt.% 2.02 0.10
S, wt.% 0.70 1.40
Metals
As, ppm 7.5
Na, ppm 0.3
K, ppm 0.17
V, ppm 0.17 4.4
N i , ppm 2.4 2.6
Fe, ppm 53 2.0
TBP 650°F P o i n t , v o l . % 28.24 58.64
(True B o i l i n g P o i n t )
* (0.06 u n s e t t l e d )
** (8.20 u n s e t t l e d )

15. WASILK AND ROBINSON Paraho Crude Shale Oil 225
The high n i t r o g e n content i s probably the l a r g e s t area of

concern, as i t i s an order of magnitude higher than that found
in petroleum. The technology f o r processing high nitrogen
crudes i s not n e a r l y as advanced as comparable technologies f o r
d e s u l f u r i z a t i o n or cracking ( i n c r e a s i n g y i e l d of lower b o i l i n g
hydrocarbons).
Nitrogen compounds are known poisons f o r many petroleum
processing c a t a l y s t s such as f l u i d bed catalytic cracking,
naphtha reforming and hydrocracking catalysts. In a d d i t i o n ,
n i t r o g e n compounds have been found to create s t a b i l i t y problems
i n g a s o l i n e , j e t and d i e s e l f u e l s . Fuel bound n i t r o g e n w i l l
a l s o increase the N 0 emissions from p r a c t i c a l l y any type of
X
combustor. F i n a l l y , n i t r o g e n compounds q u i t e o f t e n have a

p e c u l i a r and o f f e n s i v e odor which i s uncommonly d i f f i c u l t to
remove (2).
Shale O i l R e f i n i n g Process
A schematic of the process developed f o r t h i s program i s

shown i n Figure 1. The crude shale o i l i s i n i t i a l l y allowed to
s e t t l e batchwise at above ambient temperature. This has been
found to be e f f e c t i v e i n breaking the w a t e r / o i l emulsion,
thereby p r e c i p i t a t i n g suspended water and ash to the bottom of
the tank. The shale o i l i s a l s o pumped through a 20 micron
filter enroute to the h y d r o t r e a t e r to remove any entrained
debris l e f t i n the tank.
After settling, the shale o i l i s mixed with hydrogen,
preheated and passed through a guard bed. The purpose of the
guard bed i s to remove the organic i r o n and a r s e n i c as w e l l as
any ash and s o l i d s which survived the s e t t l i n g and filtering
procedure.
Following the shale o i l pretreatment steps ( s e t t l i n g and
guard bed demetall'ization) the whole shale o i l i s c a t a l y t i c a l l y
hydrotreated at elevated temperature and hydrogen partial
pressure. Hydrotreating, the most important processing step,
i s the c a t a l y t i c r e a c t i o n of hydrogen with s u l f u r , oxygen and
nitrogen compounds to form H2S, H2O and NH3,
r e s p e c t i v e l y , plus heteroatom-free hydrocarbons. In a d d i t i o n ,
aromatic s a t u r a t i o n and c r a c k i n g occur to some extent
thereby i n c r e a s i n g the hydrocarbon/carbon r a t i o and i n c r e a s i n g
the y i e l d of m i l i t a r y f u e l feedstock (650°F minus m a t e r i a l ) .
The hydrotreated shale o i l i s f r a c t i o n a t e d by d i s t i l l a t i o n
methods into gasoline, jet, diesel, and 650°F bottoms
(residua). The j e t and diesel fuel boiling ranges were
determined experimentally to meet f l a s h point and freeze or
pour point requirements. Some of the r e s i d u a was r e c y c l e d back
to the h y d r o t r e a t e r to increase j e t and d i e s e l f u e l y i e l d s .

A final finishing step, acid and c l a y t r e a t i n g , was

included to meet m i l i t a r y specification gum and s t a b i l i t y
requirements•
Refinery M o d i f i c a t i o n s
P r i o r to the shale o i l operation, f a c i l i t i e s m o d i f i c a t i o n s

at the Toledo r e f i n e r y were r e q u i r e d to be able to r e c e i v e ,
store and process the shale o i l and i t s products without
contamination from normal r e f i n e r y stocks.
Raw shale o i l was shipped from the Paraho f a c i l i t i e s to
Toledo by r a i l r o a d tank c a r . An u n d e r u t i l i z e d r a i l c a r rack was
revamped to provide a new unloading as w e l l as a product
loading system. A new steam heated tank was b u i l t i n which to
store the shale o i l as i t was r e c e i v e d over a 3 month p e r i o d .

A hydrocracker which normally processes d i s t i l l a t e fuels
i n t o gasoline products was modified to process the shale o i l .
New c a t a l y s t (Shell 324) was charged to the f i r s t stage
reactor. A guard bed packed with alumina extrudate was placed
i n the feed preheat t r a i n . A 20 micron f i l t e r was i n s t a l l e d on
the i n l e t l i n e from the shale o i l storage tank. A new s t r i p p e r
tower was i n s t a l l e d on the d i s t i l l a t i o n tower to s t r i p the DFM
product. Numerous p i p i n g and instrumentation m o d i f i c a t i o n s
were made to allow f o r a s i n g l e stage h y d r o t r e a t e r o p e r a t i o n .
For a c i d t r e a t i n g of the d i e s e l f u e l and j e t f u e l products
a "new" a c i d t r e a t e r was designed and b u i l t , the major v e s s e l
of which were refinery surplus equipment. These v e s s e l s
included a s e t t l e r , c l a y contactor and sludge storage tank.
To provide product storage f o r JP-5 and DFM, two tanks were
removed from r e f i n e r y s e r v i c e and cleaned p r i o r to p r o c e s s i n g .
A l l l i n e s used f o r shale o i l m a t e r i a l which interconnected
with lines c o n t a i n i n g normal r e f i n e r y stocks were either
blanked or had the i s o l a t i n g valves chained and locked.
Refinery L o g i s t i c s and Process Flow
When a l l the shale o i l had been r e c e i v e d , the storage tank

was heated to 185°F, and an attempt was made to drawoff any
free water. No free water was found. The shale o i l r e c e i v e d
at Toledo measured only 0.07 v o l . % sediment and water,
(B.S.&W.), whereas e a r l i e r p i l o t plant samples contained 0.8
vol.% B.S.&W. The shale o i l was pumped continuously from the
tank through the 20 micron feed f i l t e r into the h y d r o t r e a t e r
surge drum. From here i t was pumped through the feed preheat
s e c t i o n and guard bed together with hydrogen gas and i n t o the
reactor. Reactor e f f l u e n t was cooled, water washed and r e c y c l e
hydrogen and l i g h t ends removed, p r i o r to e n t e r i n g a muiltidraw
d i s t i l l a t i o n column. Here four products were recovered from

the e f f l u e n t : an overhead g a s o l i n e stock, a j e t f u e l cut (JP-5

or JP-8), a marine d i e s e l f r a c t i o n (DFM) and a bottoms r e s i d u a l
fuel fraction. The gasoline stock was sampled, but not
recovered i n bulk, instead i t was used as feed to another
hydrocracker. The JP-8 was acid t r e a t e d on rundown to a
r a i l c a r , while JP-5 and DFM were run down to storage f o r l a t e r
acid treating. Any o f f spec JP-5, JP-8 or DFM were returned to
the shale o i l storage tank. Part of the bottoms r e s i d u a were
r e c y c l e d through the h y d r o t r e a t e r to increase conversion, while
the remainder was used as cat cracker feed with a small amount
rundown d i r e c t l y to r a i l c a r s f o r recovery as heavy f u e l o i l .
Refinery Run
The h y d r o t r e a t i n g run began on November 4, 1978 and ended

on December 4, 1978. In that time 73,100 b a r r e l s of the 88,225
b a r r e l s of shale o i l r e c e i v e d were h y d r o t r e a t e d . However, some
of the products fom t h i s volume were returned to the shale o i l
storage tank as o f f s p e c i f i c a t i o n product. An e x c e s s i v e l y high
pressure drop across the Guard Bed caused the run to be
terminated before a l l the shale o i l was processed. The
hydrocracker was f i r s t shutdown on day 25 of the run because of
a high guard bed pressure drop. The top 25% opf the Guard Bed
packing was removed because a black viscous sludge was present
on the top of the bed. When returned to o p e r a t i o n , the Guard
Bed soon redeveloped a high pressure drop and the run was
terminated due to c o n t r a c t u r a l time l i m i t a t i o n s .
O r i g i n a l plans c a l l e d f o r the JP products to be acid
t r e a t e d on rundown to tankage or r a i l c a r . This plan was
modified a f t e r a c i d t r e a t i n g s t a r t u p problems r e s u l t e d i n poor
denitrification. The JP-5 was rundown to tankage without a c i d
t r e a t i n g , as was the DFM, and both were t r e a t e d a f t e r the
h y d r o t r e a t i n g run was complete. F o r t u n a t e l y , the a c i d t r e a t i n g
problems were resolved i n time to t r e a t the JP-8 on rundown to
a railcar.
The r e s i d u a l hydrotreated shale o i l was mixed with r e g u l a r
r e f i n e r y cat cracker feed at a rate of 3%, with no d e t e c t a b l e
s h i f t s i n y i e l d s or other adverse consequences. S i m i l a r l y , the
g a s o l i n e range cut had no detectable e f f e c t s on hydrocracker
operations at 1.5% of feed.
The shale o i l which remained a f t e r the processing run was
burned as b o i l e r f u e l . No problems developed over the 1 month
combustion p e r i o d .
Following c o n c l u s i o n of the run, an examination of the
Guard Bed contents revealed two separate problems, the sludge
at the top of the bed and F e S f i n e s throughout the bed.
x The
sludge was t h e o r i z e d to have been formed by a r e a c t i o n between
shale o i l , iron, and sulfuric acid. The acid had been

unwittingly introduced into the shale o i l feed tank by

r e c y c l i n g o f f - s p e c JP-5 from the a c i d t r e a t e r during s t a r t u p .
A large q u a n t i t y of f i n e s c o n t a i n i n g a high c o n c e n t r a t i o n of
FeS x was found throughout the bed. Apparently FeS had x
been d e p o s i t i n g throughout the run and f i l l e d the i n t e r s t i t i a l

spaces among the extrudate, thus causing a high pressure drop.
M a t e r i a l Balances
E s s e n t i a l l y a l l of the conversion of 650°F plus bottom

m a t e r i a l to t r a n s p o r t a t i o n f u e l occurs i n the h y d r o t r e a t i n g
step. Table I I compares the o v e r a l l m a t e r i a l balance and y i e l d
and n i t r o g e n l e v e l s obtained at Toledo with o r i g i n a l pilot
plant r e s u l t s . These data i n d i c a t e that the d e n i t r i f i c a t i o n
a c t i v i t y of the c a t a l y s t was c o n s i s t e n t with p r i o r r e s u l t s ,

however the apparent yield s t r u c t u r e was different. The
d i f f e r e n c e s i n y i e l d s are a t t r i b u t e d to two factors: (1)
poorer d i s t i l l a t i o n e f f i c i e n c y i n the r e f i n e r y operation and
(2) lower DFM pour point and f l a s h point t a r g e t s during the
r e f i n e r y run. The a c t u a l conversion of 650°F plus bottoms
m a t e r i a l a t t a i n e d i n the r e f i n e r y run i s very s i m i l a r to the
pilot plant results. The distillation curve of whole
hydrotreated products (minus r e c y c l e ) shown i n Figure 2,
i l l u s t r a t e s this observation.
Net hydrogen consumption metered i n the r e f i n e r y run was
s i g n i f i c a n t l y l e s s than p i l o t plant r e s u l t s ( ^ 1500 versus
1050 SCFB). Chemical a n a l y s i s of the v a r i o u s hydrotreated
products i n d i c a t e that the level of aromatic saturation,
c r a c k i n g and heteroatom removal f o r both r e f i n e r y and pilot
plant were n e a r l y the same. The d i f f e r e n c e i n measured
hydrogen consumption i s most probably a r e s u l t of scaleup and
p i l o t plant e r r o r . Needless to say, hydrogen consumption i s a
very important parameter i n determining overall shale o i l
economics.
The t o t a l amount of each f i n i s h e d f u e l produced i s shown i n
Table I I I . In a c i d t r e a t i n g the y i e l d losses were found to be
p o r p o r t i o n a l to n i t r o g e n content and molecular weight of the
fuel. For a 3300 ppm n i t r o g e n JP-5 stock, y i e l d l o s s was 4
wt.% and on a 3300 ppm n i t r o g e n DFM the l o s s was 5.4 wt.%.
Other l o s s e s i n c u r r e d i n the system were s t a r t u p and l i n e - o u t
slop, h e e l l e f t i n feed tanks and t r e a t i n g v e s s e l s and losses
during the c l a y column changes.
Product Analyses
Gasoline Stock. Analyses of the r e f i n e r y and p i l o t p l a n t

gasoline stocks are shown i n Table IV. Both m a t e r i a l s are very
s i m i l a r i n aromatic content, n i t r o g e n l e v e l and octane number.

15. WASILK A N D ROBINSON Paraho Crude Shale Oil 229
Table I I
Shale O i l H y d r o t r e a t i n g Y i e l d s
Toledo Refinery P i l o t Plant

Bbls. V o l . % Wt.%N Vol.% Wt.%N
Gasoline Stock 8743 11.96 0.067 11.00 0.050
(including
Butanes)
JP-5 9546 13.73 0.220 25.30 0.250

JP-8 490
DFM 18939 25.90 0.340 34.50 0.430
Residual Fuel 37220 50.91 0.380 35.20 0.220
TOTAL 74939 102.50 106.00
H 2 Cons. SCFB 1050 1500
Table I I I
Net Fuels Produced A f t e r A c i d / C l a y T r e a t i n g
Bbls.
Gasoline Stock 7,718
JP-5 6,615
JP-8 462
DFM 16,357
Residual F u e l 37,220
Table IV
Gasoline Stocks Analyses
P i l o t Plant Toledo
API G r a v i t y 57.8 54.7

Reid Vapor Pressure, p s i 1.3 5.6
Distillation D-86 D-86
I n i t i a l B o i l i n g P o i n t , °F 190 100
10 V o l % Off, °F 226 249
50 V o l % O f f , °F 258 283
90 V o l T Off, °F 288 317
End Point 332 370
% Recovered 99.0 98.0
% Residue 1.0 1.0
Paraffins 58.87 49.95
Monocyclo. P a r a f f i n s 29.61 31.62
Dicyclo Paraffins 9.97 2.40
Alkylbenzenes 9.97 15.20
Indans + T e t r a l i n s 0.11 0.51
Naphthalenes 0.33 0.32
Carbon No. P a r a f f i n s 8.01 9.36
Carbon No. Alkybenzenes 7.81 7.85
Nitrogen, Wt.% 0.040 0.078
Research Octane Number, c l e a r 47 Not run

LIGHT ENDS
Ho
GASOLINE
COMPONENTS
JP-5 FINISHED
ACID/
CLAY JP-5
DFM FINISHED
GUARD BED ACID/
SHALE OIL
CLAY DFM
SETTLING HYDRO-
TREATER
550 F + BOTTOMS RESIDUAL

RECYCLE FUEL
Figure 1. Shale oil processing block-flow diagram
• PILOT PLANT PRODUCT
• REFINERY PRODUCT
• RAW SHALE OIL
10 20 30 40 50 60 70 80 90 100
CUMULATIVE VOLUME %
Figure 2. T.B.P. distillation comparison of pilot plant and refinery whole hydro-
treated product

Neither i s s u i t a b l e as a d i r e c t g a s o l i n e blending stock or as

reformer feed. A d d i t i o n a l h y d r o t r e a t i n g i s required to reduce
the nitrogen content to levels acceptable to catalytic
reforming, which i s required to boost the octane number of t h i s
material.
Jet F u e l s . Product JP-5, before and a f t e r a c i d t r e a t i n g i s

compared to p i l o t p l a n t prepared m a t e r i a l i n Table V. Again both
stocks have s i m i l a r n i t r o g e n , hydrogen and aromatic content.
Note that the thermal s t a b i l i t y of the untreated f u e l i s poor.
However, once the n i t r o g e n compounds are s e l e c t i v e l y removed by
1
a c i d t r e a t i n g , the f u e l s s t a b i l i t y as determined by gum and
JFTOT (ASTM D-3241) measurements i s very good. In a d d i t i o n ,
storage s t a b i l i t y c h a r a c t e r i s t i c s of the f u e l s were tested by

aging the m a t e r i a l f o r 1 month at 140°F and then repeating the
JFTOT and gum t e s t s . The aging t e s t s r e s u l t s , shown i n Table VI
f o r a composite sample of a l l treated JP-5 produced at the
r e f i n e r y , i n d i c a t e that t h i s f u e l has very good storage s t a b i l i t y
properties.
D i e s e l Fuel Marine. P h y s i c a l i n s p e c t i o n s of p i l o t plant

and r e f i n e r y DFM are compared i n Table V I I . As previously
mentioned, the d i s t i l l a t i o n (hence n e a r l y everything e l s e ) are
d i f f e r e n t due to r e f i n e r y f r a c t i o n a t i o n p r a c t i c e s and a l t e r e d
target specs. Again, a c i d t r e a t i n g i s r e q u i r e d to meet f u e l
stability specifications, i.e. ASTM 2274 - (accelerated
oxidation gum test). These fuels have good combustion
p r o p e r t i e s , as shown by the cetane number (^50) and hydrogen
contents ( 13 wt.% hydrogen).
Residual Fuel. The r e s i d u a l f u e l produced by both the

p i l o t and r e f i n e r y meets a l l government s p e c i f i c a t i o n s f o r low
s u l f u r , high pour point #6 f u e l o i l . The r e s i d u a l f u e l s are i n
f a c t very " c l e a n " as shown i n Table VIII by the high hydrogen
and low s u l f u r , metals, carbon and asphaltenes content. This
stock i s b e t t e r u t i l i z e d as cat cracker feed than r e s i d u a l
f u e l , since higher value gasoline and kerosene f u e l can be
e a s i l y produced v i a c a t a l y t i c processing.
Product Fuels D i s t r i b u t i o n
A l l 6165 b b l s . of the treated JP-5 produced at the Toledo

refinery was shipped to Rickenbacher Air Force Base in
Lockbourne, OH. The treated DFM was shipped to four
destinations: 3021 b b l s . were sent to General Motors D e t r o i t
D i e s e l , A l l i s o n Plant #5 i n I n d i a n a p o l i s , IN, 8334 b b l s . were
shipped to P h i l a d e l p h i a Naval Base i n P h i l a d e l p h i a , PA, 235
b b l s . were sent to Wright Patterson A i r Force Base, F a i r b o r n ,
OH and 4785 b b l s . went to the Defense Fuel Support Point i n
C i n c i n n a t i , OH. Of the 4670 b b l s . of r e s i d u a l f u e l reserved

Table V
JP-5 Analyses
A - Untreated JP-5
T-5624 K
P i l o t Plant Toledo M i l l Spec.
API G r a v i t y 41.8 42.7 36<API<48

GR
Flash Point °F 157 158 140 Min.

Freeze Point, °F -52 -57 -51 Max.
E x i s t e n t gum (D-381) 12.2 Not Run 7.0 Max.
Mg/100 cc
Distillation D-86 D-86 D-86
IBP, °F 356 370 Report

10 Vol %, °F 380 384 401 Max.
50 Vol %, °F 415 400 Report
90 Vol %, °F 456 436 Report
End P o i n t , °F 477 480 554 Max.
Nitrogen, Wt. % 0.32 0.29
Paraffins, Vol. % 43.9 42.5
Naphthenes, V o l . % 33.1 36.0
Aromatics, V o l . % 23.0 21.5 25% Max.
JFTOT, V i s u a l (D-3241) 4 (Fail) - 3
B - Treated JP-5
P i l o t Plant Toledo Mill Spec.
API G r a v i t y
43.0 43.6 36<API<48
GR
Nitrogen, PPM 8 0.5
T o t a l A c i d Number,
mg KOH/gm Nil 0.005 0.0015 Max.
Water Separation
Index, M o d i f i e d 86 95 85 Min.
E x i s t e n t gum (D-381)
Mg/100 cc 0.6 1.4
JFTOT @ 500°F (D-3241)

Visual 2 1 3
Max. Spun Rate 10 0 17
Max. AP mm Hg 1.0 0.5 25
Paraffins Vol.% 46.0 43.7
Naphthenes V o l . % 33.1 34.5
Aromatics V o l . % 20.9 21.8 25% Max.

Table VI
Refinery JP-5 S t a b i l i t y Properties
Aged @ 140°F
Unaged Fuel f o r 1 month
JFTOT Break P o i n t , °F 625 I 500
Color +30 +30
D-381 E x i s t e n t gum 1.4 1.6
Mg/100 cc
JFTOT @ 500°F, v i s u a l (D-3241) 2 2
JFTOT @ 500°F, Max. Spun Tube 1.0 3.0
JFTOT @ 500°F, Max. Spot Tube 2.0 2.0
JFTOT @ 500°F, 27TDR 1.5 6.5
JFTOT @ 500°F, AP MM Hg 0.0 0.0
Table VII
D i e s e l Fuel Marine Analyses
A - Untreated DFM
F-16884G
Pilot Plant Toledo M i l ;Spec.
API G r a v i t y 33.4 36.8 Report
Pour Point, °F 15 0 20 Max.

Flash P o i n t , °F 290 162 140 Min.
Distillation D-86 D-86 D-86

I n i t i a l B o i l i n g Point,°F 507 396 -
10 V o l . % Off 529 456 -
50 V o l . % Off 553 512 R
90 V o l . % Off 595 562 675 Max.
Endpoint, °F 1.0 1.0 3 Max.
Nitrogen, Wt.% 0.40 0.33
Cetane Index 50.1 52.5 45 Min.

B - Treated DFM
API G r a v i t y 34.8 38.1 Report
Carbon, Wt.% 86.75 86.27 -

Hydrogen, Wt.% 13.02 13.28 -
Nitrogen, ppm 90 3.9
Paraffins Vol.% 42.2 45.5 -
Naphthenes, V o l . % 25.8 25.5 -
Aromatics, V o l . % 32.0 29.0 -
T o t a l A c i d Number, Mg KOH/gm 0.029 0.010 -
Cetane Number 55.3 50.1 0.30 Max
ASTM 2274 Mg/100 cc 0.37 0.51 2 .5 Max
( a c c e l e r a t e d to o x i d . t e s t )

Table VIII
Residual Fuel Analyses
P i l o t Plant Toledo
API G r a v i t y 30.3 29.6

Pour Pt., °F 105 80
Rams Bottom Carbon, Wt.% Not Run 0.096
Asphaltenes, Wt.% 0.244 0.059
V i s . @ 210°F, CST 6.45 2.00
Distillation D-2887 D-2887
I n i t i a l B o i l i n g P o i n t , °F 689 331
10 V o l . % O f f , °F 739 582
50 V o l . % O f f , °F 830 732
90 V o l . % O f f , °F 958 900
Endpoint, °F 1000 1032
Carbon Wt.% 87.32 86.71
Hydrogen, Wt.% 12.59 12.75
Nitrogen, Wt.% 0.33 0.44
Oxygen, ppm 102 182
S u l f u r , ppm 20 20
Saturates, V o l . % 57.1 Not run
Aromatics, V o l . % 42.9 Not run
Iron, ppm 0.93 0.10
A r s e n i c , ppm 0.13 0.4
Vanadium, ppm 0.36 0.02
Sodium, ppm 0.79 0.6
Potassium, ppm 0.10 0.6

for shipment, 4345 b b l s . were sent to the U.S. Navy at

Mechanicsburg, PA, and the remaining 325 b b l s . were shipped to
the E.P.A. at the Naval Ship Yard i n Long Beach, CA. These
f u e l s are undergoing extensive engine t e s t i n g and e v a l u a t i o n by
the p a r t i e s i n v o l v e d . In a d d i t i o n to the f u e l s produced,
numerous samples o f feed, intermediate and product streams were
taken f o r h e a l t h e f f e c t studies by the D.O.D. and D.O.E.
Conclusions
1. Fuels meeting m i l i t a r y specifications and possessing

good storage s t a b i l i t y c h a r a c t e r i s t i c s can be produced
from shale o i l , utilizing conventional refinery
equipment.
2. The processing scheme u t i l i z e d i n t h i s study r e q u i r e s :

a. S e t t l i n g and a guard bed to protect the
hydrotreating catalyst.
b. H y d r o t r e a t i n g to remove heteratoms, increase the
hydrogen/carbon r a t i o and improve the 650°F minus
l i q u i d y i e l d of shale o i l .
c. A c i d and c l a y t r e a t i n g to meet thermal and storage
s t a b i l i t y requirements of the j e t and d i e s e l f u e l .
Acklowledgement
This program was administered by the U.S. Navy Energy and

Natural Resources R & D o f f i c e s under the d i r e c t i o n of L t .
Commander Lawrence Lukens.
In a d d i t i o n , we wish to acknowledge the long hours and
skillful a s s i s t a n c e and operation provided by the Toledo
Refinery Operations S t a f f and the C e n t r a l Engineering D i v i s i o n .
References
1. Jones, J.B., Heistand, R.N., "Recent Paraho Operations",
12th Oil Shale symposium Proceedings, Colo. School of
Mines, april 18-20, 1979 pg. 184-194.
2. Robinson, E.T., "Refining of Paraho Shale Oil Into
Military specification Fuels", IBID, pg. 195-212.
RECEIVED April 30, 1981.

16
Relation Between Fuel Properties and Chemical
Composition. Chemical Characterization of
U.S. Navy Shale-II Fuels
1
JEFFREYSOLASH ,ROBERT N. HAZLETT, JACK C. BURNETT,
ERNA BEAL, and JAMES M. HALL
Naval Research Laboratory, Washington, D.C. 20375
As domestic and imported petroleum supplies dwindle and

petroleum increases dramatically in cost, it is imperative for
the Navy to consider future liquid fuel options. The Navy has
two thrusts in transportation fuels: (a) explore the relaxation
of fuel specifications and (b) examine alternate sources of fuels.
This paper deals with one of the alternate sources, shale oil.
The bulk of the Navy's vehicles utilize middle distillate
fuels; a kerosene type jet fuel, JP-5, for aircraft and diesel fuel
marine, DFM, for ships and boats. Reasonable yields of these
fuels can be obtained from shale oil. Further, shale crude oil
has a good hydrogen content which allows upgrading to finished
fuel with modest additions of expensive hydrogen. Thus the
interest in Navy fuels from shale oil.
The Navy has completed two crude production/refining exer-
cises with shale. The first of these, a 10,000 barrel operation
(Shale-I), is described in two reports (1,2). The second, a
73,000 barrel operation (Shale-II), was completed in 1979 at the
Toledo refinery of The Standard Oil Company (Ohio) (3). This
paper describes the chemical characterization of the JP-5 and
DFM from the Shale-II project.
Experimental
Samples. One g a l l o n samples of the v a r i o u s r e f i n e r y streams

were obtained from Sohio throughout the approximately one month
of production. P e r i o d i c samples of f i n i s h e d JP-5 and DFM were
a l s o obtained during the a c i d treatment process which was com-
p l e t e d subsequent to the hydrocracking and f r a c t i o n a t i o n steps.
Drum samples of the f i n i s h e d homogeneous JP-5 and DFM products
were a l s o examined.
1
Current address: Department of Energy, Germantown, MD, 20767.


T o t a l Nitrogen. The f u e l samples were pyrolyzed/combusted at

1000°C i n a flow of argon/oxygen and the chemiluminescence f o r the
r e a c t i o n of NO with ozone measured ( 4 ) . Types of s p e c i f i c n i t r o -
gen compounds found are d i s c u s s e d elsewhere i n t h i s book (5).
GC Analyses. The n-alkanes i n the f u e l samples were d e t e r -

mined with a 100 meter OV-101 w a l l coated glass c a p i l l a r y column.
The i n l e t s p l i t r a t i o was 50:1, the column oven was temperature
programmed from 80 to 240°C, and the i n l e t temperature was 310°C.
The i n t e r n a l standard procedure was used f o r q u a n t i t a t i o n .
LC Separation. P r e p a r a t i v e s c a l e l i q u i d chromatography was

performed with Waters PrepPak r a d i a l l y compressed s i l i c a columns.
F u e l charges of 6 to 10 ml were c a r r i e d through the column with
n-pentane at a flow of 200 ml/minute. R e f r a c t i v e index, 254 nm

u l t r a v i o l e t , and 313 nm u l t r a v i o l e t d e t e c t o r s monitored the LC
e f f l u e n t and keyed the c o l l e c t i o n of f r a c t i o n s .
Mass Spectrometry. E l e c t r o n impact (EI) mass spectrometry was

done at NRL on the e f f l u e n t from a 6 f t . OV-101 packed GC column
programmed from 70 to 210°C. F i e l d i o n i z a t i o n mass spectrometry
(FIMS) was performed by SRI I n t e r n a t i o n a l on contract to NRL. In
t h i s l a t t e r a n a l y s i s , the f u e l sample was frozen on a s o l i d s i n l e t
probe p r i o r to i n s e r t i o n i n t o the mass spectrometer. The s p e c t r a
accumulated f o r each mass during a temperature program were nor-
mally t o t a l e d f o r data p r e s e n t a t i o n ( 6 ) . Molecules b o i l i n g below
140°C are l o s t or depleted with t h i s technique but such compounds
comprise a very small f r a c t i o n of JP-5 or DFM. Since the i o n i z a -
t i o n e f f i c i e n c y f o r hydrocarbon c l a s s e s i s c u r r e n t l y under study,
the FIMS data are u t i l i z e d p r i m a r i l y i n a q u a l i t a t i v e sense.
NMR Examination. Fuel samples and f r a c t i o n s were analyzed by

13
proton and C NMR at the Naval B i o s c i e n c e s Laboratory. The spec-
t r a were taken on a V a r i a n FT-80A.
Results
Nitrogen Content. The bulk of the shale o i l n i t r o g e n was r e -

moved i n the hydrocracking step. A l l four products from f r a c t i o n -
a t i o n of the h y d r o c r a c k a t e — n a p h t h a , j e t , d i e s e l and heavy o i l —
contained s u b s t a n t i a l amounts of n i t r o g e n , however. The data i n
Table I i n d i c a t e that the l i g h t e r products had l e s s t o t a l n i t r o g e n .
A l l products increased i n n i t r o g e n content as the r e f i n i n g
run progressed. For i n s t a n c e , the 25 day hydrocrackate contained
2 h times the n i t r o g e n found i n the 12 day product. The j e t and
d i e s e l f r a c t i o n s almost doubled i n n i t r o g e n over the same time
span. The hydrocracking c a t a l y s t l o s t a c t i v i t y throughout the
run.

16. SOLASH E T A L . Fuel Properties and Chemical Composition 239
The n i t r o g e n content of the JP-5 and DFM f r a c t i o n s , the pro-

ducts important to the Navy, was too high to a f f o r d s a t i s f a c t o r y
s t a b i l i t y . Extensive a c i d treatment with s u l f u r i c a c i d reduced
the n i t r o g e n content i n the f i n i s h e d f u e l s , however, to one
ppm(w/v) f o r the JP-5 and 18 ppm (w/v) f o r DFM. As a consequence
the f i n i s h e d f u e l s had e x c e l l e n t s t a b i l i t y . Somewhat higher n i t -
rogen contents would undoubtedly be acceptable with regard to
s t a b i l i t y but the Shale-II program demonstrates that s t a b l e f u e l s
can be made from shale crude o i l using standard r e f i n i n g processes.
n-Alkane Content. Shale f u e l s e x h i b i t higher f r e e z e and pour

p o i n t s than s i m i l a r f u e l s made from most petroleum crudes. This
i s r e l a t e d to the symmetrical n-alkane molecules which are major
components of shale derived f u e l s ( 7 ) . The content of these
molecules i n the Shale-II middle d i s t i l l a t e f u e l s i s l i s t e d i n

Table I I . The r e l a t i o n s h i p between f r e e z i n g p o i n t and composition
i s d e s c r i b e d i n another chapter of t h i s book ( 8 ) .
FIMS F i n g e r p r i n t . F i e l d i o n i z a t i o n mass spectrometry of a

mixture a f f o r d s a spectrum of the molecular ions s i n c e fragmen-
t a t i o n i s minimal. Thus a d i s t r i b u t i o n of molecular s i z e s and
hydrocarbon c l a s s e s can be obtained from a s i n g l e a n a l y s i s . This
i s i l l u s t r a t e d i n F i g u r e 1 which compares the FIMS f i n g e r p r i n t s
f o r JP-5 from Shale-I and Shale-II r e f i n i n g . D i s t i n c t d i f f e r e n c e s
c S
can be noted. The preponderance of alkanes ( ^2 +2^ ^ k i g h " n n
l i g h t e d i n Shale-I f u e l which was produced by c r a c k i n g the shale

crude by delayed coking. S h a l e - I I , using a hydrocracking process,
produced a product much lower i n alkanes. A n a l y s i s f o r t o t a l
n-alkane content agrees with t h i s f i n d i n g , 3 7 % i n Shale-I JP-5
( 7 ) and 22% f o r S h a l e - I I . Other s i g n i f i c a n t d i f f e r e n c e s between
the two j e t f u e l s can be noted i n the much higher peaks f o r sub-
s t i t u t e d benzenes (C L ,) and t e t r a l i n s (C L ) i n the Shale-II
0
« n zn—o n zn—o
product.
Other d i f f e r e n c e s can be noted i n the FIMS data assembled i n
Table I I I . For i n s t a n c e , Shale-II a l s o has higher peak sums f o r
c H t h a n
monocyclic alkanes (C H ) and d i c y c l i c alkanes ( -2^ n 2 n
Shale-I. Data f o r a JP-5 sample, a ten g a l l o n q u a n t i t y pro-

duced by f r a c t i o n a t i o n of Paraho shale crude followed by 1200 p s i
c a t a l y t i c hydrogenation of the j e t f u e l cut (9), i s a l s o shown i n
Table I I I . Again t h i s f u e l has a d i s t i n c t l y d i f f e r e n t FIMS f i n g e r -
p r i n t i n response to the r e f i n i n g process used.
P r e p a r a t i v e Scale LC. Separation of JP-5 and DFM on the

Waters r a d i a l l y compressed s i l i c a column gave many f r a c t i o n s .
This i s i l l u s t r a t e d i n F i g u r e 2 f o r s i x ml of DFM. F r a c t i o n one,
beginning at 3.2 min, i s the s a t u r a t e f r a c t i o n which was detected
w i t h a r e f r a c t i v e index d e t e c t o r . F r a c t i o n 2, i n d i c a t e d by s l i g h t
a b s o r p t i o n on the 254 nm uv d e t e c t o r , corresponds to the o l e f i n
fraction* The subsequent f r a c t i o n s , as i n d i c a t e d by the strong
absorption on one or both of the uv d e t e c t o r s , are comprised of

1 0
SHALE-I JP-5
>•
t
CO
z
w
I-
z
z
o
LU JfflyLll L 4
1|]
<
SHALE-II JP-5
J 1— Ui i i r
100 150 200 250
WE
Figure 1. Field ionization MS of Shale-I and Shale-II JP-5 jet fuels

as

Figure 2. Preparative-scale LC separation of Shale-II DFM; 254-nm UV detector ( ); 313-
nm UV detector ( ), RI detector trace not shown. Small numbers indicate times when frac-
tion collection began; the large peak at 16-18 min on the 254-nm trace went off scale. Column,
Prep PAK-500/silica; flow rate, 200 mL/min. to
Table I. Shale-II R e f i n i n g Nitrogen Content*
Product
Jet DFM
Days of Hydro- Pre- Pre- Fractionation
Operation crackate Naphtha Acid Acid Residue
12 1400 1700 2500 1940

18 2000 2300 2900 2700
21 3000 640 2500 4000

25 3800 2900 4700
* PPM (wt/vol), r e p e a t a b i l i t y + 5%
Crude shale o i l contained 2.1% n i t r o g e n
Table I I . n-Alkanes i n Shale-II Fuels
n-Alkane Weight Percent

JP-5 DFM
0.06
0.14 0.13
4.20 0.46
:io
7.23 0.93
:n
6.08 1.40
:i2
3.30 2.22
;i3
0.93 2.39
;u
0.28 2.61
:i5
0.06 2.19
;i6
0.01 2.11
:i7
1.40
;is
0.65
;i9
0.04
•"20
Total 22.23 16.59
R e p e a t a b i l i t y + 4%

16. SOLASH ET AL. Fuel Properties and Chemical Composition 243
aromatic f r a c t i o n s . I t i s noteworthy that f r a c t i o n s 7,8 and 9

e x h i b i t s i g n i f i c a n t a b s o r p t i o n at 254 nm but none at 313 nm. The
JP-5 sample gave only f i v e f r a c t i o n s i n the same type of a n a l y s i s .
Evaporation of the n-pentane s o l v e n t gave an estimate of the
amount of the v a r i o u s f r a c t i o n s . The percentages normalized to
t o t a l 100% are l i s t e d i n Table IV. Recoveries of input sample
amounted to 96 and 93% f o r the DFM and JP-5, r e s p e c t i v e l y . The
l o s s e s were due to evaporation of v o l a t i l e components during the
removal of the s o l v e n t . As expected, f r a c t i o n s 1 and 3 comprised
the bulk of the f u e l samples, 88.5% of the DFM and 95.3% of the
JP-5. The Fluorescent I n d i c a t o r Adsorption (FIA) method, ASTM
D1319, gave data which g e n e r a l l y agrees with the LC p r e p a r a t i v e
s c a l e s e p a r a t i o n . The JP-5 gave an aromatic content of 24.0% by
FIA (versus 23.6% by LC, f r a c t i o n s 3,4 and 5) and an o l e f i n con-

tent of 1.6% (2.9% by LC, f r a c t i o n 2 ) . The DFM had aromatics of
26.0% by FIA (versus 30.4 by LC, f r a c t i o n s 3 through 9) and o l e -
f i n s of 5% (versus 0.8 by LC, f r a c t i o n 2) (10).
Mass Spectrometry of LC F r a c t i o n s . The f r a c t i o n s from the

p r e p a r a t i v e s c a l e LC were subjected to GC/MS a n a l y s i s with e l e c -
t r o n impact i o n i z a t i o n . The t o t a l f r a c t i o n s were a l s o analyzed by
f i e l d i o n i z a t i o n mass spectrometry with a d i r e c t i n s e r t i o n probe.
The FIMS m/e p l o t f o r DFM f r a c t i o n f i v e i s depicted i n F i g u r e 3.
The two major hydrocarbon s e r i e s observed i n t h i s f r a c t i o n are
C H 0 n and C H« -, naphthalenes and acenaphthenes.
r
Trace
n 2n-12 n 2n-14,
amounts of the C H 0 and C H. 0 s e r i e s a l s o appear i n F i g u r e 3.
n zn-lU n zn-o
The f r a c t i o n seven FIMS p l o t (Figure 4) e x h i b i t s aromatic
hydrocarbons with lower hydrogen contents. The two major s e r i e s
present i n t h i s f r a c t i o n are acenaphthenes and f l u o r e n e s , but
methyl phenanthrene or anthracene (m/e = 192) i s a l s o a s i g n i f i -
cant component of f r a c t i o n seven.
A summary of the hydrocarbon s e r i e s i n the nine DFM and f i v e
JP-5 LC f r a c t i o n s are l i s t e d i n Tables V and VI. The data are
q u a l i t a t i v e i n nature and based on both MS techniques, EI and F I .
The trends with f r a c t i o n number are as expected, hydrocarbons
with l e s s hydrogen appear i n the l a t e r f r a c t i o n s . F u r t h e r , the
trend i n aromatic r i n g s i z e was 1 r i n g ( f r a c t i o n 3 ) , 2 r i n g s
( f r a c t i o n 4 ) , and 3 r i n g s ( f r a c t i o n s 5-9). The JP-5 has very
l i t t l e three r i n g m a t e r i a l but the DFM e x h i b i t s evidence f o r con-
s i d e r a b l e amounts of acenaphthenes, f l u o r e n e s , and phenanthrenes/
anthracenes.
The LC s e p a r a t i o n d i d not give sharp s e p a r a t i o n by r i n g s i z e ,
however. For i n s t a n c e , t e t r a l i n s appeared i n f r a c t i o n s 3-5 and
naphthalenes occurred i n f r a c t i o n s 4-7. Larger molecules i n a
p a r t i c u l a r series eluted i n l a t e r fractions. Significantly better
s e p a r a t i o n has been observed with semi-prep LC columns.
S i g n i f i c a n t amounts of p a r t i a l l y or f u l l y saturated r i n g com-
pounds were found i n the j e t and d i e s e l products. Mono- and
d i c y c l i c alkanes were a major p o r t i o n of the s a t u r a t e f r a c t i o n

25
100 150 200 250

M/E
Figure 3. FIMS of DFM, LC Fraction 5; major hydrocarbon series are C Hi

Q
and CH . .
n 2n H

5
100
-f—l—i—r-*i—Y
150
Ik
200 250
M/E
Figure 4. FIMS of DFM, LC Fraction 7; major hydrocarbon series are CJi i n . ,

u
C H -i6>
n 2n and C H . . n 2 n J 8

Table I I I . Hydrocarbon Classes i n JP-5 Samples

by FIMS*
AF-Exxon
Hydrocarbon Shale-I Shale-II (Fractionation &
Series (Coking) (Hydrocracking) Hydrogenation)
C H
50.8 30.4 40.6
n 2n+2
C H 0 12.2 16.9 20.8
n 2n
C H 0 0 4.1 7.1 11.2
n 2n-2
C H 1.9 0.8 3.2

n 2n-4
C H
16.6 19.6 14.4
n 2n-6
C H
12.2 23.8 7.3
n 2n-8
C H
1.7 1.0 2.2
n 2n-10
* Ion i n t e n s i t i e s (total 100)
Table IV. Y i e l d s From LC Separation
Percent Y i e l d
Fraction DFM JP-5
1 68.9 73.6
2 0.8 2.9
3 19.6 21.7
4 7.1 1.6
5 1.2 0.3
6 0.6
7 0.7
8 0.5
9 0.7
% recovered 96 93

SOLASH ET A L . Fuel Properties and Chemical Composition 247
+
I I
M r
+ +
i i i
g
ao
+
II +
*
o
•H
M
M
4->
a
+ +
1
CD
tH
CO
cO
u i I +
&
CO
M i l *
•H
CO
CD
•H
CD
C
o I I
u
co
o
* t H ' *
o
o
>
I I I * "
•H
1
O O
tH CO
u
co
H M-l
CD
W w (0
CD CD
•H •H
CO U
CD CD
W o (0
•H
>-t <H
O •H CD
C O
CO 00 CO
•H M
O CN VD 00
s CO H
I *
CN VO 00 tH tH tH rH
tH
+ I I I I I I I I I
c c C a a a a c
CN CM CN CN CN CN CN CN CN CN CN
American Chemical
Society Library
1155 16th St. N. W.
ACS Symposium Series;Washington, D. C.
American Chemical 20036
Society: Washington, DC, 1981.
00
Table VI. Hydrocarbon S e r i e s i n Shale-II JP-5
LC Fraction
Mass S e r i e s
2n + 2
2n
2n - 2
2n - 4
X
>
2n - 6 + -H- +++ ++ + r
2n - 8 + +++ -H-+ + >
2n - 10 + +f ++ |
s
2n - 12 + >
2:
o
2n - 14 + -H-+
W

>
+++ Major s e r i e s i n f r a c t i o n £
a

++ Significant series in fraction ^
>
+ Trace s e r i e s i n f r a c t i o n H
w
2
> 1
r
Table V I I . Average Molecule i n F r a c t i o n Three
Parameter JP-5 DFM
Aromaticity 0.49 0.39
Aromatic Rings/Molecule 1.0 1.0
Average Mol. Wt. 164 206
Average Mol. Formula C H

C H
12.2 16.8 15.2 23.3
A l k y l Substituents/Molecule 3.2 3.1
Carbons/Alkyl Substituent 2.0 3.0
Naphthene Rings/Molecule 0.5 0.7

and a f a i r amount of t r i c y c l i c alkanes were a l s o found.

T e t r a l i n s / i n d a n e s were a l s o found i n abundance. Some p a r t i a l l y
C t e t r a t i d r o a c e n a l l L
hydrogenated t r i c y c l i c aromatics — n<2n-10 ( y P ~
thene, hexahydrofluorene, and octahydrophenanthrene) — were a l s o
observed. The presence of these types of compounds i s evidence of
the h i g h pressure hydrocracking step i n the r e f i n i n g process.
NMR analyses. F r a c t i o n 3 from the LC s e p a r a t i o n was subjected

to proton nmr examination. The i n f o r m a t i o n from t h i s examination
was t r e a t e d by the method of C l u t t e r and co-workers (11) to des-
c r i b e the average molecule. The c a l c u l a t e d parameters are sum-
marized i n Table V I I . The values obtained are c o n s i s t e n t with the
other information i n t h i s paper and i n the d e s c r i p t i o n of the
Shale-I JP-5 reported i n an e a r l i e r a r t i c l e (7).
D i s c u s s i o n and Conclusions
The information presented i n t h i s paper shows that shale o i l

has an e x c e l l e n t p o t e n t i a l as a source f o r high q u a l i t y middle
d i s t i l l a t e fuels. The Shale-II program produced f u e l s with pro-
p e r t i e s s i g n i f i c a n t l y improved compared to the p r o p e r t i e s of the
f u e l s produced i n Shale-I. In p a r t i c u l a r , Shale-II f u e l s e x h i b i t
v a s t l y b e t t e r s t a b i l i t y , lower f r e e z i n g p o i n t s , and lower oxides of
n i t r o g e n during combustion.
T e s t i n g of the Shale-II JP-5 j e t f u e l , which i s c u r r e n t l y
underway i n four d i f f e r e n t gas t u r b i n e engines, shows good com-
b u s t i o n performance. No problems have been encountered. Likewise,
t e s t i n g of ship steam b o i l e r s , marine gas t u r b i n e s , and d i e s e l
engines on the Shale-II d i e s e l f u e l marine (DFM) i s demonstrating
h i g h l y acceptable performance.
The composition of shale f u e l s may vary widely, however,
depending on the o v e r a l l r e f i n i n g process. Much work i s needed
to explore other r e f i n i n g options and to examine the e f f e c t of
r e f i n i n g on f i n i s h e d f u e l composition and p r o p e r t i e s .
Acknowledgment
The authors thank Dr. S. E. B u t t r i l l , J r . , of SRI I n t e r -

n a t i o n a l f o r performing the FIMS analyses and LCDR W i l l i a m Coleman
of the Naval B i o s c i e n c e s Laboratory f o r conducting the nmr
analyses.
Literature Cited
1. Bartick, H.; Kunchal, K.; Switzer, D.; Bowen, R.; Edwards, R.;
"The Production and Refining of Crude Shale Oil into Military
Fuels," Applied Systems Corp., Vienna, Va., ONR Contract
N00014-75-C-0055, Aug. 1975.

16. SOLASH ET AL. Fuel Properties and Chemical Composition 251
2. Applied Systems Corp., Vienna, Va., "Compilation of Oil Shale

Test Results,"ONRContract N00014-76-C-0427, Apr. 1976.
3. Robinson, E. T.; Wasilk, N. J.; "The Commercial Scale Refin-
ing of Paraho Crude Shale Oil into Military Specification
Fuels," in this book.
4. Drushel, H. F.; Anal. Chem., 1977, 49, 932.
5. Nowack, C. J.; Del Fosse, R. J.; Speck, G.; Solash, J.;
Hazlett, R. N.; "Relation Between Fuel Properties and Chemical
Composition. IV. Stability of Oil Shale Derived Jet Fuel,"
in this book.
6. St. John, G. A.; Buttrill, S. E. Jr.; Anbar, M.; Ch. 17 "Field

Ionization and Field Desorption Mass Spectrometry Applied to
Coal Research," in Organic Chemistry of Coal, ACS Sym. Series
No. 71, John Larson, Ed., 1978.
7. Solash, J.; Hazlett, R. N.; Hall, J. M.; Nowack, C. J.; FUEL,
1978, 57, 521.
8. Affens, W. A.; Hall, J. M.; Beal, E.; Hazlett, R. N.; Nowack,
C. J.; Speck, G.; "Relation Between Fuel Properties and Chemi-
cal Composition. III. Physical Properties of U. S. Navy
Shale-II Fuels," in this book.
9. AFAPL-TR-75-10, USAF Tech. Rpt. "Evaluation of Methods to Pro-
duce Aviation Turbine Fuels from Synthetic Crude Oils, Phase
2," Exxon R&E Co., Linden, N. J., May 1976.
10. White, E. W.; private communication, Naval Ship R&D Center,
Annapolis, MD, 1979.
11. Clutter, L.; Petrakis, L.; Stenger, R. L.; Jensen, R. K.;
Anal. Chem., 1972, 44, 1395.

17
Relation Between Fuel Properties and
Chemical Composition. Physical Properties of
U.S. Navy Shale-II Fuels
W. A. AFFENS, J. M. HALL, E. BEAL, R. N. HAZLETT,
and J. T. LEONARD
C. J. NOWACK and G. SPECK
Naval Air Propulsion Center, Trenton, NJ 08628
The U.S. Navy has been involved for some time in the develop-
ment of Navy fuels from alternative sources (shale oil, tar sands
and coal). As a part of this effort, the Naval Research Labora-
tory and the Naval Air Propulsion Center have been studying the
characteristics of these fuels (1,2). NRL and NAPC are currently
participating in a program to characterize the products from the
Shale-II refining process conducted by the Standard Oil Company
of Ohio (SOHIO) at their refinery in Toledo, Ohio. This paper is
concerned with a part of this program and is a summary of the
work on the physical and related properties of three military
type fuels derived from shale: JP-5 and JP-8 jet turbine fuels,
and diesel fuel marine (DFM) (3,4,5). Another paper of this
symposium (6) will discuss the chemical characterization of the
fuels.
JP-5 (3) is a "high flash point" Navy fuel for carrier-based
jet aircraft and helicopters and occasionally for shipboard power
plants and propulsion. JP-8 (4), a U.S. Air Force jet fuel, is
very similar to "Jet A" kerosene used by commercial jet aircraft
in the United States and elsewhere. DFM (5) is a multipurpose
distillate fuel used by the Navy for ship propulsion in steam
generating, gas turbine, and diesel power plants.
The shale derived fuels used i n these studies were derived
from Paraho crude shale o i l . The fuels were prepared by hydro-
cracking of the total crude, and then fractionation. Both the
JP-5 and DFM Shale-II fuels were acid and clay treated i n f i n a l
finishing steps. The refining process which was used i s described
elsewhere (7).
A t o t a l of thirty-six Shale-II fuel samples have been
examined including seventeen JP-5 samples, five JP-8 samples and
fourteen DFM samples. Of the t h i r t y - s i x samples, twenty-six
were "finished" fuels i n that they had been treated with sulfuric
acid to remove organic bases, and ten were "pre-acid treatment"
samples. Six of the finished samples did not contain additives
but the remaining twenty samples did. The l a t t e r group included
two p i l o t plant samples, a JP-5 ("J-PP") and a DFM ("D-PP").

GC SijmLated D i s t i l l a t i o n
The boiling range of a representative sarrple of each of three

types of fuels was determined by gas chromatography (GC Simulated
Distillation) using ASTM method D 2887 (8). This was also done
for representative petroleum derived JP-5 and DFM samples for
comparison. Data are plotted for the j e t fuels i n Figure 1 and
for DFM i n Figure 2. JP-8 data have been emitted frcm Figure 1
since the Shale-II data for JP-5 and JP-8 are quite similar. The
temperature for the JP-8 (Shale-II) averaged 4°C lower than for
the JP-5 sample at the various percentages. The only exception
was the 0.5% d i s t i l l e d point, for which JP-5 was 5° lower. I t was
concluded from the d i s t i l l a t i o n data and other data which follow
that the JP-8 Shale-II samples can be considered to be JP-5 for
a l l practical purposes.
The Shale-II d i s t i l l a t i o n temperature data, as seen i n the
figures, are somewhat low compared to that of the corresponding
petroleum fuels. As a rule, data obtained by a GC simulated
d i s t i l l a t i o n do not agree with analogous data by actual d i s t i l -
lation. Temperatures by the simulated d i s t i l l a t i o n are lower
than that of simple ASTM pot d i s t i l l a t i o n s (10) at the i n i t i a l
temperatures, higher near the end point temperatures, and i n
close agreement near the midpoint temperatures P,<4).
Miscellaneous Physical Properties
Specific gravity, freezing point and pour point data are

shown i n Table I. For each fuel four kinds of data are given
(where available): the range of the data (nrinimum and maximum
values obtained), the average value for a l l the samples examined,
the military specification requirement for that property, and an
average value for a representative petroleum derived fuel. Also
shown i n the table are the number of fuel samples which were
examined i n each case. This format i s also used for Table II
which w i l l follow.
Specific Gravity. The specific gravities of the Shale-II

jet fuels (one sample of each type) were very similar to each
other, met specification requirements, and were about the same as
that of an average petroleum derived fuel. The two Shale-II DFM
specific gravities were very similar but s l i g h t l y lower than that
of an average petroleum derived fuel.
Freezing Point. With the exception of one JP-8 sample

( J - l l ) , a l l the samples of the j e t fuels froze below the s p e c i f i -
cation maximum. The single exception froze less than 0.5°C
above the allowed value for JP-8, 50°C. The similar freezing
points for the JP-5 and JP-8 samples reinforce the conclusion

AFFENS E T A L . U.S. Navy Shale-II Fuels 255
Figure 1. GC-simulated distillation of JP-5 fuels: petroleum (80-•10) (A); Shale-II

(J-18) (O).

256 OIL SHALE, TAR SANDS, A N D R E L A T E D MATERIALS
Figure 2. GC-simulated distillation of DFM fuels: petroleum (PE-76-79) (A);

Shale-II (D-1)(0).

17. A F F E N S E T A L . U.S. Navy Shale-II Fuels 257
TABLE I. Miscellaneous Physical Properties
Freezing Pour
Specif. Grav. Point Point
C
(25/25°C) a
(°C) D
(°C)
JP-5 (10 samples)
Range -46.8 - -51.7

Average 0.8122 -49.7
Specification 0.788 - 0.845 -46 (max.)
Petroleum 0.818 -49
JP-8 (2 samples)
Range -49.6 - -50.4

Average 0.8098 -50.0
Specification 0.775 - 0.830 -50 (max.)
Petroleum 0.810 -54
DFM (2 samples)
Range 0.8390 - 0.8393 -20.6

Average 0.8392
Specification
Petroleum 0.850 -14
a - ASTM D 1217 (13)

b - ASTM D 2386 (14)
c - ASTM D 97 (15)
d - One sample tested.
e - Data for representative petroleum derived fuel (9,11,12)
f - Same result for both samples,
g - Maximum

TABLE I I . Flammability and Ignition Properties

a b
Flash Point (°C) AIT (°C)
JP-5 (6 samples)
Range 55.1 61.2

C
Average 58.0 , 232
Specification 60 (min.)
Petroleum 64 241
JP-8 (2 samples)
Range 53.4 58.7

c
Average 56.1 238
0
Petroleum 53 238
DFM (2 samples)
Range 71-75
C
Average 73.4 - 238
Petroleum 79 240
a ASTM D 56 (16)
b - ASTM D 2155 (17)
c - One sample tested
d - ASTM D 93 (20)
e - Data for representative petroleum derived fuel (9,11,12,21)

17. AFFENS ET AL. U.S. Navy Shale-II Fuels 259
from the d i s t i l l a t i o n data that the two types of j e t fuels made i n

the SOHIO process are very siioilar. The highest JP-5 freezing
point was that of the pre-acid treatment sample (J-7) which froze
at -46.8°C. The freezing point of j e t fuel i s greatly affected
by the concentration of the higher n-alkanes, such as n-hexadecane
(1). The relationship between freezing point and the concentra-
tion of n-hexadecane i n the fuel appears to be consistent with
that of the Shale-I studies. The amount of the larger alkanes i n
the Shale-II j e t fuels i s r e l a t i v e l y low (6), a result of keeping
the d i s t i l l a t i o n end point lower than normal (3/4). A comparison
of Shale-II and petroleum derived JP-5 d i s t i l l a t i o n end points i s
made i n Figure 1, and was discussed previously. I t was seen that
the Shale-II JP-5 end point i s lower than that of the petroleum
fuel and this i s i n accord with the freezing point data.
Pour Point. The pour points of each of two samples of DFM

were 20.6°C. This value i s well below the specification maxi-
mum of -6.7°C (4) and that of an average petroleum derived DFM
(11,12). As i n the case of the j e t fuel freezing points
discussed above, the lower pour point of the Shale-II DFM i s
consistent with i t s lower d i s t i l l a t i o n end point compared to
that of the petroleum DFM as seen i n Figure 2.
Flammability and Ignition Properties
Flammability and ignition properties are shown i n Table II.

As i n the case of the miscellaneous physical properties (Table
I), the range of the data, averages, specification requirements,
and representative values for petroleum derived fuels are given
i n the table.
Flash Point. Flash points were determined by the Tag

closed cup method (16) rather than by the Pensky-Martens method
(20) as called for i n the specifications for JP-5 (3) and DFM
(5). The Tag closed cup, however, i s specified for JP-8 (4).
The Tag method was chosen i n order to have a basis of comparison
for a l l three fuels and because i t gives values which are closer
to the lower flammability temperature l i m i t which i s important
from the standpoint of safety. For fuels i n the JP-5/DFM flash
point range, the Tag method gives values which are 2-4°C lower
than that of the Pensky-Martens method (12). The JP-8 and the
DFM flash points are seen to be well above the specification
requirements of 38° and 60°C (4,5). i n the case of the JP-5
samples, four of the six samples had Tag flash points which
were below the required 60°C (3). However, i f we assume that
the Pensky-Martens flash points would average about 3°C higher,
four of the six samples would then meet the 60 °C minimum and the
other two would be less than two degrees low. The Shale-II JP-8
flash point data are somewhat higher than that of an average

petroleum derived JP-8 and quite close to that of the Shale-II

JP-5.
Autoignition Temperatures. The autoignition data (AIT) shown

i n Table II were determined by ASTM D 2155 (17). The Shale-II
JP-8 and DFM AIT values (238°C) were identical and similar to
that of their petroleum derived counterparts. The Shale-II JP-5
AIT (232°C), however, was s l i g h t l y lower than that of the other
two fuels as well as that of a representative petroleum JP-5
(241°C), but was well within the 11°C reproducibility l i m i t set
by the method (17). There are no AIT requirements i n the m i l i -
tary specifications for JP-5, JP-8 and DFM (3^,5^ .
Electrostatic Properties
The e l e c t r i c a l conductivity and charging tendency of j e t

fuels are important for predicting electrostatic charge buildup
i n fuel handling equipment, particularly f i l t e r separators.
Electrostatic charge buildup can result i n a spark discharge
capable of igniting flammable vapors i f they are present. This
i s a frequent cause of accidental f i r e s and explosions and i s an
important factor i n safety. Therefore, these properties were
measured on the Shale-II j e t fuels to determine i f these fuels
posed a lesser or greater hazard than their petroleum-derived
counterparts. The only electrostatic specification requirement
for current U.S. military fuels i s that of an e l e c t r i c a l conduct-
i v i t y range for JP-4 (3) and JP-8 (4). This requirement, how-
ever, i s a recent one and d i d not apply to the JP-8 fuels of this
study.
E l e c t r i c a l conductivity was determined by the ASTM method

(18) and charging tendency with the EXXON Mini-Static Tester (19).
The l a t t e r method measures the amount of e l e c t r i c a l charge
generated by flowing a fuel sample through a paper f i l t e r .
Electrostatic data are shown i n Table III. Shale-I data (2)
are included i n the table for comparison. The Shale-I fuels were
also derived from Paraho shale o i l . However, the Shale-I fuels
were prepared by coking of the t o t a l crude, rather than by hydro-
cracking as i n the case of the Shale-II fuels. After the coking,
the Shale-I fuels were then fractionated. For finishing steps,
the JP-5 was subjected to mild hydrotreatment, and the DFM was
treated by acid extraction. The Shale-I refinery process i s
described i n d e t a i l elsewhere (22). The petroleum data are
based on a fuel survey. The Shale-II values i n the table are i n
the normal ranges found for petroleum derived j e t fuels. The
response to the addition of static dissipator additive, ASA-3,
i s also normal. The sharp increase of charging tendency i n the
fuel sample to which ASA-3 had been added at f i r s t glance appears
to be at cross purposes with the intent of an anti-static agent.
However, this i s not the case, since most of the charge would

Table III. Electrostatic Properties of Shale Jet Fuels

Charging
Conductivity Tendency
Fuel Source Treatment (pS/m) (pC/mV
JP-5 Shale-I 246 c
ti
Filtered 215 7035
it
ii
Shale-II - 6.6 2100
1 ppm ASA-3 added 228 16600
ii
Petroleum 6
- 0.8-15 1500 - 4000
JP-8 Shale-II _ 5.3 890

II
1 ppm ASA-3 added 142 12300
ti
(Specification) 200 (min.) -
600 (max.) -
a - ASTM D 3114 (18)

b - Exxon Mini tester (Measured with Type 10 f i l t e r paper) (19)
c - Fuel contained a sediment which clogged the f i l t e r of the
charging tendency apparatus
d - F i l t e r e d thru 0.45y millipore
e - Data for representative petroleum derived fuels
f - MIL-T-83133A, 18 May 1979 (4)

r e l a x v e r y r a p i d l y ( l e s s than one second) because o f the

i n c r e a s e d c o n d u c t i v i t y due t o the ASA-3. However, i t i s seen i n
Table I I I , t h a t a c o n c e n t r a t i o n o f more than 1 ppm ASA-3 would
be r e q u i r e d f o r the S h a l e - I I JP-8 sample t o meet the new e l e c t r i -
c a l c o n d u c t i v i t y s p e c i f i c a t i o n requirement.
The Shale-I JP-5 e x h i b i t e d abnormally h i g h e l e c t r i c a l
c o n d u c t i v i t y and c h a r g i n g tendency. T h i s f u e l was an o f f s p e c i -
f i c a t i o n p r o d u c t c o n t a i n i n g sediment which clogged the f i l t e r
of t h e c h a r g i n g tendency apparatus making i t impossible t o
o b t a i n a charge d e n s i t y measurement. The v a l u e s shown i n the
t a b l e were obtained a f t e r the sample was f i l t e r e d through a
0.45y M i l l i p o r e f i l t e r .
Copper C o r r o s i o n
T e s t s f o r c o r r o s i o n a r e o f a q u a l i t a t i v e type and a r e made

to determine whether the f u e l i s f r e e o f tendency t o corrode cop-
per b e a r i n g a l l o y s i n a i r c r a f t pumps. The r e s u l t s o f the ASTM
copper s t r i p c o r r o s i o n t e s t s (23) a r e shown i n Table IV. The
samples i n the t a b l e a r e grouped i n accordance w i t h t h e i r
r e f i n i n g treatment and by the a d d i t i v e s the f u e l s were r e p o r t e d
to c o n t a i n . I n t h e t a b l e , t h e two p i l o t p l a n t samples were
f i n i s h e d samples and contained both a n t i o x i d a n t (AO-29) and f u e l
system i c i n g i n h i b i t o r (FSII). The remaining twenty nine
samples were r e f i n e r y prepared and a r e i n three groups: t h e
f i r s t group o f n i n e samples was taken b e f o r e the' a c i d t r e a t -
ment and contained no a d d i t i v e s . The second group o f s i x
samples was a c i d and c l a y t r e a t e d b u t contained no a d d i t i v e s .
The t h i r d group o f f o u r t e e n samples was f i n i s h e d ( a c i d and
c l a y treated) and was r e p o r t e d t o c o n t a i n AO-30 a n t i - o x i d a n t .
The JP-5 samples i n the t h i r d group were found t o c o n t a i n FSII
(24). The a d d i t i v e s a r e i d e n t i f i e d i n the t a b l e . The t e s t
r e s u l t s a r e summarized on t h e r i g h t hand s i d e o f the t a b l e .
I t i s seen i n T a b l e IV t h a t both p i l o t p l a n t samples
( f i n i s h e d samples p l u s a d d i t i v e s ) passed the copper c o r r o s i o n
t e s t , as d i d most o f t h e a d d i t i v e - f r e e r e f i n e r y samples. How-
ever, a l l f o u r t e e n o f t h e a d d i t i v e - c o n t a i n i n g r e f i n e r y samples
f a i l e d . These f o u r t e e n samples were a l l f i n i s h e d samples and
c o n t a i n e d AO-30. S i n c e t h e s i x DFM samples which f a i l e d the
t e s t d i d n o t c o n t a i n F S I I , i t i s assumed t h a t t h i s a d d i t i v e d i d
not p l a y a p a r t . S i n c e the two p i l o t p l a n t samples ( c o n t a i n i n g
AO-29) passed the t e s t , and t h e f o u r t e e n r e f i n e r y samples
(containing AO-30) f a i l e d , q u e s t i o n s a r e r a i s e d concerning the
a n t i - o x i d a n t a d d i t i v e s which were used. These r e s u l t s need t o
be r e l a t e d t o the sequence o f o p e r a t i o n s i n the r e f i n e r y process
and t o t h e nature o f the a d d i t i v e s which were used. I t seems
probable t h a t e i t h e r t h e r e was a problem w i t h the a c i d treatment
process by which a c o r r o s i v e s p e c i e s was produced which ended
up i n the f i n i s h e d samples, o r t h a t t h e a d d i t i v e s used may have
been contaminated. Both a s p e c t s may be i n v o l v e d .

Number of Samples
Fuel Treatment Additives Total Passed Failed
P i l o t Plant Preparation:
JP-5 Acid Treated AO-29 & FSII 1 1 0

DFM " " AO-29 1 1 0
Total 2 2 0
Refinery Preparation:
JP-5, JP-8 Pre-Acid None 6 5 1

DFM 3 3 0
Total 9 8 1
JP-5, JP-8 Acid Treated 5 5 0

DFM 1 0 1
Total 6 5 1
JP-5 " " AO-30 & FSII 8 0 8

DFM " " AO-30 6 0 6
14 0 14

Total
a - ASTM D 130 (23).

b - Fuel System Icing Inhibitor (Ethylene glycol monomethyl
ether) (3,4) - j e t fuels only; Anti-oxidants "AO-29" (2,6-
11
ditertiary-butyl-4-methyl-phenol) or "AO-30 (2,4-dimethyl-
6-tertiary-butyl phenol).
Free sulfur (17 ppm) and mercaptans (10 ppm) have been
detected i n the Shale-II JP-5. Model studies found that the
combined presence of these two species, each at about the 10 ppm
l e v e l , can cause f a i l u r e of the copper corrosion test. The a n t i -
oxidant, AO-30, exhibited indications of reinforcing the effects
of the sulfur species i n the model studies.
An attempt was made to correct the copper corrosion problem
by different types of fuel treatments (25). JP-5 samples were
subjected to clay or s i l i c a gel f i l t r a t i o n , or treatment with
activated charcoal to remove the corrosive compounds. None of
these treatments was successful. Samples were also treated with
barium nitrate (to precipitate out sulfonates), sodium hydroxide
(to extract mercaptans), and a i r bubbling to oxidize the corrosive
compounds. These chemical treatments also were unsuccessful.
However, JP-5 fuel (which f a i l e d the copper corrosion test) passed

i f benzotriazole, sometimes used to passivate copper surfaces,
was added to the fuel i n low concentrations (2 ppm) using FSII as
a solvent. This technique i s effective for reducing j e t fuel
attack on copper-nickel pipes used aboard a i r c r a f t carriers (26).
Conclusions
The physical properties of the Shale-II fuels were similar

to that of equivalent fuels derived frcm petroleum. The d i f f e r -
ences observed could be irtinimized by modest changes i n refining
steps. Based on these results and other Navy R and D, shale o i l
can be considered a premising alternative source for the produc-
tion of U.S. Navy d i s t i l l a t e fuels.
Acknowledgment
The authors thank Mr. Charles Stansky of UOP, Inc. for

determination of free sulfur i n the JP-5 and for consultation on
the copper corrosion problem.
The authors are also indebted to Mr. John De Guzman for
assistance i n obtaining the flash point and freezing point data.
Literature Cited
1. Solash, J.; Hazlett, R.N.; Hall, J.M.; Nowack, C.J.; Fuel,
1978, 57, 521.
2. Affens, W.A.; Leonard, J.T.; McLaren, G.W.; Hazlett, R.N.,
Preprints, Symposium on Oil Shale, Tar Sands, and Related
Materials, Division of Fuel Chemistry, Amer. Chem. Soc.,
Sept. 1976, 21, (No. 6), 249.
3. Military Specification, Turbine Fuel, Aviation Grades, JP-4
and JP-5, MIL-T-5624L, 18 May 1979.

4. Military Specification, Turbine Fuel, Aviation, Kerosene

Type, Grade JP-8, MIL-T-83133A, 18 May 1979.
5. Military Specification, Fuel Oil, Diesel Marine, MIL-F-16884G,
7 March 1973; Amend. 22 March 1978.
6. Solash, J; Hazlett, R.N.; Burnett, J.C.; Beal, E.; Hall, J.M.,
"Relation Between Fuel Properties and Chemical Composition.
II. Chemical Characterization of U.S. Navy Shale-II Fuels",
This Symposium.
7. Robinson, E.T.; Wasilk, N.J.; "The Commercial Scale Refining
of Paraho Shale Oil into Military Specification Fuels",
This Symposium.
8. "Boiling Range Distribution of Petroleum Fractions by Gas

Chromatography", Amer. Soc. for Test. and Mater., ASTM
D2887, 1973.
9. Shelton, E.M.; "Aviation Turbine Fuels, 1978," Bur. of Mines,
Petrol. Survey 109, May 1979.
10. "Distillation of Petroleum Products," Amer. Soc. for Test.
and Mater., ASTM D86 (1972).
11. "Distillate Fuel Economic Study," Nav. Ship Engr. Center, May
1974.
12. Affens, W.A.; "Shipboard Safety - A Meaningful Flash Point
Requirement for Navy Fuels," Naval Research Laboratory
Report 7999, Oct. 28, 1976.
13. "Density and Relative Density (Specific Gravity) of Liquids
by Bingham Pycnometer," Amer. Soc. for Test. and Mater.,
ASTM D1217 (1976).
14. "Freezing Point of Aviation Fuels," Amer. Soc. forTest.and
Mater., ASTM D2386 (1972).
15. "Pour Point of Petroleum Oils," Amer. Soc. for Test. and
Mater., ASTM D97 (1971).
16. "Flash Point by Tag Closed Tester," Amer. Soc. forTest.and
Mater., ASTM D56 (1975).
17. "Autoignition Temperature of Liquid Petroleum Products",
Amer. Soc. for Tes. and Mater., ASTM D2155 (1976).

18. "D-C Electrical Conductivity of Hydrocarbon Fuels," Amer.

Soc. for Test. and Mater., ASTM D3114 (1972).
19. Young, D.A.; "Mini-Static Test Procedure", Exxon Research
and Engineering Co., Linden, N.J., June 1972.
20. "Flash Point by Pensky-Martens Closed Tester," Amer. Soc.
for Test. and Mater., ASTM D93 (1974).
21. Coordinating Research Council, "A Survey of Electrical
Conductivity and Charging Tendency Characteristics of Air-
craft Turbine Fuels," CRC Report 478, April 1975.
22. Bartick, H.; Kunchal, K.; Switzer, D.; Bowen, R.; Edwards, R.,

Fuels", Final Report of Applied Systems Corp., Vienna, Va.
to the Office of Naval Research, under Navy Contract No.
N-00014-75-C-0055, August 1975.
23. "Detection of Copper Corrosion from Petroleum Products by
the Copper Strip Tarnish Test," Amer. Soc. for Test. and
Mater., D130 (1976).
24. "Fuel System Icing Inhibitor in Hydrocarbon Fuels (Iodo-
metric Method)," Fed. Test Method Std. 791B, Method
5327.3, Jan. 15, 1969.
25. Speck, G; "Correction of Shale-II Copper Corrosion Problem,"
Naval Air Propulsion Center, Final Report NAPC-LR-80-6,
22 April 1980.
26. Shertzer, R.; "Investigation of the Reduction of Thermal
Stability of Fuel by Copper Contamination on Aircraft
Carriers," Naval Air Propulsion Test Center, NAPTC-PE-14,
January 1973.

18
Relation Between Fuel Properties and Chemical
Composition. Stability of O i l Shale-Derived
Jet Fuel
C. J. NOWACK, R. J. DELFOSSE, and G. SPECK
Naval Air Propulsion Center, Trenton, NJ 08628
1
J.SOLASH and R. N. HAZLETT
The Navy has been interested in the use of alternate fossil

fuels for sometime (1-4). Our interest is focused primarily in
establishing the effects of chemical composition on fuel proper-
ties since such relations will lead to greater availability and
better use of fuels. We recently reported some of our results on
jet fuels derived from coal, tar sands and oil shale (1). Other
papers in this series report on some aspects of oil shale derived
fuels obtained from a large production experiment, Shale II, per-
formed by Paraho, Inc. (5,6). In this paper, we report on some
aspects of stability of a jet fuel prepared in an earlier Navy
Program, Shale-I (3).
Previous work with shale oil derived middle distillates has
noted the very high freezing point of these fuels (1,7). In addi-
tion, shale oil fuels which were high in nitrogen gave as much as
45% conversion of fuel bound nitrogen to NO emissions when burned
x
under typical jet engine conditions (4). The high nitrogen content
in shale oil jet fuels leads to particulates and gums upon standing
at ambient temperatures in the absence of light (7).
Stability concerns the tendency of fuels to form particulates
and/or coatings on engine surfaces under two different sets of con-
ditions. One set of conditions is that of storage: weeks or
months at temperatures of >^40 C, quiescent exposure to air, and no
light. The fuel encounters much different conditions in a jet air-
o
craft: a few hours at temperatures up to 80 C with agitation and
exposure to air in the fuel tanks plus a minute or so at 150-250 C
in the fuel system components with only dissolved air present.
Again, no light is present during the high temperature exposure.
Shale oil derived fuels used in this work were much poorer than
petroleum derived fuels under both stability regimes and a thorough
study of the stability of these fuels was undertaken.
1
Current address: Department of Energy, Germantown, MD, 20767.

Experimental
The shale o i l derived j e t f u e l (designated Shale-I) used i n

t h i s work was produced from a crude shale o i l ( s u p p l i e d by Paraho,
Inc.) by delayed coking, f r a c t i o n a t i o n , and m i l d hydrotreatment at
the Gary-Western r e f i n e r y . The e n t i r e production operation has
been f u l l y described elsewhere (3). The p h y s i c a l p r o p e r t i e s of the
j e t f u e l have been reported (1).
High temperature s t a b i l i t y of the f u e l s was measured using an
A l c o r , Inc. J e t F u e l Thermal Oxidation Tester (JFTOT) ( 8 ) . Low
temperature (storage) s t a b i l i t y was determined by measurement of
gums, contamination and peroxide concentration ( a l l by ASTM stand-
ard methods) before and a f t e r exposure to temperatures of 60 C f o r
four weeks. The f u e l s were stored i n l£ low a c t i n i c , dark pyrex
g l a s s b o t t l e s and were l o o s e l y covered to prevent exposure to a i r -

borne p a r t i c u l a t e s . A i r could s t i l l d i f f u s e i n t o the v e s s e l . The
v e s s e l s with f u e l and v a r i o u s a d d i t i v e s were thermostated at 60 C
f o r the s p e c i f i e d length of time.
I s o l a t i o n of shale o i l j e t f u e l b a s i c n i t r o g e n compounds was
accomplished by e x t r a c t i o n with IN aqueous HC1 followed by n e u t r a l -
i z a t i o n of the HC1 adducts (7). The b a s i c n i t r o g e n compounds thus
obtained were analyzed by gas chromatography using a Perkin-Elmer
model 3920B gas chromatograph equipped with a 100m OV-101 g l a s s
WCOT column and n i t r o g e n - s p e c i f i c detector. This column separated
the n i t r o g e n compounds i n t o at l e a s t 70 incompletely r e s o l v e d com-
ponents. T e n t a t i v e i d e n t i f i c a t i o n of some of the components was
made by combined gas chromatography-mass spectrometry (gc-ms) using
a Hewlett-Packard model 5982 gc-mass spectrometer with a Hewlett-
Packard model 5933A dedicated data system. The mass spectrometer
was equipped with a 33m SE-30 SCOT column and was operated i n the
EI mode at 70 eV. In a d d i t i o n , the extracted b a s i c n i t r o g e n com-
pounds were subjected to f i e l d i o n i z a t i o n mass spectroscopy (FIMS).
Ions produced by f i e l d i o n i z a t i o n tend not to fragment and an
accurate molecular weight p r o f i l e of a mixture can be constructed
<£>.
Results and Discussion
E a r l y work with r e f i n e d shale o i l c l e a r l y showed (7) that the

j e t f u e l used (M.000 ppm nitrogen) was unstable and r a p i d l y plugged
f i l t e r s upon standing f o r s e v e r a l days. Removal of nitrogenous
m a t e r i a l by a c i d e x t r a c t i o n or by passing the f u e l over c l a y or
s i l i c a g e l gave improved storage p r o p e r t i e s . The chemical con-
s t i t u t i o n of the n i t r o g e n c o n t a i n i n g m a t e r i a l s was sought i n an
e f f o r t to d i s c o v e r s p e c i f i c c l a s s e s of compounds which could cause
s t a b i l i t y problems. I t i s w e l l known that p y r r o l e s and i n d o l e s
are q u i t e r e a c t i v e toward a i r and l i g h t (10-14) and i f present i n
l a r g e q u a n t i t i e s i n these f u e l s might account f o r the observed
instability.

18. NOWACK ET AL. Oil Shale-Derived Jet Fuel 269
B a s i c Nitrogen Compounds. The Shale-I j e t f u e l contained

976 ppm n i t r o g e n of which 860 ppm n i t r o g e n was a c i d e x t r a c t a b l e .
The n e u t r a l i z e d e x t r a c t was subjected to gas chromatography using
an a l l g l a s s system with a high e f f i c i e n c y c a p i l l a r y column. A
chromatogram of the a c i d e x t r a c t obtained using a n i t r o g e n - s p e c i f i c
d e t e c t o r i s shown i n F i g u r e 1. As shown, r e t e n t i o n time matching
i m p l i e s that the m a j o r i t y of compounds are p y r i d i n e - t y p e bases.
The mixture was a l s o subjected to gc-mass spectroscopy. The t o t a l
i o n chromatogram i s shown i n F i g u r e 2. The lower r e s o l u t i o n SCOT
column used on the mass spectrometer d i d not permit unequivocal
assignment of each peak. T e n t a t i v e assignments of the numbered
peaks are noted i n Table I. In many cases, the e l e c t r o n impact
mass spectrum c l e a r l y showed the presence of more than one com-
pound. However, the main compound type observed was a l k y l s u b s t i -
tuted p y r i d i n e with l e s s e r q u a n t i t i e s of q u i n o l i n e s . We used

another mass s p e c t r a l technique to help confirm our gc-ms a s s i g n -
ments. The FIMS r e s u l t s are tabulated i n Table I I . Since mole-
cules tend not to fragment when f i e l d i o n i z e d , the FIM spectrum
can be scanned f o r parent masses; compound c l a s s e s and higher a l k y l
s u b s t i t u t e d homologs are r e a d i l y recognized. The FIMS data confirm
the presence of major amounts of p y r i d i n e compounds with l e s s e r
q u a n t i t i e s of q u i n o l i n e and t e t r a h y d r o q u i n o l i n e types.
While i o n i z a t i o n e f f i c i e n c i e s f o r various c l a s s e s of compounds
under FI c o n d i t i o n s are not known with c e r t a i n t y , we do not expect
them to be very d i f f e r e n t f o r the aromatic n i t r o g e n types observed
here. We have observed that FIMS data on b a s i c n i t r o g e n compounds
r e s u l t i n a higher than expected i n t e n s i t y f o r parent +1 peaks.
This was observed f o r our b a s i c n i t r o g e n e x t r a c t s but not f o r
n-alkane or n e u t r a l f u e l samples. We a t t r i b u t e t h i s phenomenon to
the presence of water i n the b a s i c n i t r o g e n e x t r a c t s ; water r a p i d l y
l o s e s a hydrogen atom to the r a d i c a l c a t i o n generated by F I .
E x t r a c t i o n of the Shale-I j e t f u e l with HC1 i s approximately
90% e f f i c i e n t f o r removal of n i t r o g e n c o n t a i n i n g m a t e r i a l . Remain-
ing i n the f u e l are 116 ppm of non-basic n i t r o g e n compounds. Pre-
sumably, these compounds w i l l be comprised p r i m a r i l y of p y r r o l e ,
i n d o l e and carbazole types. Only traces of s u b s t i t u t e d p y r r o l e s
and i n d o l e s were observed by FIMS i n the b a s i c n i t r o g e n f r a c t i o n
(Table I I ) . Shale o i l n i t r o g e n compounds have been c h a r a c t e r i z e d
p r e v i o u s l y (15) and s i n c e carbazoles and p y r r o l e s could not be
t i t r a t e d i t i s not s u r p r i s i n g that they are a l s o not e f f i c i e n t l y
e x t r a c t e d by IN HC1.
High Temperature (Thermal) S t a b i l i t y . The high temperature

s t a b i l i t y of the Shale-I j e t f u e l s was measured using the JFTOT
technique (8). The thermal o x i d a t i v e s t a b i l i t y of the r e c e i v e d
f u e l (976 ppm N) was measured. The f u e l was then a c i d e x t r a c t e d ,
the i s o l a t e d b a s i c n i t r o g e n compounds added back i n t o the e x t r a c t e d
shale f u e l i n v a r y i n g q u a n t i t y , and the thermal o x i d a t i v e s t a b i l i t y
redetermined. A petroleum d e r i v e d JP-5 was a l s o subjected to*JFTOT

-J
to
o

18. NOWACK E T A L . Oil Shale-Derived Jet Fuel 271
*«·»
S
*+-»
·»"•S»·
I
-s:
s
•S
t>
S3
s;
'S
ι
S
s
"S
s;
.o
<N
Si
S

to
Table I. T e n t a t i v e S t r u c t u r a l Assignments of GC-MS Peaks to
^ Prominent Peaks
Peak // m/e (Peak, R e l . Abundance) T e n t a t i v e Assignment
+ +
1 78(M , Base),77(M -l,20%),52(15%) benzene
+ + + +
2 107(M ,Base),106(M -l,50%),92(M -CH ,20%),79(M -HCN,30%) 3 4-ethylpyridine
+ + + +
3 121(M ,40%),120(M -l,Base),107 (M -CH ,25),93 (M -C H ,20%) 2 2 4 2-methyl-ethyl-
pyridine
+ + + +
4 121(M ,Base),120(M -l,30%),106(M -CH ,21%),79(M -C H.,35%) Q Q 4-i-propyl pyridine
3 3 6
+ + + + + ~
5 121(M ,85%),120(M -1,Base),107(M -CH ,25%),93 (M -C H.,15%),79(M —C H,, 0 0 Q 2-propylpyridine
2 2 4 3 6
35%) 2
+ + + +
6 121(M ,Base),120(M -l,55%),106(M -CH ,50%),93(M -C H.,15%) Q 0 3-ethyl-4-methyl- a
pyridine >
+ + + + +
7 135(M ,45%),134(M -l,Base),121(M -CH ,45%),107(M -C H,,25%),106(M - ? 2 2-propyl-methyl- ™
C H ,30%)
2 5 pyridine $
+ + + +
8 135(M ,Base),134(M -l,55%),121(M -CH ,20%),120(M -CH ,50%) 2 3 3,4-diethylpyridine >
+ + + + +
9 135(M ,45%),134(M -l,Base),121 (M -CH ,30%),120(M -CH ,35%),107(M - 2-propyl-methyl- S
C H.,65%)
0 pyridine >
a
+ + + + +
10 135(M ,Base),134(M -1,75%),121(M -CH ,15%),120(M -CH ,30%),107(M - 4-butylpyridine ^

C H.,28%),106(M -C H_,30%)
o o r
H
+ + + +
11 149(M ,15%),148(M -l,33%),135(M -CH ,33%),134(M -CH ,56%),121 3-propyl-4-ethyl- 5

(M -C H ,Base) 2 4 pyridine g
>
H
2
>
Continued
Prominent Peaks
m/e (Peak, R e l . Abundance) T e n t a t i v e Assignment
+ + + +
163_p4 ,6%),162(M -l,11%),149(M -CH ,53%),148(M -CH ,40%),121 2 3 3-propyl-4-ethyl-5-
(M -C HL,Base)
0 methylpyridine
J o
+ + + +
163(M ,8%),162(M -l,15%),149(M -CH ,60%),148(M -CH ,Base),134 3-ethyl-4-butylpyri-
(M -C H ,44%),121(M -C H ,30%)
2 5 3 6 dine
+ + + + +
163 (M , 25%),162(M -l,55%),149(M -CH ,34%),148(M -CH ,55%),135(M - 2 3 2-propyl-3-methyl-4-
C H ,Base)
2 4 ethylpyridine
+ + + +
163(M ,9%),162(M -l,25%),148(M -CH ,18%),134(M -C H ,30%),121 2-butyl-4-ethylpyridine
(M -C H ,Base)
3 6
+ +
163 (M ,27%) , 162 (M -l,20%) , 147 (45%) , 121 Qi'-C^, Base) 3,4-dipropylpyridine +
tetrahydromethyl quino-
line
+ + + +
176 (M -l,11%),163(M -CH ,30%),162(M -CH ,37%),147(M ,80%),146(70%),
2 3 ^ - p y r i d i n e + 3-methyl-
143(M ,Base) quinoline + tetrahydro-
methyl q u i n o l i n e
Complex spectrum probable species i n c l u d e
C . - p y r i d i n e , C^- quino-
l i n e , methyl-tetrahydro-

quinoline, ethyl t e t r a -
hydroquinoline
+ + + + +

177(M ,6%),176(M -l,10%),162(M -CH ,18%),161(M ,18%),135(M - 2 probable components:
C H ,Base)
3 6 ^ - p y r i d i n e (one b u t y l
group), e t h y l - t e t r a -
hydroquinoline, methyl
tetrahydroquinoline,
methylquinoline
Table I - Continued to
Prominent Peaks
A
Peak // m/e (Peak, Rel> Abundance) T e n t a t i v e Assignment
B + + + + +
20 177(M ,8%),176(M -l,15%),160(M -l,15%),134(M -C H ,26%),121(M - 3 ?
major: C^-pyridine
C^HgjBase) (with 2-pentyl gp)
21 Complex spectrum probable major com-

ponents: C~-quinoline,
C^-tetrahyaroquinoline;
minor: C^-pyridine

ponents: C2~quinoline;
minor components: C^- o
tetrahydroquinoline, P
C^-pyridine; trace:
C^-tetrahydroquinoline r
m
23 Complex spectrum probable major com- H
>
ponent: Cg-pyridine; 90
very minor components;

C -quinoline, C ^ t e t r a -
2
hydroquinoline
+ + + + +
>
24 191(M ,14%),190(M -l,5%),171(M ,45%),170(M -l,25%),121(M -70,Base) major: C - p y r i d i n e ,
R
O
C - q u i n o l i n e ; minor:
3
C^-quinoline, C ^ - t e t r a - w

r
hydroquinoline >
H
W
B + + +
25 171(M ,Base),170(M -l,30%),156(M -CH ,25%),149(25%) 3
3-methyl-4-ethyl quino- a

l i n e ; minor: Cg-
>
p y r i d i n e , other quino- H
M
l i n e types
2
>
Table I - Continued
Prominent Peaks
Peak // m/e (Peak, R e l . Abundance) T e n t a t i v e Assignment
ponents: C ^ - p y r i d i n e ,
C^-quinoline
ponents: C^-pyridine +
C ..-quinoline
'Refer to F i g u r e 2 f o r numbered peak p o s i t i o n i n t o t a l i o n chromatogram of gc-mass spectrum.
'EI s p e c t r a showed evidence of more than one compound.

Table I I . F i e l d I o n i z a t i o n Mass Spectrum

Base F r a c t i o n from Shale-I JP-5
Range of Relative
Series "n" Values* Compounds Ion Count
C H_ N 12-14 Piperidines 10
n 2n+l
C H 0N 9-15 Pyrroles 28
n 2n-3
C H _N
0 9-16 Pyridines 1000
n 2n-5
C H _N
0 9-11-16 Tetrahydro- 170
n 2n-7
quinolines
A3 15 Indoles 13
n 2n-9
C H_ N 11 14 Quinolines 157
n 2n-ll
* Underlined value of "n" i n d i c a t e s components i n l a r g e s t amount.

t e s t i n g . The petroleum f u e l had a breakpoint temperature of 275°C

and at 260 C d i d not produce s i g n i f i c a n t tube deposit r a t i n g s (TDR)
or develop a s i g n i f i c a n t pressure drop across the i n - l i n e JFTOT
filter. A number of n i t r o g e n compounds, t y p i c a l of those found i n
t h i s study, were then added to the petroleum derived JP-5 and the
high temperature s t a b i l i t y redetermined. The r e s u l t s with shale
and petroleum f u e l s are d i s p l a y e d i n Table I I I .
In p r e v i o u s l y reported s t a b i l i t y work with shale o i l derived
j e t f u e l s (16) i t was shown that the JFTOT thermal s t a b i l i t y im-
proved as the t o t a l n i t r o g e n content decreased. In Table I I I , i t
i s observed that the thermal s t a b i l i t y of the Shale-I f u e l improves
as the c o n c e n t r a t i o n of b a s i c n i t r o g e n compounds decreases. In
previous work (16) the lower n i t r o g e n contents of the shale o i l
j e t f u e l s were achieved by more severe hydrotreatment.

I t can a l s o be observed that there apparently are two major
modes of high temperature thermal i n s t a b i l i t y and the e f f e c t of
b a s i c n i t r o g e n i s d i f f e r e n t i n each. I f thermal s t a b i l i t y i s
measured only by tube d e p o s i t s , a s l i g h t r i s e i n breakpoint temper-
ature i s observed as the b a s i c n i t r o g e n content i s reduced (break-
point by TDR from 244°C to 254°C as b a s i c N changes from 838 to 7
ppm). However, i f the f i l t e r pressure drop i s used f o r determining
breakpoint, then a much l a r g e r change, 227 to 279 C, i s observed
as b a s i c n i t r o g e n content i s reduced.
Pure compounds which are s i m i l a r to those found i n the Shale-I
b a s i c n i t r o g e n f r a c t i o n s (Tables I and I I ) were added to a p e t r o -
leum based j e t f u e l of high s t a b i l i t y (Table I I I ) . Most of the
b a s i c n i t r o g e n compounds used r e s u l t e d i n n e g l i g i b l e deposit (TDR)
formation with the exception of 2-amino-3-methylpyridine. 4-t-
B u t y l p y r i d i n e showed evidence of f i l t e r plugging but only s l i g h t
d e p o s i t s were formed. P y r r o l e , however, was found to produce a
very high deposit r a t i n g (TDR) and a l s o plugged the i n - l i n e f i l t e r .
Much more work with pure compounds i n simple c a r r i e r v e h i c l e s i s
necessary before d e f i n i t i v e mechanistic i n f e r e n c e s can be drawn
regarding the e f f e c t s of the v a r i o u s c l a s s e s of n i t r o g e n compounds.
Storage S t a b i l i t y . The low temperature or storage s t a b i l i t y

of the Shale-I f u e l was followed by determining changes i n per-
oxides, gums, contamination, and high temperature s t a b i l i t y (JFTOT
behavior). The l a t t e r method was employed s i n c e deposit precursors,
which might form at low temperatures, could s e r i o u s l y degrade
engine operation i f present i n s u f f i c i e n t concentration. The t e s t
f u e l was placed i n 1£ g l a s s b o t t l e s which were l o o s e l y covered to
permit a i r d i f f u s i o n to the f u e l . Ten ml of d i s t i l l e d water and
1 g of i r o n f i l i n g s were placed i n each sample. These c o n d i t i o n s
simulated a c t u a l storage tank c o n d i t i o n s s i n c e water i s always
present i n f u e l storage tanks and the f u e l i s f r e q u e n t l y i n contact
with uncoated metal surfaces of storage tanks. The samples were
maintained at 60 C f o r four weeks. The r e s u l t s of the storage
s t a b i l i t y experiments are presented i n Table IV.

to
Table I I I . High Temperature S t a b i l i t y of J e t Fuels -o
B o„ 00
Fuel Type Acid Extractable Total Heater Tube (TDR) Filter

Shale O i l - 860 976 _ 232
Jet F u e l C
838 954° 244 227
C
97 213° 243 232
C
50 166° 251 241
C C
7 12 3 254 279
260°C
D
Petroleum A d d i t i v e Cone., ppm Max TDR AP, mm o
4-_t-butylpyridine, 56 1 20 r
2-jt-butylpyridine, 49 10 1
X
5-ethyl-2-methylpyridine, 107 11 3 >
r
4-benzylpyridine, 56 7 2 w
2-amino-3-methylpyridine, 134 45 14 H
N,N-dimethylaniline, 82 6 >
p y r r o l e , 100 32 Bypass
>
A,
Measured using A l c o r , Inc. JFTOT according to ASTM Standard Method D-3241. a
Breakpoint i s defined as the temperature of t e s t at which a maximum TDR of >17 i s >
B, observed or a pressure drop of >25 mm Hg i s a t t a i n e d across the i n - l i n e JFTOT f i l t e r .
O

Shale O i l JP-5 e x t r a c t e d with HC1, washed, and the i s o l a t e d b a s i c n i t r o g e n r
C, compounds r e i n t r o d u c e d to the shale o i l f u e l . >
H
w
o

The petroleum d e r i v e d j e t f u e l had a breakpoint temperature of 275°C and g
D, had n e g l i g i b l e TDR or f i l t e r pressure drop at 260 C. >
H
Pressure drop of >25mm developed a f t e r which the t e s t continued f o r standard w

E, 2.5 hr. p e r i o d with the hot f u e l bypassing the f i l t e r .
1
r
Table IV. Results of Storage S t a b i l i t y Tests of Treated Shale-I JP-5
Storage Results 2
U
Q Existent Gums, JFTOT 260 C

B i
Experiment # N-Additive, ppm mg/100 ml Peroxide, meq/kg Max TDR
Inhibitor, ppm o
Before After Before After Before A f t e r
1 0 0 0 0 0.14 60 1 10 w
2 8.4 0 0 1.4 1.4 64.3 9 13 H
3 25 0 0 5.4 1.0 96.8 4 27 >
4 125 0 0 1.6 0.2 42.5 5 48
D
5 o 25-DA 0 0 0 1.0 0 2
05
6 39° 25-DA 0 0 0 0.6 0 2
7 123° 25-DA 0 0 0.1 0.1 5 13

8 0 24-HP 0 0 0.7 0.7 4 9
9 5-ethyl-2- 0 0 5 0.6 83 4 35
methylpyridine, 50
tt
10 24-HP 0 0 0.6 0.6 0 0
11 2,5-dimethylpyrrole, 50 0 0 0.4 0.09 4.2 25 25
it
12 24-HP 0 0.6 0.07 0.5 26 25
A,
Shale-I JP-5 c o n t a i n i n g 976 ppm n i t r o g e n was f i r s t a c i d e x t r a c t e d then t r e a t e d with s i l i c a g e l to
y i e l d a nitrogen-free fuel. Conditions of storage: temp=60 C; time=4 weeks; no a g i t a t i o n ; a i r
allowed to f r e e l y d i f f u s e i n t o f u e l .
B,

A n t i o x i d a n t s used were commercial products q u a l i f i e d f o r Navy f u e l use; DA=phenylene diamine
(1,4-diamino benzene); HP=hindered phenol (2,6-di-tert-butyl-4-methylphenol).
C,
A c i d e x t r a c t e d n i t r o g e n compounds added to n i t r o g e n - f r e e Shale-I JP-5 to b r i n g n i t r o g e n content to

designated l e v e l .
D,
Corrected f o r a n t i o x i d a n t n i t r o g e n content.
to
-o
VO
Storage s t a b i l i t y measurements have been performed on some

shale d e r i v e d f u e l (17). In that study, a Paraho j e t f u e l (very
s i m i l a r to our Shale-I) was found to form some gums (increase i n
gums of about 2 mg/100 ml f u e l a f t e r 32 weeks storage at 43 C) but
there was only a small i n c r e a s e i n a c i d number and no increase i n
viscosity. In our storage t e s t s , we t r i e d to determine the e f f e c t s
of b a s i c n i t r o g e n compounds on the storage s t a b i l i t y of the Shale-I
fuel. The combination of a c i d e x t r a c t i o n followed by s i l i c a g e l
chromatography of the Shale-I f u e l was found to be e f f e c t i v e f o r
removing a l l n i t r o g e n c o n t a i n i n g compounds. The n i t r o g e n - f r e e
Shale-I f u e l showed some tendency to accumulate peroxides under our
t e s t c o n d i t i o n s , but no a p p r e c i a b l e gums were formed. In a d d i t i o n ,
the high temperature (JFTOT) s t a b i l i t y of the aged n i t r o g e n - f r e e
f u e l was s i m i l a r l y acceptable (Table IV).
Increasing q u a n t i t i e s of b a s i c n i t r o g e n compounds, which were

a c i d e x t r a c t e d from the f u e l , were then reintroduced i n t o the f u e l
and the storage s t a b i l i t y redetermined. As the concentration of
b a s i c n i t r o g e n compounds increased from 8.4 to 125 ppm N, both the
gum and peroxide concentration a f t e r storage rose to a maximum
(25 ppm N) then f e l l back to lower l e v e l s (Table IV, expt. //2, 3,
4). However, the JFTOT deposit r a t i n g a f t e r storage was monotoni-
c a l l y degraded by i n c r e a s i n g n i t r o g e n l e v e l s . The f i l t e r pressure
drop was three mm or l e s s f o r experiments #1-4 except f o r the 125
ppm N sample which exceeded 25 mm a f t e r storage.
The r e s u l t s imply a r e l a t i o n s h i p between gum formation and
peroxide concentration. I t i s p o s s i b l e that the r e l a t i o n between
the gum and peroxide i s of the form:
°2
RH > [peroxide] >gum
We propose that some f u e l components, p a r t i c u l a r l y those c o n t a i n -

ing s u l f u r , n i t r o g e n , oxygen, and o l e f i n i c f u n c t i o n a l groups, a l s o
r e a c t under storage c o n d i t i o n s with peroxides. Condensation or
d i m e r i z a t i o n of the f r e e r a d i c a l intermediates formed i n these
r e a c t i o n s can b u i l d the h i g h l y p o l a r , medium molecular weight
(400-500) gums observed i n some s t u d i e s (18). A n t i o x i d a n t s of
e i t h e r the phenylene diamine or hindered phenol type were e f f e c t i v e
f o r i n h i b i t i n g both peroxide and gum formation i n the current
s t u d i e s (Table IV, expts. #5, 6, 7, 8). The i n h i b i t o r s a l s o im-
proved high temperature s t a b i l i t y a f t e r storage.
The contamination l e v e l i n experiments #l-#8 e x h i b i t e d no
patterns with n i t r o g e n content. Further, the phenylene diamine
a n t i o x i d a n t exerted l i t t l e e f f e c t . In any case, the contamination
did not exceed 2.4 mg/i i n any of these t e s t s .
A p y r i d i n e compound was found to storage degrade the Shale-I
f u e l f a s t e r than a p y r r o l e compound (Table IV, expt. #9, 11).
A f t e r storage the Shale-I f u e l doped with 50 ppm 5-ethyl-2-methyl-
p y r i d i n e had an order of magnitude more gums and 20 times the

peroxide l e v e l compared to the same f u e l c o n t a i n i n g 50 ppm 2,5-

d i m e t h y l p y r r o l e . A n t i o x i d a n t s were e f f e c t i v e at i n h i b i t i n g both
gums and peroxides i n the n i t r o g e n doped f u e l s a f t e r storage
(Table IV, expt. #10, 12), p a r t i c u l a r l y f o r the p y r i d i n e compound.
5-Ethyl-2-methylpyridine caused a l a r g e change i n JFTOT r e -
s u l t s a f t e r storage. The TDR increased from four p r i o r to s t o r -
age to 46 a f t e r storage. Correspondingly, the f i l t e r pressure
drop changed from three mm to bypass c o n d i t i o n (>25 mm i n 120
minutes). In c o n t r a s t , 2,5-dimethylpyrrole caused e q u a l l y poor
JFTOT performance before and a f t e r storage. Not only d i d the
before and a f t e r t e s t s give high TDR values, but the f i l t e r
pressure drop exceeded 25 mm i n s i x and ten minutes, r e s p e c t i v e l y .
The hindered phenol a n t i o x i d a n t was e f f e c t i v e with the p y r i d i n e
for maintaining good JFTOT behavior during the four week storage
s t a b i l i t y (no i n c r e a s e i n TDR or f i l t e r pressure drop). This

a d d i t i v e was not a c t i v e i n the presence of the p y r r o l e , however.
The TDR values were about the same and the f i l t e r pressure drop
exceeded 25 mm i n seven and one-half and eight minutes, respec-
t i v e l y , f o r the before and a f t e r storage t e s t s .
Summary
High temperature thermal s t a b i l i t y and storage s t a b i l i t y ex-

periments were conducted using Shale-I j e t f u e l . As b a s i c n i t r o -
gen compounds are removed by a c i d e x t r a c t i o n from the Shale-I f u e l ,
JFTOT s t a b i l i t y improves ( e s p e c i a l l y f i l t e r pressure drop perform-
ance). A f t e r four weeks of a c c e l e r a t e d storage, the Shale-I f u e l
c o n t a i n i n g b a s i c n i t r o g e n compounds formed more gums and peroxides,
and e x h i b i t e d degraded JFTOT performance. The b a s i c n i t r o g e n com-
pounds e x t r a c t e d from the Shale-I f u e l were c h a r a c t e r i z e d by way
of v a r i o u s mass s p e c t r a l methods. Compounds s i m i l a r to those
found i n the b a s i c n i t r o g e n f r a c t i o n were used as a d d i t i v e s f o r
JFTOT and storage t e s t s on a petroleum f u e l and n i t r o g e n - f r e e
Shale-I f u e l s . Both p y r i d i n e s and p y r r o l e s c o n t r i b u t e to f u e l
i n s t a b i l i t y . Much more work must be performed i n order to estab-
l i s h c l e a r trends and to deduce a d e t a i l e d mechanism of f u e l
degradation.
Acknowledgement
The authors thank Dr. S. E. B u t t r i l l , J r . , of SRI Interna-

t i o n a l f o r conducting the f i e l d i o n i z a t i o n mass s p e c t r a l a n a l y s i s
on a Naval Research Laboratory c o n t r a c t .
Literature Cited
1. Solash, J.; Hazlett, R. N.; Hall, J. M. and Nowack, C. J.;

Fuel, 1978, 57, 521.

2. Eisen, F. S.; Sun Oil Company Final Report on U.S. Navy Con-
tract No. N-00140-74-C00568, February 6, 1975.
3. Bartick, H.; Kunchal, K.; Switzer, D.; Bowen, R.; Edwards, R.;
Fuels," Applied Systems Corp. Final Report on Office of Naval
Research Contract No. N-00014-75-C-0055, August 1975.
4. Klarman, A. F. and Rollo, A. J.; Naval Air Propulsion Center
Report No. NAPC-PE-1, November 1977.
5. Solash, J.; Hazlett, R. N.; Burnett, J. C.; Beal, E. and Hall,
J. M.; "Relation Between Fuel Properties and Chemical Composi-
tion. II. Chemical Characterization of U.S. Navy Shale-II
Fuels," in this book.

6. Affens, W. A.; Hall, J. M.; Beal, E.; Hazlett, R. N.; Nowack,
C. J. and Speck, G.; "Relation Between Fuel Properties and
Chemical Composition. III. Physical Properties of U.S. Navy
Shale-II Fuels," in this book.
7. Solash, J.; Nowack, C. J. and Delfosse, R. J.; Naval Air Pro-
pulsion Center Report No. NAPTC-PE-82, May 1976.
8. ASTM Method D-3241.
9. Buttrill, Jr., S. E.; "Analysis of Jet Fuels by Mass Spectrome-
try," in Naval Research Laboratory Workshop on Basic Research
Needs for Synthetic Hydrocarbon Jet Aircraft Fuels, Naval Air
Systems Command, June 15-16, 1978, and references therein.
10. Frankenfeld, J. E. and Taylor, W. F.; Final Report under Naval
Air Systems Command Contract No. N-0019-76-0675, February 1979,
and references therein.
11. Witkop, B.; J. Amer. Chem. Soc., 1950, 72, 1428.
12. Witkop, B. and Patrick, J. B.; J. Amer. Chem. Soc., 1951, 73,
713.
13. Saito, I.; Matsuura, T.; Nakagawa, M. and Hino, T.; Accts.
Chem. Res., 1977, 10, 346.
14. Beer, R. J. S.; McGrath, L. and Robertson, A.; J. Chem. Soc.,
1950, 3283.
15. Frost, C. M. and Poulson, R. E.; Amer. Chem. Soc., Div. Petro-
leum Preprints, 1975, 20, 176.

18. NOWACK ET AL. Oil Shale-Derived Jet Fuel 283
16. Reynolds, T. W.; National Aeronautics and Space Administration,

Technical Memorandum No. TM-X-3551, June 1977.
17. Brinkman, D. W.; Whisman, M. L. and Bowden, J. N.; Bartlesville
Energy Technology Center, Report of Investigation No. 78/23,
March 1979.
18. Ward, C. C.; Schwartz, F. G. and Whisman, M. L.; Technical
Report #11 under Ordnance Project TB5-01-010, Bartlesville
Energy Technology Center, July 1961.

19
Pyrolysis of Shale Oil Residual Fractions
ROBERT N. HAZLETT, ERNA BEAL, THOMAS VETTER,
RICHARD SONNTAG, and WILLIAM MONIZ
JP-5, the Navy jet fuel, must meet many stringent require-
ments if satisfactory performance in aircraft and fuel handling
and storage systems is to be attained (1). Among the critical
requirements are those for a low freezing point and a low vis-
cosity. The freezing point is the property of concern in this
paper. Jet aircraft are exposed to low temperatures and the
fuels must not interfere with flying operations by freezing and
plugging filters. It has not been practical to make JP-5 from
some petroleum crudes because the specification freezing point
of -47°C (maximum) is difficult to meet along with the minimum
required flash point of 60°C. The freezing point situation
could be relieved by lowering the initial distillation point but
this would simultaneously decrease the flash point. Since mil-
lions of gallons of jet fuel are stored on most aircraft carriers,
the 60°C flash point is required to reduce the fire hazard due
to the fuel.
Thus we are emphasizing f u e l f r e e z i n g point phenomena i n a
program to i n c r e a s e the a v a i l a b i l i t y of JP-5 from petroleum and
shale o i l . D i m i t r o f f et a l C2) examined the i n f l u e n c e of compo-
s i t i o n on f r e e z i n g point of s e v e r a l types of f u e l s . They found
the s a t u r a t e f r a c t i o n of a f u e l u s u a l l y exerted the g r e a t e s t
e f f e c t on f r e e z i n g point but the aromatic f r a c t i o n seemed to be
important i n some cases.
The Naval Research Laboratory has r e l a t e d the f r e e z i n g
point of JP-5 type f u e l s to the n-alkane content, s p e c i f i c a l l y
n-hexadecane (1). This r e l a t i o n s h i p a p p l i e s to j e t f u e l s de-
r i v e d from a l t e r n a t e f o s s i l f u e l resources, such as shale o i l ,
c o a l , and t a r sands, as w e l l as those derived from petroleum.
In general, j e t f u e l s from shale o i l have the h i g h e s t and those
from c o a l the lowest n-alkane content. The o r i g i n of these
n-alkanes i n the amounts observed, e s p e c i a l l y i n shale
derived f u e l s , i s not r e a d i l y explained on the b a s i s of l i t e r a -
ture i n f o r m a t i o n . Studies of the processes, p a r t i c u l a r l y the


ones i n v o l v i n g thermal s t r e s s , used to produce shale derived

f u e l s are needed to d e f i n e how the n-alkanes form from l a r g e r
molecules. The information developed w i l l s i g n i f i c a n t l y con-
t r i b u t e to the s e l e c t i o n of processes and r e f i n i n g techniques
f o r f u t u r e f u e l production from shale o i l .
In t h i s work, a shale crude o i l residue was separated i n t o
three chemical f r a c t i o n s . The f r a c t i o n s were then subjected to
nmr a n a l y s i s to estimate the p o t e n t i a l f o r n-alkane production
and to p y r o l y s i s s t u d i e s to determine an experimental n-alkane
yield.
P y r o l y s i s Mechanisms
A l a r g e n-alkane breaks apart by a f r e e r a d i c a l mechanism to

y i e l d smaller hydrocarbons, both n-alkanes and 1 - o l e f i n s . T h i s

process, as o r i g i n a l l y diagnosed by Rice (3), u l t i m a t e l y y i e l d s
mostly small o l e f i n s with 2 to 4 carbon atoms. This behavior i s
encouraged by high temperatures and low pressures. At the
moderate temperatures and higher pressures more t y p i c a l of shale
r e t o r t i n g and delayed coking, however, F a b u s s - S m i t h - S a t t e r f i e l d
(4) behavior occurs. In t h i s s i t u a t i o n , a s i n g l e fragmentation
step occurs and equal amounts of n-alkanes and o l e f i n s form.
F u r t h e r , the y i e l d of hydrocarbons i n the intermediate carbon
range i s about the same. Unbranched o l e f i n s formed i n the p y r o l y -
s i s r e a c t i o n s r e a d i l y convert to n-alkanes by hydrogenation.
Thus, formation of n-alkanes i n the j e t f u e l d i s t i l l a t i o n
range can be explained i f l a r g e n-alkanes are present i n the
crude o i l source. Q u a n t i t i e s of l a r g e n-alkanes are i n s u f f i c i e n t ,
however, to e x p l a i n the amounts found (up to 37%) i n the j e t f u e l
made from shale (1). Other p o s s i b l e precursors to small s t r a i g h t
chain molecules are branched compounds or s u b s t i t u t e d c y c l i c com-
pounds. Attack i n a s i d e chain obviously a f f o r d s a path to an
n-alkane. E s t e r s , a c i d s , amines, and ethers a l s o have the poten-
t i a l to form n-alkanes i f an unbranched a l k y l chain i s present
i n the molecule.
Carbon-13 nmr s t u d i e s i n d i c a t e that o i l shale rock contains
many long unbranched s t r a i g h t chain hydrocarbon groups (5). The
shale o i l derived from the rock a l s o gives i n d i c a t i o n of c o n s i d e r -
able s t r a i g h t chain m a t e r i a l with l a r g e peaks at 14, 23, 30, and
32 ppm i n the C-13 nmr spectrum.
Experimental Studies
Separation. A residue from Paraho shale o i l was obtained by

vacuum d i s t i l l a t i o n at 40 t o r r to an end point of 300°C (equiva-
l e n t to 420°C at one atmosphere p r e s s u r e ) . The r e s i d u e was then
separated on a c t i v a t e d s i l i c a g e l i n t o a saturate f r a c t i o n , an
aromatic f r a c t i o n , and a p o l a r f r a c t i o n . The s a t u r a t e f r a c t i o n
was removed from the s i l i c a with n-pentane s o l v e n t , then the

19. HAZLETT ET AL. Pyrolysis 287
aromatic f r a c t i o n was removed with a 25:75 benzene: n-pentane

s o l v e n t . The p o l a r f r a c t i o n was desorbed with 25:75 benzene:
methanol s o l v e n t . Although the p o l a r f r a c t i o n r e q u i r e d methanol
f o r d e s o r p t i o n , i t was only s l i g h t l y s o l u b l e i n methanol. I t d i s -
solved r e a d i l y i n benzene, however. The n i t r o g e n content of
v a r i o u s eluates was determined by Drushel's method (6) as an i n d i -
c a t i o n of the s e p a r a t i o n e f f i c i e n c y . The pentane eluant contained
no n i t r o g e n and the p o l a r f r a c t i o n (benzene:methanol) contained
97% of the recovered n i t r o g e n . If 100% benzene was used to de-
sorb the aromatic f r a c t i o n , up to 20% of the n i t r o g e n was found
i n the aromatic f r a c t i o n . The n i t r o g e n c o n c e n t r a t i o n i n the
separated f r a c t i o n s was 2.5% i n the p o l a r , 0.13% i n the aromatic
and l e s s than 0.01 wt% i n the saturate f r a c t i o n . The input N
concentration i n the residue was 2.2 wt%.

The d i s t i l l a t i o n residue comprises 48% of the shale crude
o i l . On a chemical b a s i s , the p o l a r compounds comprise 71%, the
s a t u r a t e s 13% and the aromatics 16% of the recovered r e s i d u e .
Mass recovery from the separation was 85% but n i t r o g e n recovery
was much l e s s , 70%. The m a t e r i a l r e t a i n e d on the s i l i c a g e l , con-
sequently, appears to be h i g h l y p o l a r and high i n n i t r o g e n .
Carbon-13 nmr A n a l y s i s . Samples of the v a r i o u s f r a c t i o n s

were submitted to a n a l y s i s by C-13 nmr. The C-1,3 spectrum a f f o r d s
a d i s t i n c t separation of the aromatic and a l i p h a t i c absorption
regions plus a good r e s o l u t i o n of many peaks due to s p e c i f i c
molecular s t r u c t u r e . Thus, a good amount of u s e f u l information
can be obtained even f o r a complex mixture such as a f u e l f r a c -
tion. With respect to the present study, the a l i p h a t i c r e g i o n
of the spectrum i s of p a r t i c u l a r importance.
Q u a n t i t a t i v e a n a l y s i s of the a l i p h a t i c region was a t t a i n e d
by i n c l u d i n g a known amount of methanol i n the sample as an
i n t e r n a l standard. A long unbranched fragment w i l l e x h i b i t peaks
at s e v e r a l p o s i t i o n s i n the a l i p h a t i c region of the spectrum.
The peak corresponding to the methyl end group (a-carbon) appears
at 14 ppm with reference to t e t r a m e t h y l s i l a n e at zero ppm. The
CH group adjacent to the methyl group ($-carbon) absorbs at
2
23 ppm and subsequent absorptions appear at 32 and 29.5 ppm f o r

the Y" and 6- carbons. Beyond t h i s , a l l other CH groups i n a 2
long unbranched chain absorb at 30 ppm. Therefore, t h i s l a t t e r

peak would be q u i t e l a r g e f o r a long chain. In f a c t , the r a t i o
e a k c a n
of the area of t h i s peak to the a- $- or Y " P afford i n -
formation on the average chain length of the unbranched fragment.
A spectrum f o r the a l i p h a t i c region of the p o l a r f r a c t i o n
from the shale residue i s shown i n F i g u r e 1 . The d i s t i n c t i v e
peaks at 14, 23, 32, and 30 ppm demonstrate the presence of
s i g n i f i c a n t amounts of long unbranched groups i n t h i s f u e l f r a c -
tion. The 29.5 peak appears as a shoulder on the 30 peak and
these two peaks were i n t e g r a t e d together. Q u a n t i t a t i o n of the
s p e c t r a l information using the methanol i n t e r n a l standard gives

the data l i s t e d i n Table I. As expected, the content of long

unbranched a l k y l groups i s greatest f o r the s a t u r a t e f r a c t i o n s .
F u r t h e r , the s t r a i g h t chain a l k y l groups i n the s a t u r a t e f r a c t i o n
are longer on the average than those i n the aromatic and p o l a r
f r a c t i o n s . We conclude that there i s a d e f i n i t e p o t e n t i a l f o r
making n-alkanes and 1 - o l e f i n s i n the j e t f u e l d i s t i l l a t i o n range
by c r a c k i n g compounds found i n the h e a v i e r shale o i l c u t s .
Pyrolysis. The residue f r a c t i o n s were s t r e s s e d at tempera-

t u r e and pressure c o n d i t i o n s t y p i c a l of the petroleum r e f i n i n g
process known as delayed coking (7). The c o n d i t i o n s used were
450°C and about 90 p s i pressure. Each thermal s t r e s s was conducted
i n a s i x inch long, 1/4 i n c h o.d. 316 s.s. tube c l o s e d at one end
and f i t t e d at the other end with a s t a i n l e s s s t e e l v a l v e v i a a
Swagelok connection. The tube, with a weighed amount of sample

(approximately 0.1 g ) , was attached to a vacuum system, cooled
to -78°C, and pumped to remove a i r . The tube was then thawed and
the cooling/pumping process repeated. The tubes were heated by
i n s e r t i n g them i n t o 9/32 inch holes i n a s i x inch diameter alumi-
num b l o c k f i t t e d with a temperature c o n t r o l l e r .
At the c l o s e of the h e a t i n g p e r i o d , the tubes were cooled
to -78°C and the v a l v e removed. A mixed solvent of n-pentane and
benzene (50:50) was added to the tube which was then capped and
warmed to room temperature. The s o l u t i o n and a subsequent r i n s e
were t r a n s f e r r e d to a screw cap v i a l which was then stored i n a
f r e e z e r u n t i l a n a l y s i s . The sample c o n c e n t r a t i o n i n the solvent
was t y p i c a l l y 3 to 5%. A weighed amount of toluene was added
as an i n t e r n a l standard p r i o r to a n a l y s i s .
The s t r e s s e d samples were analyzed by two techniques, both
based on gas chromatography. In the f i r s t , the s o l u t i o n with
i n t e r n a l standard was i n j e c t e d i n t o a 10 f t , 1/8 i n c h o.d., 5%
OV-101 column which was programmed to 260°C at 12°/min a f t e r a
5.0 min i n i t i a l hold at 60°C. The JP-5 cut was i n t e g r a t e d as
a s i n g l e sum and compared to the i n t e r n a l standard to determine
the y i e l d of JP-5 from the p y r o l y s i s experiment. The i n i t i a l gc
cut point f o r the JP-5 was set midway between n-octane and
n-nonane and the f i n a l point midway between n-hexadecane and
n-heptadecane. The gc b a s e l i n e d i d not r i s e during t h i s p o r t i o n
of the a n a l y s i s , hence r e l i a b l e i n t e g r a t i o n was obtained.
The second gc technique determined the i n d i v i d u a l n-alkanes
and 1-alkenes i n the pyrolyzed sample. A 100 m w a l l - c o a t e d g l a s s
c a p i l l a r y gave the r e q u i r e d r e s o l u t i o n and the n-alkanes and
1-alkenes stood out as d i s t i n c t , w e l l resolved peaks. OV-101 or
0V-17 w a l l coatings provide adequate s e p a r a t i o n . A c a r r i e r gas
flow of one cc/min was combined with an i n l e t s p l i t r a t i o of
50:1 and a 310°C i n j e c t o r temperature. The column temperature
was r a i s e d to 250°C at 4°/min a f t e r an 8.0 min i n i t i a l hold at
80°C. Peak i d e n t i f i c a t i o n was based on r e t e n t i o n time matching
with n-alkane and 1-alkene standards.

19. H A Z L E T T E T A L . Pyrolysis 289
TMS
32 30 0 PPM
Figure 1. C-13 NMR spectrum of shale oil residual polar fraction; aliphatic
region, TMS reference, methanol internal standard; integration trace (upper curve)
Table I. Carbon-13 nmr Examination

of Shale O i l R e s i d u a l F r a c t i o n s
Wt. % Carbon Average

in Aliphatic Unbranched Carbon Chain
Fraction Region Alkyl-Groups* Length**
Saturate 100 40 43
Aromatic 60 21 14-22
Polar 56 30 20
* Sum of areas of absorption peaks at 14, 23, 30, and 32 ppm.
** For unbranched a l k y l groups: based on r a t i o of 30 ppm peak

area to average of 14, 23, and 32 peak areas.
Precision: + 10%

P y r o l y s i s of the s a t u r a t e f r a c t i o n f o r 30 min at 450°C gave

the n-alkane and 1-alkene y i e l d s shown i n Figure 2. The n-alkanes
predominated over the 1-alkenes at a l l carbon numbers f o r t h i s
sample. This was g e n e r a l l y true f o r a l l f r a c t i o n s and a l l s t r e s s
times. The 1-alkenes were l e s s s t a b l e than the n-alkanes and the
l a r g e r alkenes were very minor products f o r s t r e s s times 60 min
and longer. Figure 2 i n d i c a t e s that the product e x h i b i t s a p l a t e a u
i n the 10-14 carbon number range, an i n t e g r a l part o f the JP-5
d i s t i l l a t i o n range.
The e f f e c t of s t r e s s time on y i e l d i s i l l u s t r a t e d i n F i g u r e
3. The n-alkane + 1-alkene sum f o r each carbon number i s p l o t t e d .
For a 16 min s t r e s s the y i e l d s f o r carbon numbers 10 through 14
are almost i d e n t i c a l . Consequently, one-step Fabuss-Smith-Satter-
f i e l d p y r o l y s i s (4) i s c o n t r o l l i n g . The t o t a l y i e l d i n c r e a s e s
at 30 min but the s h i f t to a maxima at C-10 i n d i c a t e s product
i s forming and undergoing secondary decomposition. This trend
i s extended s i g n i f i c a n t l y a t longer times such as shown by the
60 min data. Here the maximum i s o u t s i d e the JP-5 range and
the y i e l d of molecules with 16 or more carbons i s q u i t e low.
For the p o l a r f r a c t i o n , the combined n-alkane + 1-alkene
y i e l d increased up to 60 min s t r e s s time, then reversed (Figure
4). The y i e l d of the l a r g e r molecules - 15 carbons and above -
was d r a s t i c a l l y reduced at 180 min. Even at 16 min the products
obtained i n l a r g e s t y i e l d were* on the low end of the JP-5 d i s -
t i l l a t i o n range. This was c o n s i s t e n t with the lower value found
by nmr f o r the average unbranched a l k y l chain l e n g t h . The a r o -
matic y i e l d p a t t e r n f e l l between that f o r the s a t u r a t e and p o l a r
f r a c t i o n s . The maximum y i e l d f o r the aromatic f r a c t i o n always
f e l l at 10 or 11 carbons w i t h a f a i r l y sharp maximum.
A summary of the JP-5 y i e l d data f o r a l l f r a c t i o n s s t r e s s e d
for v a r i o u s times at 450°C i s presented i n Table I I . The s a t u -
r a t e f r a c t i o n a f f o r d s the highest y i e l d of JP-5 but the other
f r a c t i o n s a l s o give good y i e l d s at intermediate s t r e s s times.
The p o l a r f r a c t i o n r e q u i r e s a longer s t r e s s time to a t t a i n i t s
maximum y i e l d of JP-5.
The p o t e n t i a l n-alkane y i e l d s i n the JP-5 cut a r e l i s t e d i n
Table I I I . These values were obtained by summing the c a p i l l a r y
gc y i e l d s of n-alkanes and 1-alkenes f o r carbon numbers 9 through
16. T h i s t o t a l was d i v i d e d by the corresponding JP-5 y i e l d i n
Table I I to give the p o t e n t i a l n-alkane y i e l d .
A l l f r a c t i o n s a t t a i n e d s i m i l a r maximum n-alkane y i e l d s ,
20-25%. S u r p r i s i n g l y , the p o l a r f r a c t i o n gave the highest y i e l d s
of p o t e n t i a l n-alkanes. F u r t h e r , the p o l a r f r a c t i o n gave a h i g h
conversion of the weight percent unbranched a l k y l groups to
n-alkanes, 24.9% (Table I I I ) vs 30% (Table I ) . The maximum
aromatic conversion r a t i o was even h i g h e r , 19.9 vs 21% whereas
the s a t u r a t e r a t i o was much lower, 22.7 vs 40%. The p o t e n t i a l
n-alkane y i e l d s f o r a l l f r a c t i o n s f e l l o f f at longer s t r e s s times.

HAZLETT ET A L . Pyrolysis 291
<
LU
<
<
(/) 0.40 I V ^.e> n - A L K A N E S
o
^ 0.30 I
Q
>- 0.20 J
1-ALKENES \
J . L _J i
ie 20
CHAIN LENGTH
Figure 2. Pyrolysis of shale oil residual saturate fraction at 450°C for 30 min

Figure 3. Pyrolysis of shale oil residual saturate fraction at 450°C. The yield is
the sum of n-alkane plus 1-alkene for the indicated chain length.

HAZLETT ET A L . Pyrolysis
\ \
\
\X •0
—*-~30min.
8
J10_ J12 i L
14
I
16
. I .
18
L
20
CHAIN LENGTH
Figure 4. Pyrolysis of shale oil residual polar fraction at 450°C. The yield is
sum of n-alkane plus 1-alkene for the indicated chain length.

Table I I . Product Y i e l d *
Pyrolysis JP-5 Y i e l d (Percent)
Time (min) SAT. AROM. POLAR
16 20.4 18.8 5.7
30 28.0 23.6 14.1
60 27.3 23.9 19.6
120 - 12.0 16.3
180 - 16.8
* - P y r o l y s i s temperature - 450°C.
Precision: + 6%.
Table I I I . P o t e n t i a l n-Alkane Y i e l d
from Various R e s i d u a l F r a c t i o n s
Pyrolysis Yield
Time (min.) Saturate Aromatic Polar
16 22.7 14.4 14.7
30 20.8 19.6 24.9
60 15.5 19.9 21.7
120 - 15.1 24.9
180 _ _ 20.1
* - P y r o l y s i s temperature - 450°C; y i e l d i n percent i s sum

of n-alkanes + 1-alkenes f o r C to C... hydrocarbons
q
d i v i d e d by JP-5 y i e l d from Table I I .
P r e c i s i o n : + 10%

19. H A Z L E T T ET AL. Pyrolysis 295
D i s c u s s i o n and Conclusions
A l l three r e s i d u a l f r a c t i o n s a f f o r d good y i e l d s of JP-5

range m a t e r i a l by p y r o l y s i s at 450°C. This i s p a r t i c u l a r l y impor-
tant f o r the p o l a r f r a c t i o n s i n c e i t comprises 71% of the vacuum
r e s i d u e . The best y i e l d of the JP-5 cut comes at d i f f e r e n t times
f o r the v a r i o u s f r a c t i o n s , but a time i n the 30 to 60 min range
would appear to be the optimum time f o r good y i e l d at 450°C f o r
a l l three chemical f r a c t i o n s .
The p o l a r f r a c t i o n gave the h i g h e s t p o t e n t i a l ri-alkane y i e l d
i n the JP-5 cut. This i n d i c a t e s that the bulk of the p o l a r
molecules fragment c l o s e to the f u n c t i o n a l group, thus a f f o r d i n g
e f f i c i e n t production of n-alkanes and 1-alkenes. The data f o r
the r e s i d u a l aromatic f r a c t i o n a l s o shows that fragmentation of

the s i d e c h a i n occurs c l o s e to the r i n g , probably between the 3
and y carbons. The s a t u r a t e f r a c t i o n i s l e s s s e l e c t i v e i n the
s i t e of fragmentation s i n c e s t r o n g l y a c t i v a t i n g groups are absent.
Thus, a s i g n i f i c a n t p o r t i o n of unbranched a l k y l m o i e t i e s end
up i n branched chain and a l i c y c l i c hydrocarbons a f t e r p y r o l y s i s .
The p o t e n t i a l n-alkane y i e l d f o r the s a t u r a t e f r a c t i o n
decreases as p y r o l y s i s time i n c r e a s e s . On the other hand, the
n-alkane y i e l d s go through a maximum w i t h time f o r the aromatic
and p o l a r r e s i d u a l f r a c t i o n s . P y r o l y s i s times i n excess of 60
minutes are p r e f e r r e d with respect to lower p o t e n t i a l n-alkane
y i e l d but t h i s would be at some l o s s i n JP-5 y i e l d .
Although a l l f r a c t i o n s gave p o t e n t i a l n-alkane y i e l d s much
higher than those found i n JP-5 derived from petroleum, none of
the shale r e s i d u a l f r a c t i o n s gave n-alkane y i e l d s approaching the
37% amount found i n the Shale-I JP-5 (1). A temperature d i f f e r e n t
from the 450°C used here might a f f e c t the conversion percentage.
F u r t h e r , the combined s a t u r a t e , aromatic, and p o l a r f r a c t i o n s may
i n t e r a c t under p y r o l y s i s c o n d i t i o n s to give higher p o t e n t i a l
n-alkane y i e l d s than the f r a c t i o n s s t r e s s e d independently. T h i s
t h e s i s i s being t e s t e d i n current s t u d i e s . In a d d i t i o n , the
vacuum d i s t i l l a t e from the shale crude, p a r t i c u l a r l y the s a t u r a t e
f r a c t i o n s , can c o n t r i b u t e markedly to n-alkane y i e l d i n a j e t
f u e l (8).
Acknowledgement
The authors thank Dr. Hyman Rosenwasser of the Naval A i r

Systems Command f o r funding support.
Literature Cited
1. Solash, J.; Hazlett, R. N.; Hall, J. M.; Nowack, C. J.;
"Relation between Fuel Properties and Chemical Composition,
I. Jet Fuels from Coal, Oil Shale, and Tar Sands," Fuel, 1978,
57, 521.

2. Dimitroff, E.; Gray, J. T. Jr.; Meckel, N. T.; Quillian, R.

D. Jr. Seventh World Petroleum Congress, Individual Paper
No. 47, Mexico City, Mexico, Apr. 2-9, 1967.
3. Rice, F. O. J. Am. Chem. Soc., 1933, 55, 3035.
4. Fabuss, B. M.; Smith, J. O.; Satterfield, C. N. Adv. Pet.
Chem. Refin. 1964, 9, 157.
5. Resing, H. A.; Garroway, A. N.; Hazlett, R. N. "Determination
of Aromatic Hydrocarbon Fraction in Oil Shale by C-13 nmr
with Magic-angle Spinning," Fuel, 1978, 57, 450.
6. Drushel, H. F. Anal. Chem., 1977, 49, 932.
7. Gary, J. H.; Hardwerk, G. E. Petroleum Refining, Ch. 5,
Marcel Dekker, Inc., New York, N. Y., 1975.
8. Hazlett, R. N., "Free Radical Reactions Related to Fuel
Research," Frontiers of Free Radical Chemistry, ed. W. A.

Pryor, Academic Press, N. Y., N. Y., 1980.

20
Synfuel Stability:
Degradation Mechanisms and Actual Findings
DENNIS W. BRINKMAN—U.S. Department of Energy, Bartlesville Energy
Technology Center, P.O. Box 1398, Bartlesville, OK 74003
JOHN N. BOWDEN—Southwest Research Institute, 8500 Culebra Road,
San Antonio, TX 78285
JOHN FRANKENFELD and BILL TAYLOR—Exxon Research and
Engineering, Box 8, Linden, NJ 07036
While substantial quantities of only a few experimental syn-

fuels have been generated, those which are available have demon-
strated the degradation problems that were predicted from work
with petroleum. The high heteroatom and unsaturate content of
syncrudes derived from shale and coal will necessitate closer
attention to processing parameters required to produce a commer-
cially viable product. This paper presents basic and applied
data which should aid in the tradeoff decisions between further
costly processing and product stability. Because this is a
progress report on continuing work, many of the conclusions are
preliminary in nature.
Degradation Mechanisms
Considerable work has been published on degradation mech-
anisms for compounds found in petroleum(1-4). Much of the pre-
viously reported research involved pure compounds in pure hydro-
carbon solvents. The work reported here was performed with
additive-free #2 diesel fuel or JP-8, both of which are middle
distillate fuels in increasing demand. Much of this work is in
progress and only preliminary results can be presented here.
S t r u c t u r a l E f f e c t s . The r e s u l t s of s t u d i e s on s t r u c t u r a l
e f f e c t s which have been c a r r i e d out so f a r are summarized i n
Figure 1. Here the n i t r o g e n compounds are grouped as " s t r o n g l y
d e l e t e r i o u s " , "moderately d e l e t e r i o u s " and " r e l a t i v e l y harmless"
w i t h regard t o t h e i r r e l a t i v e tendencies t o form sludge i n hydro-
carbon f u e l s . The d i f f e r e n c e s between groupings, e s p e c i a l l y
between s t r o n g l y and moderately d e l e t e r i o u s i s q u i t e l a r g e .
These l i m i t e d data seem t o i n d i c a t e t h a t , w i t h few exceptions,
the d e l e t e r i o u s compounds are those which contain h e t e r o c y c l i c
nitrogens with an a l k y l group adjacent t o n i t r o g e n . F i n a l l y , as
observed p r e v i o u s l y Q > A ) the 2,5-dimethyl p y r r o l e (DMP) con-
f i g u r a t i o n appears s i g n i f i c a n t l y more r e a c t i v e than 2,4-dimethyl
0097-6156/81/0163-0297$05.00/0

formation
Structural effects on sediment
Figure 1.

20. BRINKMAN ET AL. Synfuel Stability 299
p y r r o l e . These observations are based on l i m i t e d data and must

be regarded as t e n t a t i v e . However, they do support previous
suggestionsC3>4>JL) that sediment from p y r r o l i c compounds a r i s e s
from o l i g o m e r i z a t i o n through the adjacent methyl groups (see
F i g u r e 2). The p a r t i a l s t r u c t u r e s shown i n Figure 2 are sup-
ported by elemental, i n f r a r e d and mass s p e c t r a l analyses(2>A)
and provide a p o s s i b l e explanation f o r the need f o r a l k y l groups
adjacent to n i t r o g e n f o r l a r g e s c a l e sediment formation. Addi-
t i o n a l work with other model compounds i s being performed to
confirm these f i n d i n g s .
Compound I n t e r a c t i o n s . I n t e r a c t i o n s may be q u i t e important
to storage s t a b i l i t y of s y n t h e t i c f u e l s , e s p e c i a l l y those d e r i v e d
from shale and c o a l l i q u i d s . Previous w o r k ^ h a s indi-
cated that c e r t a i n compounds, which do not produce sediment by

themselves, can c o n t r i b u t e to or s t i m u l a t e sediment formation i n
others ( " p o s i t i v e " i n t e r a c t i o n ) . In some i n s t a n c e s , some mate-
r i a l s i n t e r a c t to i n h i b i t sediment formation ("negative" i n t e r -
a c t i o n ) . These i n t e r a c t i o n s have been demonstrated f o r thermal
s t a b i l i t y a n d , to a very l i m i t e d extent, f o r storage s t a b i l -
The r e s u l t s of p r e l i m i n a r y i n t e r a c t i o n s t u d i e s i n the
present program are summarized i n t h i s s e c t i o n .
The r e s u l t s of a p r e l i m i n a r y study to determine whether N-N
i n t e r a c t i o n s can occur under c o n d i t i o n s of dark storage are sum-
marized and t h e i r s i g n i f i c a n c e analyzed i n Table 1. In order to
determine whether an i n t e r a c t i o n a c t u a l l y occurred the data were
analyzed by means of 2 X 2 f a c t o r i a l experiments. A typical
design i n v o l v i n g DMP and i s o q u i n o l i n e i s shown i n F i g u r e 3. The
a n a l y s i s shown i n F i g u r e 3 i n d i c a t e s a l i k e l y p o s i t i v e i n t e r a c t i o n
a f t e r 28 days and c l e a r cut i n t e r a c t i o n a f t e r 56 days. Thus,
a f t e r 56 days the t o t a l sediment obtained with both n i t r o g e n
compounds together (127.5 mg/100 cc) was more than double the sum
of the two which would be expected i f they acted independently
(61.8 mg/100 c c ) . To determine the s i g n i f i c a n c e of the r e s u l t s ,
the data were subjected to Students " t " t e s t , ( i ) R e s u l t s are
summarized i n Table 1. These p r e l i m i n a r y r e s u l t s suggest that
i n t e r a c t i o n s can occur between DMP and v a r i o u s n i t r o g e n c o n t a i n i n g
s p e c i e s . These have important i m p l i c a t i o n s f o r f u e l s t a b i l i t y .
C e r t a i n compounds, f o r example, t r i o c t y l a m i n e and i s o q u i n o l i n e ,
while r e l a t i v e l y innocuous when present alone, can c o n t r i b u t e
s i g n i f i c a n t l y to sediment formation i n the presence of compounds
such as DMP. On the other hand, some m a t e r i a l s , such as 2-methyl-
i n d o l e , may a c t u a l l y have a s t a b i l i z i n g e f f e c t . The r e s u l t s of
the four t e s t s with 2-methylindole are e s p e c i a l l y i n t e r e s t i n g and
surprising. They a l l i n d i c a t e a s t a t i s t i c a l l y s i g n i f i c a n t
negative i n t e r a c t i o n . This needs to be confirmed i n f u t u r e ex-
periments.
Previous work suggested that important i n t e r a c t i o n s can occur
between n i t r o g e n and s u l f u r or oxygen compoundsC3 *4>,Z>.§).
S e v e r a l of these i n t e r a c t i o n s were "negative" ( i . e . , s t a b i l i z i n g ) .
S e v e r a l experiments were performed i n the present program to t e s t

Figure 2. Proposed partial structures for dimethylpyrrole sediment (5)

20. BRINKMAN E T A L . Synfuel Stability 301
PRESENCE OF COMPOUND A
NO YES
Q
0 0.5 40.9(2)
1
U
Pn
O
W 0.0(3) 54.9
U
w
CO
w
PH
28-DAYS STORAGE AT 110°F
PRESENCE OF COMPOUND A
NO YES
0 0.5 61.3(2)
1
o
w
0.0(3) 127.5
§
CO
s
PH
56 DAYS STORAGE AT 110°F
(1) Sediment shown as mg/100 cc.

(2) Amount expected from 150 ppm DMP alone.
(3) Amount from 1350 ppm Isoquinoline alone.
Figure 3. Sediment increase due to interaction between 2,5-dimethylpyrrole (A,

150 ppm) and isoquinoline (B, 1350 ppm) in No. 2 diesel (1)

Table I O
Summary of N-N I n t e r a c t i o n Runs
Storage Type o f (b)

(a)
Compound A (ppm) Compound B (ppm) Time (Days) Interaction Significance Test
DMP (150) 28 Positive Doubtful

3-Methylindole (1350) (t = 1.9, p = 0.1)
DMP (150) 56 Positive Significant

3-Methylindole (1350) (t = 5.2, .025 > p > .01)
DMP (150) 28 Positive Likely

Isoquinoline (1350) (t = 3.5, .05 > p > .025)
DMP (150) 56 Positive Significant O

Isoquinoline (1350) (t= 6.3, .025 > p > .01) F
DMP (150 28 Positive Doubtful
Trioctylamine (1350)
(t = 0.6, p = <0.1) w
DMP (150) 56 Positive Significant H
Trioctylamine (1350) >
(t = 4.5, p = .01)
DMP (150) 1,2,5-Trimethylpyrrole 28 Positive Highly Significant >

(150) (t = 73, p = <.005)
2-Methylindole 28 Negative Highly Significant

(750)
3 - M e t h y l i n d o l e (750) (t = >100, p = <.005)
>
o
2-Methylindole 56 Negative Highly Significant w
3 - M e t h y l i n d o l e (750)

(750) $t = 86, p = <.005)
>
H
28 Negative Highly Significant w
DMP (150) 2-Methylindole (1350) o
(t = 52, p = <.005)

56 Negative Significant
s
DMP (150) 2-Methylindole (1350) >
(t = 6.5, p = .05)
H
W
(a) " P o s i t i v e " i n t e r a c t i o n means combination gave more sediment than sum o f two compounds t e s t e d alone. 2
> 1
(b) Student's t e s t ( s e e r e f e r e n c e 9, s e c t i o n 4 ) . r
f o r these i n t e r a c t i o n s i n broad range f u e l s . The i n t e r a c t i o n s

discovered and t h e i r s i g n i f i c a n c e are summarized i n Table 2. The
t h i o l s , e s p e c i a l l y the aromatic t h i o l s , gave s i g n i f i c a n t negative
i n t e r a c t i o n s with DMP at l e a s t up to 28 days storage (see a l s o
F i g u r e 4 ) . Such i n t e r a c t i o n s were observed i n e a r l i e r work, but
the e f f e c t was reversed on long term s t o r a g e . I t has been
suggested that t h i s was due to o x i d a t i o n of the t h i o l s t o s u l f o n i c
a c i d s ; the former being i n h i b i t o r s and the l a t t e r a c c e l e r a t o r s .
Longer term storage t e s t s are being conducted t o i n v e s t i g a t e t h i s
phenomena.
S u r p r i s i n g l y , no e f f e c t s were observed with e i t h e r decanoic
a c i d or 2,6-di-t-butylphenol when t e s t e d with DMP i n No. 2 d i e s e l
f u e l . Work i n p u r i f i e d decane has i n d i c a t e d a s i g n i f i c a n t a c c e l -
e r a t i n g e f f e c t with most organic a c i d s i n c l u d i n g decanoic while

phenols are i n h i b i t o r s \ 2 . . I t would appear that important N-S
and, p o s s i b l y , N-0 i n t e r a c t i o n s can occur i n broad range f u e l s .
E f f e c t s of Base F u e l Hydrocarbon Content. The d i f f e r e n c e s i n
sediment formation r a t e s were observed with v a r i o u s d i l u e n t s
i n d i c a t i n g the chemical c h a r a c t e r i s t i c s of the base f u e l s can
exert a s i g n i f i c a n t i n f l u e n c e on the amounts of nitrogenous s e d i -
ment obtained. T h i s may be due to d i f f e r e n c e s i n s o l u b i l i t y
c h a r a c t e r i s t i c s of the base f u e l s or to the presence of t r a c e im-
p u r i t i e s which a c c e l e r a t e or i n h i b i t sediment formation. The
e f f e c t s of the hydrocarbon content of the base f u e l s i s c u r r e n t l y
being s t u d i e d with p r e l i m i n a r y r e s u l t s reported here. These
experiments are c a r r i e d out by adding r e p r e s e n t a t i v e s of the most
p r e v a l e n t hydrocarbon types, n - p a r a f f i n s , branched p a r a f f i n s ,
naphthenes ( c y c l o p a r a f f i n s ) and aromatics to the base f u e l s and
determining t h e i r i n f l u e n c e on sediment formation with v a r i o u s
n i t r o g e n compounds. The hydrocarbons are added at l e v e l s approx-
imating t h e i r normal occurrence i n most d i s t i l l a t e f u e l s ^ In
a d d i t i o n , c e r t a i n r e a c t i v e o l e f i n s , known t o c o n t r i b u t e t o gum
formation i n petroleum f u e l s , are being t e s t e d . The more h i g h l y
r e f i n e d JP-8 i s being used f o r these experiments because adding
small q u a n t i t i e s of o l e f i n s t o a complex f u e l such as No. 2 d i e s e l
would l i k e l y lead to e q u i v o c a l r e s u l t s .
P r e l i m i n a r y s t u d i e s on hydrocarbon e f f e c t s are summarized i n
Table 3. DMP at the 1500 ppm N l e v e l was employed as the n i t r o g e n
compound. The data obtained so f a r i n d i c a t e only minor e f f e c t s ,
i f any, due t o hydrocarbon type. However, a d d i t i o n a l work i s
r e q u i r e d , e x p e c i a l l y with more r e a c t i v e s p e c i e s such as d i o l e f i n s .
The e f f e c t s of storage temperature on sediment formation were
s t u d i e d u s i n g 2,5-dimethylpyrrole as the model compound. A r -
rhenius p l o t s f c r both #2 d i e s e l and JP-8 are shown i n Figures 5
and 6. The f a i r l y l i n e a r p l o t s permit e s t i m a t i o n of apparent
r e a c t i o n a c t i v a t i o n energies of 10.7 kcal/mole i n #2 d i e s e l and
14.4 kcal/mole i n JP-8. These are r a t h e r low and suggest some
i n t e r a c t i v e or c a t a l y t i c e f f e c t s are i n v o l v e d .
Synfuel Test R e s u l t s . A number of s y n f u e l s (meeting essen-
t i a l l y a l l f u e l s p e c i f i c a t i o n s ) and syncrude l i q u i d s produced from

TABLE I I
Summary o f I n t e r a c t i o n s Between 2 , 5 - D i m e t h y l p y r r o l e (DMP)

and S and 0 Compounds i n No. 2 D i e s e l F u e l
Compound A Storage Type o f

a 0 ( d )
(ppm)< > Compound B (ppm) (b) Time (days) Interaction^ ' Significance Test
( e
DMP (750) Decanoic A c i d ( 1 0 0 ) 14 None )
e
DMP (750) Decanoic A c i d ( 1 0 0 ) 28 None< )
DMP (750) Benzylphenyl Sulfide (3000) 14 None

DMP (750) Benzylphenyl Sulfide (3000) 28 None
DMP (750) £-Thiocresol (3000) 7 Negative Significant (t= 6 0 ; p = 05)

DMP (750) £-Thiocresol (3000) 14 Negative H i g h l y S i g n i f i c a n t ( t =1 3 . 0 ; p < .005)
DMP (750) £-Thiocresol (3000) 28 Negative H i g h l y S i g n i f i c a n t ( t =1 9 . 1 ; P < .005)
DMP (750) Thiophenol (3000) 7 Negative Highly Significant ( t =1 1 . 1 ; p < .005)

DMP (750) Dodecanethiol (3000) 14 None

DMP (750) Dodecanethiol (3000) 28 Positive Not Significant
DMP (750) 2,6-Di-t-Butylphenol (100) 14 None

DMP (750) 2,6-Di-t-Butylphenol (100) 28 None

(a) N Basis.

(b) S or 0 basis.
(c) " N e g a t i v e " means combination gave l e s s sediment than sum o f components alone.
(d) R e f e r e n c e 9.
(e) P o s i t i v e i n t e r a c t i o n s were observed i n o t h e r f u e l systems.
S T O R A G E T I M E , days
Figure 4. Interaction between 2,5-dimethylpyrrole and aromatic thiols in No. 2

diesel at 110°F: (O) DMP only, 750 ppm; (*) 750 ppm DMP + 3000 ppm p-
thiocresol; — 750 ppm DMP + 3000 ppm thophenol.

o
ON
TABLE I I I
E f f e c t s of Hydrocarbon Types on Sediment Formation
(2)
Hydrocarbon Vol. % T o t a l Sediment ( m g / l 0 0 m l )
Base F u e l Added Added 14 Days 28 Days 56 Days
No. 2 D i e s e l None — 217.5 572.8 795.8
s^-Butylbenzene 15 176.1 833.3 o

r
Cyclohexane 20 152.0 888.0

m
JP-8 None — 108.5 313.7 586.3
H
>
_a_-Bu t y lben z ene 15 93.5 313.2 630.5
C/i
>
i-Dodecene 5 112.0 311.2 685.5 O
676.0 >
_cV-Methylstyrene 5 118.1 327.8
a

(1) DMP L e v e l : 1500 ppm N; storage temp: 110°F. >
(2) Average of 2 or more r e p l i c a t e s ; " t o t a l sediments" i s H
w
sum of i n s o l u b l e and adherent sediments. a

>
H
W
>
600i
11 I I I I I I
2.9 3.0 3.1 3.2 3.3 3.4 3.5
1
1000 / T (°K- )
Figure 5. Arrhenius plot of 2,5-dimethylpyrrole in No. 2 diesel fuel

600
_ I
1000/T (°K )
Figure 6. Arrhenius plot of 2,5-dimethylpyrrole in JP-8

TABLE IV
Upgrading E f f e c t on Composition and S t a b i l i t y

of J e t F u e l From Shale O i l
Properties Original Upgraded
S u l f u r , t o t a l , wt-pct 0.015 0.005

Carbon, wt-pct 86.2 85.43
Hydrogen, wt-pct 13.32 14.42
Oxygen, wt-pct 0.28 0.05
Nitrogen, ppm 1500 3.2
T o t a l gum a f t e r 32 weeks
at 110° F, mg/100 ml 6.4 1.8

Table V
E l e m e n t a l A n a l y s e s o f O r i g i n a l Syncrude and
Gums A f t e r P r o l o n g e d S t o r a g e
Elemental A n a l y s i s Gum, Storage,

Element Fuel Gum mg/100ml Weeks
Naphtha SRC-II ( c o a l ) 532 32

c 84.94 65.99
H 12.78 6.55
N 0.32 8.59
0 1.92 12.91
s 0.72 2.00
Middle D i s t i l l a t e SRC-II ( c o a l ) 1629 32

c 86.28 75.60
H 9.05 6.65
N 0.98 5.46
0 3.36 10.99
S 0.32 0.67
Heavy D i s t i l l a t e SRC-II ( c o a l ) 6434

c 90.13 88.54
H 7.41 6.73
N 1.05 1.60
0 1.53 2.81
S 0.40 0.31
Naphtha-EDS (#6 I l l i n o i s c o a l ) 876 32

c 85.25 70.01
H 12.45 6.65
N 0.223 6.26
0 1.92 10.27
S 0.61 6.82
Naphtha-EDS (Wyodak c o a l ) 1035 32

c 85.14 66.28
H 12.56 6.19
N 0.21 7.21
0 1.84 17-36
s 0.21 2.86
Gas O i l - T a r Sands 7438 16

c 87.67 82.54
H 12.18 11.38
N 0.026 0.25
0 0.90 0.87
S 0.43 0.55
Kerosene - T a r Sands 30.1 16

c 87.05 83.52
H 12.42 8.41
N Trace Trace
0 0.30 7.34
S 0 0.01
Naphtha - T a r Sands 20.7 32

c 84.80 75.41
H 14.73 9.08
N 0.015 0.05
0 0.54 16.02
S 0.05 0.15

TABLE VI
JFTOT E v a l u a t i o n s by ASTM Test Method D3241 Conducted

f o r 2.5 Hours at 260°C C o n t r o l Temperature
JFTOT Ratings
Spun Spot
Description ^ Visual Tube Deposit AP, mm Hg/time, minutes
Paraho shale o i l J P - 5 ^ 4 24.5 34.5 1/30 1/90 1.5/150

3
Tar sands JP-5^ ) 4 15 17 0/30 0.5/90 0.5/150
COED c o a l l i q u i d JP-5 (4) 4 12 24 2/30 76/90 197/150
5
Paraho shale o i l J e t A(#4)< > 3 15 18 1/30 1/90 1/150
Paraho shale o i l J e t A(#23) ' 4 17 19 0.5/30 0.5/90 0.5/150
7
Paraho shale o i l J e t A(#10)< ) 4 30 35 1/30 1/90 1/150
Petroleum based JP-5 1 4 6 1/30 1/90 2/150
1) For d e t a i l e d d e s c r i p t i o n s , see Ref.(11).

2) Paraho I , N = 1500 ppm.
3) Hydrotreated Athabasca kerosene.
4) Navy sample from W. Kentucky c o a l .

5) Refined from Paraho I m a t e r i a l ; N = 347 ppm.
6) Same as (5), N = 3.2 ppm.

7) Same as (5), N = 146 ppm.
s h a l e , c o a l , and t a r sands have been subjected to 110°F storage

9 9
f o r up to 32 weeks i n sealed g l a s s c o n t a i n e r s . ^H — ^) It i s
normally accepted that one week of storage at 110°F i s e q u i v a l e n t
to four weeks storage at ambient f o r middle d i s t i l l a t e s v i z ) ,
while e q u i v a l e n t to up to ten weeks at ambient f o r l i g h t e r f r a c -
tions ( i l ) . During t h i s t e s t samples were removed f o r analyses at
4, 8, 16, and 32 weeks and a l l stored samples were aerated every
4 weeks. While the experimental d e t a i l s have been published
e l s e w h e r e ( i i > i 2 > i 2 ) , i n general the f u e l s r e f i n e d to meet r e q u i r e -
ment of petroleum-based f u e l s p e c i f i c a t i o n s showed r e l a t i v e l y
good s t a b i l i t y . Table 4 shows an example of a j e t f u e l before
and a f t e r upgrading good s t a b i l i t y . Table 4 shows an example of
a j e t f u e l before and a f t e r upgrading by a d d i t i o n a l h y d r o t r e a t -
ment. As can be seen, the more severe the l e v e l of h y d r o t r e a t -
i n g , the more s t a b l e the f u e l . I t i s f o r t h i s reason that the

s t a b i l i t y s p e c i f i c a t i o n s may d i c t a t e the u l t i m a t e p r o c e s s i n g
costs.
Elemental composition of s e v e r a l s y n f u e l s d e r i v e d from c o a l
by two d i f f e r e n t processes and from t a r sands are compared i n
Table 5 to the composition of gum produced i n each f u e l during
prolonged storage. In some f u e l s c o n s i d e r a b l e q u a n t i t i e s of
sediment and gum were formed i n a few weeks, t h e r e f o r e , the aging
was d i s c o n t i n u e d before 32 weeks were completed. G e n e r a l l y speak-
i n g , the heavy d i s t i l l a t e s and gas o i l s (the more v i s c o u s prod-
ucts) produced the l a r g e s t amount of d e p o s i t s followed by the
middle d i s t i l l a t e s and then the naphthas. The elemental composi-
t i o n of the gums produced during storage show that the n i t r o g e n ,
oxygen and s u l f u r compounds tend to p a r t i c i p a t e i n the degradation
reactions. In the more v i s c o u s f u e l s the tendency toward h i g h e r
heteroatom c o n c e n t r a t i o n i n the gum i s much l e s s , probably because
of c o n s i d e r a b l e f u e l entrainment.
In some a p p l i c a t i o n s , thermal degradation can be more of a
concern than storage s t a b i l i t y . Table 6 presents data on s e v e r a l
middle d i s t i l l a t e s y n f u e l s as compared to a petroleum-based f u e l .
The tube d e p o s i t s from the J e t F u e l Thermal Oxidation Test (ASTM
D3241) are s i g n i f i c a n t l y higher f o r the s y n f u e l s , but the pressure
buildup i s normal except f o r one case. This indicates either
r a p i d r e a c t i o n s at the hot s u r f a c e or slow agglomeration. In
e i t h e r case, the deposit l e v e l i s of concern and may d i c t a t e
f u r t h e r upgrading.
Conclusion
A l l i n f o r m a t i o n p u b l i s h e d to date i m p l i e s that the production

of s t a b l e s y n f u e l s i s p o s s i b l e but w i l l r e q u i r e r e f i n i n g processes
a l t e r e d from those now r e q u i r e d f o r petroleum. S t a b i l i t y research
i s c u r r e n t l y f o c u s s i n g on both b a s i c and a p p l i e d c o n s i d e r a t i o n s ,
and the r e s u l t s are encouraging. By c o n t i n u i n g these e f f o r t s , i t
i s hoped that s t a b i l i t y w i l l not be the l i m i t i n g f a c t o r i n p r o -
v i d i n g adequate f u t u r e f u e l s u p p l i e s .

20. BRINKMAN E TAL. Synfuel Stability 313
Literature Cited
1. Whisman, M. L., Goetzinger, J. W., and Ward, C. C., "Storage
Stability of Aviation Turbine Fuels," BOM RI 7325, 1969,
23 pp.
2. Whisman, M. L., Cotton, F. O., Goetzinger, J. W., and Ward,
C. C., "Radiotracer Study of Turbine Aircraft Fuel Stability,"
BOM RI 7493, 1971, 30 pp.
3. Frankenfeld, J. W. and Taylor, W. F., "Alternate Fuels Ni-
trogen Chemistry", Final Technical Report for Naval Air
Systems Command AIR 310C Contract No. N0001976C0675,
November, 1977.
4. Frankenfeld, J. W. and Taylor, W. F., "Continuation Study of
Alternate Fuels Nitrogen Chemistry", Final Technical Report
for Naval Air Systems Command AIR 310C, Contract No. N00019-
78-C-0177.
5. Frankenfeld, J. W. and Taylor, W. F., "Continuation Study of
Alternate Fuels Nitrogen Chemistry" Quarterly Progress Report
No. 1, Naval Air Systems Command, AIR 310C, Contract No.
N00019-78-C-0177, May, 1978
6. Taylor, W. F. and Frankenfeld, J. W., Ind. Eng. Chem. Product
Research and Development, 17, 86 (1978).
7. Taylor, W. F. and Frankenfeld, J. W., "Development of High
Stability Fuel", Final Report for Phase III, Contract No.
N000140-74-C-0618, Naval Air Propulsion Test Center, December,
1976.
8. Taylor, W. F. and Frankenfeld, J. W., "Development of High
Stability Fuel", Final Report for Phase I, Contract No.
N00140-74-C-0618, Naval Air Propulsion Test Center, Jan.
1975.
9. Davies, O. L., Statistical Methods in Research and Production,
Hafner Pub. Co., N.Y. (1958).
10. Frankenfeld, J. W. and Taylor, W. F., Ind. Eng. Chem. Prod.
Res. Dev. 19 (1) 65 (1980).
11. Brinkman, D. W., Whisman, M. L., and Bowden, J. N., "Stabil-
ity Characteristics of Hydrocarbon Fuels from Alternative
Sources," BETC/RI-78/23, March 1979.
12. Bowden, J. N., "Stability Characteristics of Some Shale and
Coal Liquids," BETC/4162-10, September 1980.
13. Bowden, J. N. and Brinkman, D. W., "Hydrocarbon Processing,
July 1980, 77 pp.
14. Richie, J., J. Inst. Petrol., 1965, 51 (501).
15. Schwartz, F. G., Whisman, M. L., Allbright, C. S., and Ward,
C. C., "Storage Stability of Gasoline," BOM Bulletin 660,
1972, 60 pp.

21
The Chemistry of Shale Oil and
Its Refined Products
DONALD M. FENTON, HARVEY HENNIG, and RYDEN L. RICHARDSON
Union Oil Company of California, Science and Technology Division,
P.O. Box 76, Brea, CA 92621
"Oil Shale" is a term used to cover a wide range of

materials which are found in many parts of the United States.

The Green River oil shales are particularly high grade and are
the only U.S. deposits having adequate size and availability for
potential commercial value with present technology. The Green
River formation contains the equivalent of 1.8 trillion barrels
of shale oil. Assuming that only 600 billion barrels or one
third of this oil is ultimately recoverable, this would still be
20 times the U.S. proved crude oil reserves.
The Green River oil shale is a marlstone (calcareous mud-
-stone) that was formed in shallow lakes about 45 million years
ago (1). The climate at this time probably varied from sub-
tropical to arid. During wet periods these lakes may have been
as large as 75 to 100 miles in diameter.
Sediment, mineral salts, minor plant debris and wind-
-transported pollen were carried into the lakes by small local
streams, but the majority of the organic material that is in the
oil shale came from colonies of algae that thrived in the lakes.
The organic matter found i n the Green River shales formed i n
the deeper, c e n t r a l part of the l a k e . Rocks formed under these
c o n d i t i o n s a r e c h a r a c t e r i z e d by t h i n , a l t e r n a t i n g l a y e r s o f c a r -
bonate and organic matter. The l a y e r s vary i n thickness from
0.01 to 10 m i l l i m e t e r s .
The l a y e r s are b e l i e v e d to have been formed by the p r e c i p i -
t a t i o n of calcium carbonate i n e a r l y summer, when the s u r f a c e
water temperature r i s e s , followed by the seasonal high p r o d u c t i v -
i t y of algae which occurs i n l a t e summer. The heavy carbonate
m a t e r i a l s were deposited q u i c k l y ; the organic matter s e t t l e d more
s l o w l y — w h i c h gave an a l t e r n a t i o n of l i g h t and dark l a m i n a t i o n s .
The t y p i c a l composition of Green R i v e r o i l shale i s composed
of around 0-15% bitumen, e x t r a c t a b l e o r g a n i c s , and 85-100% kero-
gen, unextractable o r g a n i c s , see Table I . The kerogen i s an
organic matrix of high molecular weight, c o n t a i n i n g on the aver-
age s e v e r a l saturated r i n g s with hydrocarbon chains having an oc-
c a s i o n a l i s o l a t e d carbon-carbon double bond and a l s o c o n t a i n i n g ,
0097-6156/81/0163-0315 $05.00/0

i n a d d i t i o n to small amounts of n i t r o g e n and s u l f u r , approxi-

mately 6% oxygen. There i s a l s o the p o s s i b i l i t y that c o n s i d e r -
able amounts of non-crosslinked, long-chain compounds are
trapped i n the matrix.
I f the n i t r o g e n and s u l f u r are f o r m a l l y replaced by oxygen,
f o r example by h y d r o l y s i s with each n i t r o g e n and s u l f u r being
replaced by the two oxygens and one hydrogen, then a simple
c H a n d t t i e w e i l l t r a t i o o f C H i s
formula weight i s ^ g 2 8 ° 2 8 / 7.7.
T h i s i s about what would be expected f o r algae d e r i v e d organics,
s i n c e algae produce f a t t y a c i d s i n the C^g range as w e l l as
other hydrocarbons such as cartenoids a t C ^ Q . I t has been shown
that the e x t r a c t a b l e hydrocarbons from o i l shale have a bimodal
d i s t r i b u t i o n at and supporting t h i s contention (2) .
Strong evidence f o r the biogenesis of kerogen was shown when i t

was found that the r a t i o of odd to even number of carbon atoms
i n the extracted hydrocarbons was as high as four to one. A
r a t i o of one to one would be expected from a n o n b i o l o g i c a l
source. The higher p r o p o r t i o n of the odd number hydrocarbons
would be a n t i c i p a t e d i f t h e i r source was the d e c a r b o x y l a t i o n of
a l g a l f a t t y a c i d s , s i n c e these a c i d s are predominantly even
number a c i d s .
An i n t e r e s t i n g question i s : how d i d these predominantly
a l g a l a c i d s become c r o s s l i n k e d to form kerogen? I t can be seen
from the kerogen formula that there a r e on the average four
u n i t s of u n s a t u r a t i o n , while i t i s known that under some c o n d i -
t i o n s algae form f a t t y a c i d s that are 95% unsaturated, and with
some a c i d s , such as a r a c h i d o n i c , an e s s e n t i a l f a t t y a c i d , there
are four o l e f i n i c l i n k a g e s . I t has a l s o been shown that these
polyunsaturated a l g a l a c i d s , under m i l d heating, become c r o s s -
linked. I t i s c l e a r that the unsaturated a c i d s on diagenesis
i n the o i l shale r e a c t to form naphthenes, the c y c l i c compounds
found i n kerogen. One r e a c t i o n of t h i s type i s the D i e l s - A l d e r
r e a c t i o n which can occur at m i l d temperatures ( 3 ) .
While the D i e l s - A l d e r r e a c t i o n i s thought to be r e s p o n s i b l e
f o r the organic c r o s s l i n k i n g r e a c t i o n , i t i s a l s o proposed that
there i s a chemical attachment of the organic to the i n o r g a n i c
matrix. T h i s attachment could a r i s e from the i n t e r a c t i o n of
the c a r b o x y l group of the f a t t y a c i d with the calcium and mag-
nesium ions on the i n o r g a n i c s u r f a c e , which could l e a d to the
formation of i n s o l u b l e calcium and/or magnesium soaps. In a d d i -
t i o n to the n i t r o g e n found i n porphyrins and r e l a t e d compounds,
i t i s a l s o proposed that the s u l f u r and n i t r o g e n moieties found
i n kerogen r e s u l t from a t t a c k of ammonia and p o l y s u l f i d e s on the
unsaturated f a t s l e a d i n g to W i l l g e r o d t - t y p e r e a c t i o n products.
One b i g advantage of shale o i l as compared to c o a l i s the
more f a v o r a b l e atomic composition of kerogen noted i n Table I I .
The hydrogen content of kerogen i s almost twice that of many
c o a l s , and the oxygen content i s lower. The s u l f u r content of
kerogen i s s i m i l a r to that of c o a l . The n i t r o g e n i s higher i n
kerogen. Consequently, l e s s hydrogen i s r e q u i r e d to remove the

21. FENTON E TAL. Shale Oil and Refined Products 317
TABLE I
TYPICAL COMPOSITION OF
GREEN RIVER OIL SHALE
(25 Gal/Ton
Kerogen Content 15 wt% Shale O i l )
Kerogen Composition: Wt%
Carbon 80.5
Hydrogen 10.3
Nitrogen 2.4
Sulfur 1.0
Oxygen (Varies with Depth) 5.8
100.0
H
Simple Chemical Formula ^20 32°2
(Sulfur & Nitrogen
Replaced by Oxygen)
M i n e r a l Content 85 wt%
Carbonates 48.0
Feldspars 21.0
Quartz 15.0
Clays 13.0
Analcite & Pyrite 3.0
100.0
TABLE I I
KEROGEN VS COAL
Weight Percent
Kerogen Coal
Bit Subb Lignite
Moisture and Ash Free

Carbon 80 .5 78 .8 73. 5 72.5
Hydrogen 10 .3 5 .7 5. 3 4.9
Oxygen 5 .8 8 .9 19. 7 20.8
Nitrogen 2 .4 1 .4 1. 0 1.1
Sulfur 1 .0 5 .2 0.5 0.7
C/H Ratio 7 .8 13 .8 13. 9 14.8

unwanted oxygen, n i t r o g e n and s u l f u r , and l e s s hydrogen i s

needed to b r i n g the carbon/hydrogen r a t i o down to values r e -
quired i n l i q u i d f u e l s such as g a s o l i n e , turbine and d i e s e l
f u e l s or h e a t i n g o i l s .
Because of the impervious nature of the o i l shale and the
chemical nature of the kerogen, i t i s necessary to heat the
shale to around 450°C (900°F) to thermally break up the kerogen.
Under these c o n d i t i o n s , kerogen decomposes to give o i l (65-70%),
gas (10-15%), coke (15-20%) and water (2-7%).
A l s o , during the r e t o r t i n g operation, there i s s i g n i f i c a n t
l o s s of oxygen. About two-thirds i s l o s t as carbon d i o x i d e and
about o n e - t h i r d as water. Because of the l o s s of carbon d i o x i d e ,
the C/H r a t i o has b e n e f i c i a l l y decreased from 7.8 i n kerogen to
7.3 i n shale o i l .
Some i n s i g h t i n t o the u t i l i t y of shale o i l can be gained

by comparing i t s composition w i t h c o a l - d e r i v e d l i q u i d s and
petroleum crude o i l . See Table I I I . Two r e p r e s e n t a t i v e l i q u i d
products from c o a l a r e shown: COED product, produced by c a r b o n i -
z a t i o n or coking, which, l i k e r e t o r t i n g o f shale, i s a thermal
step (4), and a l i q u i d from the H-Coal process by c o a l hydrogena-
t i o n (5). Arabian L i g h t crude o i l i s a l s o shown.
Of the two thermally produced l i q u i d s , shale o i l has a
b e t t e r (lower) carbon-to-hydrogen r a t i o , and a lower s p e c i f i c
g r a v i t y which i n d i c a t e s the absence of h i g h b o i l i n g aromatics.
Both have h i g h pour p o i n t s ; shale o i l because of long-chain
p a r a f f i n s , COED l i q u i d because of heavy polyaromatics. The
l i q u i d y i e l d s per t o n of raw m a t e r i a l mined are i n the same order
of magnitude. The s o l i d r e s i d u e of shale r e t o r t i n g i s l a r g e l y
mineral matter, w h i l e the s o l i d residue from c o a l c a r b o n i z a t i o n ,
c a l l e d a char, i s a usable f u e l c o n t a i n i n g more energy than the
o i l f r a c t i o n . Conversion of the COED l i q u i d product to t r a n s -
p o r t a t i o n f u e l s , however, i s a more d i f f i c u l t task because of
i t s h i g h t a r , lower hydrogen and higher hetero atom contents.
The hydrogenated product from c o a l , H-Coal l i q u i d , i s more
aromatic than shale o i l but somewhat comparable i n hetero atom
content even though a c o n s i d e r a b l e amount of hydrogen has already
been added to the product.
Arabian L i g h t crude i s a wider b o i l i n g m a t e r i a l than crude
shale o i l and i s lower i n a l l hetero atoms except s u l f u r . I t
has a more f a v o r a b l e carbon/hydrogen r a t i o because i t contains
fewer aromatics and no o l e f i n s .
In the upgrading of crude shale o i l , s o l i d s removal i s
f i r s t achieved by optimal c e n t r i f u g i n g , s e t t l i n g and f i l t e r i n g .
Next, a r s e n i c removal i s achieved with a c a t a l y s t - a b s o r b e n t .
In the t h i r d step, the h y d r o t r e a t i n g step, the s u l f u r ,
n i t r o g e n , and oxygen c o n t a i n i n g compounds a r e hydrogenated over
m e t a l l i c s u l f i d e c a t a l y s t s to hydrogen s u l f i d e , ammonia, water
and hydrocarbons. O l e f i n s present i n the raw shale o i l are a l s o
hydrogenated.
The hydrotreated shale o i l (or syncrude) now, save f o r pour

21. FENTON ET AL. Shale Oil and Refined Products 319
TABLE I I I
CRUDE SHALE OIL,

COAL LIQUIDS, CRUDE OIL
Crude Arabian
Shale Coal L i q u i d s Light
Oil COED* H-Coal Crude
Gravity, Specific 0.92 1.13 0.92 0.85

°API 22.2 -4 23.0 34.7
B o i l i n g Range, °C 60-540 30-525 5-575+
Composition, Wt%
Nitrogen 1.8 1.1 0.1 0.8
Sulfur 0.9 2.8 0.2 1.7
Oxygen 0.8 8.5 0.6
C/H Ratio 7.3 11.2 8.1 6.2
Pour P o i n t , °F 60 100 <5 -15
Viscosity, 100°F, SUS 98 133 - 44
Hydrogen Added
S c f / B b l Product 0 0 6000 0
Wt% 0 0 10
Y i e l d , Gallons/Ton 25-35 30-48 60-90
*COED: Char O i l Energy Development

p o i n t , resembles crude o i l more c l o s e l y . The amount of hydrogen

consumed i s l i s t e d i n Table IV e i t h e r as the volume of hydrogen
per b a r r e l of product or the number of hydrogen atoms absorbed
per hetero atom, that i s , n i t r o g e n p l u s s u l f u r plus oxygen atoms.
The r a t i o of 10.8 exceeds the t h e o r e t i c a l hydrogen consumption
because double bonds are saturated and hetero as w e l l as other
compounds are hydrocracked.
The s p e c i f i c g r a v i t y and composition of hydrotreated shale
o i l are compared to a syncrude from c o a l . Note that we have
converted crude shale o i l to syncrude w i t h much l e s s hydrogen
than would be r e q u i r e d f o r a s i m i l a r product from c o a l : 1,350
SCF per b a r r e l compared with 6,000 SCF per b a r r e l or more, and
made a higher q u a l i t y product, as i n d i c a t e d by the composition
and carbon/hydrogen r a t i o .
The high pour p o i n t s , and a l s o h i g h v i s c o s i t i e s of the raw

shale o i l and of the hydrotreated shale o i l , are a cause f o r
concern. I t appears that both the raw shale o i l with i t s h i g h
n i t r o g e n content, i t s h i g h pour p o i n t and high v i s c o s i t y and
the hydrotreated shale o i l with i t s h i g h pour p o i n t may not be
s u i t a b l e f o r undedicated (to such o i l s ) p i p e l i n e s . In the ab-
sence of dedicated p i p e l i n e s , conversion to p i p e l i n e a b l e products
( g a s o l i n e , d i e s e l f u e l , j e t f u e l , etc.) at or near the r e t o r t i n g
s i t e i s one a l t e r n a t i v e . Another i s to subject the raw shale
to a coking o p e r a t i o n which lowers the pour p o i n t and, when
followed by h y d r o t r e a t i n g , gives a l o w - s u l f u r , low-nitrogen o i l
of about 45°F pour p o i n t . The hydrotreated shale o i l can be
doped w i t h a pour p o i n t depressant to g i v e a 35 to 40°F pour
p o i n t o i l acceptable i n common c a r r i e r p i p e l i n e s .
I f the thermal coking has to be used to make a product
s u i t a b l e f o r common c a r r i e r p i p e l i n i n g , an o v e r a l l l i q u i d y i e l d
l o s s of 15% to 20% w i l l be i n c u r r e d .
Shale o i l from the r e t o r t contains on the order of 10%
heavy naphtha, a precursor to g a s o l i n e . When h y d r o t r e a t i n g the
shale o i l to reduce the n i t r o g e n content to 1,000 ppm, some a d d i -
t i o n a l naphtha i s formed. The syncrude w i l l have c l o s e to 14%
naphtha which i s somewhat s i m i l a r i n q u a l i t y to naphtha from
L i g h t Arabian crude. See Table V. The octane number of the
naphtha i s low and w i l l have to be improved by c a t a l y t i c reform-
i n g . Reforming p r i m a r i l y dehydrogenates naphthenic r i n g s to form
high-octane aromatics, and a l s o c y c l i z e s or isomerizes low-
octane s t r a i g h t - c h a i n p a r a f f i n s and hydrocracks some of the h i g h -
b o i l i n g p a r a f f i n s . Reforming was developed to upgrade petroleum
naphthas and w i l l a l s o be r e q u i r e d f o r comparable l i q u i d stocks
from c o a l . The r e l a t i v e l y high naphthene content of shale o i l
naphtha permits reforming to high-octane g a s o l i n e w i t h only
moderate y i e l d l o s s , compared with L i g h t Arabian naphtha.
Naphthas from c o a l g e n e r a l l y c o n t a i n aromatic r i n g s as w e l l
and so would g i v e s l i g h t l y b e t t e r y i e l d s ; but, because of the
higher number of hetero compounds, l o s e some advantage.
The Department of Defense i s i n t e r e s t e d i n a l t e r n a t i v e

21. FENTON E TA L . Shale Oil and Refined Products 321
TABLE IV
HYDROGEN REQUIREMENT TO
HYDROTREAT SHALE OIL
Hydrotreated
Shale O i l H-Coal
Hydrogen Consumption
S c f / B b l Product 1350 6000
Atoms/Atom Hetero 10.8
Wt% Product 2.4 10
Gravity,
°API 34 23
0.86 0.92
Specific
+80 <5
Pour P o i n t , °F
55
V i s c o s i t y , 100°F, SUS
Composition, Wt%
Nitrogen 0.08 0.01
Sulfur 0.002 0.2
Oxygen 0.6
C/H R a t i o 6.5 8.1

TABLE V
SHALE OIL PRODUCTS VS PETROLEUM PRODUCTS

NAPHTHA (GASOLINE PRECURSOR)
Exxon
L i g h t Arabian Donor
Naphtha From: Shale Oil* Crude Solvent
B o i l i n g Range, °C 70-205 25-190 70-205

50% P o i n t , °C 154 123 177
Y i e l d , V o l % Crude 13.6 26.7 10
G r a v i t y , °API 51.6 63.0 30

Specific 0.77 0.73 0.88
S u l f u r , ppm 9 320 4700
Nitrogen, ppm 34 2100
C/H R a t i o 5.9 5.7 7.8
Octane Number
Research, C l e a r 32.5 38.3 -
+ 3 ml TEL 61.9 63.6
Composition, wt%
Paraffins 45 75 22
Naphthenes 44 14 42
Aromatics 11 11 36
*From shale o i l which has been hydrotreated to reduce s u l f u r to

530 ppm. 1350 s c f H consumed per b a r r e l of crude shale o i l .
9

TABLE VI

TURBINE FUEL
Source JP-4 From Typical

Shale O i l JP-4
B o i l i n g Range, °C 100-240 60-240

50% P o i n t , °C 182 143
G r a v i t y , °API 51.9 54
Specific 0.77 0.76
S u l f u r , ppm 5 350
Freeze P o i n t , °C <-60 -62
Aromatics, V o l % 3.0 12.3
Smoke P o i n t , mm 40 27.5
Thermal S t a b i l i t y , JFTOT
at 260°C
Pressure Drop, mm Hg 0 0.2
Preheater Deposit Code 0 1

TABLE V I I

DIESEL FUEL
Diesel Fuel
From
Source Shale O i l Typical
B o i l i n g Range, ° C 200-360 188-237
Yield, Vol% 42.3 —
G r a v i t y , °API 37.2 36
Specific 0.84 0.84
S u l f u r , ppm 19 2500
Nitrogen, Wt% 0.022 —
Pour P o i n t , °F -23 -4 to -<
Cetane Number 50 46
V i s c o s i t y , SUS @ 38°C 37.2 34.5

sources of t u r b i n e f u e l s f o r m i l i t a r y a i r c r a f t . JP-4 i s the

large-volume f u e l they r e q u i r e . See Table VI. Shale o i l i s
w e l l s u i t e d f o r y i e l d i n g t u r b i n e f u e l s because of i t s r e l a -
t i v e l y low a r o m a t i c i t y . A l l s p e c i f i c a t i o n s f o r JP-4 are met by
s e p a r a t i n g the JP-4 b o i l i n g range m a t e r i a l from crude shale o i l
by d i s t i l l a t i o n and h y d r o t r e a t i n g that f r a c t i o n .
R e f i n i n g of j e t f u e l s from c o a l syncrude poses more of a
problem becuase of the high aromatic content.
The d i e s e l f u e l f r a c t i o n from the raw shale o i l i s too
high i n s u l f u r and o l e f i n s and too low i n cetane number and
storage s t a b i l i t y t o meet s p e c i f i c a t i o n s . Product which meets
a l l s p e c i f i c a t i o n s can be made, however, by h y d r o t r e a t i n g crude
shale o i l followed by d i s t i l l a t i o n , r e f e r to Table V I I . An i n -
c r e a s i n g number of petroleum crudes a l s o r e q u i r e h y d r o t r e a t i n g
of the d i e s e l f r a c t i o n to reduce s u l f u r content.

The p o r t i o n of shale syncrude b o i l i n g above the d i e s e l
f u e l f r a c t i o n can be used as a premium l o w - s u l f u r f u e l o i l or
cracked to produce more v a l u a b l e l o w e r - b o i l i n g t r a n s p o r t a t i o n
f u e l s such as g a s o l i n e , j e t and d i e s e l f u e l s . T h i s f r a c t i o n i s
a b e t t e r m a t e r i a l than the corresponding f r a c t i o n from crude
(such as Arabian L i g h t ) , because the shale o i l has been upgraded
by p r i o r p r o c e s s i n g : r e t o r t i n g , which thermally cracked the
highest b o i l i n g f r a c t i o n s and reduced i t s carbon r e s i d u e , and
h y d r o t r e a t i n g which reduced the s u l f u r and n i t r o g e n contents.
The corresponding crude o i l f r a c t i o n (from L i g h t Arabian crude)
s t i l l contains 32% (14% of crude) as a n o n d i s t i l l a b l e a s p h a l t .
I t i s d i f f i c u l t to use as b o i l e r f u e l because of i t s 2.75% s u l f u r
content. I t i s o f t e n u t i l i z e d by blending i t i n bunker f u e l or
by converting i t to acceptable d i s t i l l a t e f u e l s by coking f o l -
lowed by h y d r o t r e a t i n g .
LITERATURE CITED
1. Cane, R. F., "Developments in Petroleum Science 5,"

Chapter 3 (Teh Fu Yen and G. V. Chilingarian, ed.),
Elsevier, N. Y. 1976, p. 27.
2. Ibid, p. 66.
3. Ibid, p. 51.
4. Synthetic Fuels Data Handbook, Cameron Engineers, Inc.,
2nd Edition, 1978, p. 193.
5. Ibid, pp. 238-42; Shaw, H.; Kalfadellis, C. D.; Jahnig,
C. E., "Evaluation of Methods to Produce Aviation Turbine
Fuels from Synthetic Crude Oils-Phase One," Air Force Aero
Propulsion Laboratory Technical Report AF-APL-TR-75-10,
Final Report for Period 24 June 1974-24 January 1975,
12008 Exxon Pt 16 5-16-75MY, p. 168.

22
The Reactivity of Cold Lake Asphaltenes
1
R. C.SCHUCKER and C. F. KEWESHAN
Corporate Research Science Laboratories, Exxon Research and Engineering
Company, P.O. Box 45, Linden, NJ 07036
As known reserves of light crudes become depleted, the con-

version of heavy crudes and residua to distillate fuels is becom-
ing increasingly important. While reserves of Canadian and
Venezuelan bitumen and Arabian heavy oils represent vast, largely
untapped resources, their usefulness to a large extent depends on
our ability to chemically convert macromolecules such as asphal-
tenes and polar aromatics to smaller molecules boiling typically
in the mid-distillate/naphtha range. To optimize the utilization
of these feedstocks, we need a much better understanding of the
structure and reactivity of petroleum macromolecules, particu-
larly asphaltenes.
While there has been a significant amount of research done
to date to elucidate structural characteristics of asphaltenes,
there appears to be no consensus of opinion even on major issues
such as the average size of asphaltene aromatic units. For exam-
ple, proposed structures for Athabasca pentane asphaltenes vary
from the twelve-ring naphtho-ovalene structure of Speight (1) to
the two-ring sulfur polymer structure of Ignasiak et al (2).
With this kind of disagreement regarding crude asphaltene struc-
tures, it is easy to see why little progress has been made in the
area of asphaltene reactivity.
Recently i t has been reported by Bearden and A l d r i d g e (3)
that c e r t a i n molybdenum c a t a l y s t s can s u b s t a n t i a l l y reduce coke
formation i n the hydroconversion o f asphaltene - c o n t a i n i n g feeds
under thermal c r a c k i n g c o n d i t i o n s . We have now a p p l i e d t h i s
method to o b t a i n asphaltene fragments i n high y i e l d s f o r charac-
t e r i z a t i o n of the s t r u c t u r e of asphaltenes from Cold Lake crude.
The goal of our work has been to d e f i n e the major b u i l d i n g blocks
i n Cold Lake asphaltenes i n order to begin to b r i n g together the
concepts of s t r u c t u r e and r e a c t i v i t y . We have approached the
problem by c a r r y i n g out m i l d , thermal hydroconversion r e a c t i o n s
on neat asphaltenes and c h a r a c t e r i z i n g both reactant and r e a c t i o n
1
C u r r e n t address: Exxon Research and Development L a b o r a t o r i e s ,
P. 0. Box 2226, Baton Rouge, L o u i s i a n a 70821.
0097-6156/81/0163-0327$05.00/0

products i n d e t a i l . While previous research has concentrated on

crude asphaltenes, we have focused on reacted asphaltenes. By
combining s t r u c t u r a l and k i n e t i c i n f o r m a t i o n obtained i n t h i s
study, we have been able to p o s t u l a t e a g l o b a l asphaltene reac-
t i o n mechanism which i s c o n s i s t e n t with a l l of our observations.
Experimental
Cold Lake asphaltenes f o r t h i s study were prepared by pre-

c i p i t a t i o n with n-heptane using a s o l v e n t to crude r a t i o of 20:1.
The p r e c i p i t a t e d asphaltenes were separated from the maltenes
(n-heptane s o l u b l e s ) by f i l t r a t i o n , then washed with an equal
volume of n-heptane and d r i e d at 100°C i n vacuo. T o t a l y i e l d of
asphaltenes on crude was 12.6% (by weight). These asphaltenes
contained approximately 0.8% (by weight) toluene insoluble,

i n o r g a n i c matter which was c o r r e c t e d f o r i n subsequent y i e l d
calculations. Elemental composition was measured by r o u t i n e
a n a l y t i c a l techniques. Oxygen was measured d i r e c t l y by neutron
a c t i v a t i o n a n a l y s i s and not obtained by d i f f e r e n c e . Number aver-
age molecular weights were obtained by vapor pressure osmometry
(VPO) i n toluene at 50°C. N i c k e l and vanadium concentrations
were measured by atomic absorption spectrophotometry. Mole f r a c -
t i o n s of aromatic carbon and hydrogen were determined d i r e c t l y by
pulsed F o u r i e r transform nmr techniques. A summary of a n a l y t i c a l
data f o r the reactant asphaltenes i s given i n Table I.
A l l r e a c t i o n s were c a r r i e d out as batch experiments i n
tubing bomb r e a c t o r s (30cc) using e i t h e r Cold Lake asphaltenes as
p r e c i p i t a t e d or Cold Lake asphaltenes impregnated with a s o l u b l e
molybdenum c a t a l y s t which had been p r e v i o u s l y shown to reduce
coke formation i n the hydroconversion of heavy hydrocarbons (3).
In a t y p i c a l experiment the r e a c t o r was charged with f i v e grams
of asphaltenes and p r e s s u r i z e d to 6 MPa with hydrogen. I t was
then plunged i n t o a preheated, f l u i d i z e d sandbath, held f o r the
d e s i r e d r e a c t i o n time while a g i t a t i n g , removed from the bath and
quenched i n c o l d water. The temperature of the r e a c t i o n mixture
was monitored at a l l times using a thermocouple l o c a t e d i n the
bomb. T y p i c a l heatup time from ambient temperatures to 95% of
r e a c t i o n temperature was three minutes. At the end of a run
gases were vented through an H S scrubber i n t o a gas bag.
2 Hydro-
carbon gases ( C - C ) were analyzed by gas chromatography using
1 4
flame i o n i z a t i o n d e t e c t i o n and 1,1-difluoroethane as an i n t e r n a l

standard. Toluene was used to remove the l i q u i d and s o l i d
products from the bomb and the toluene s o l u t i o n was filtered
to determine the coke (toluene i n s o l u b l e s ) y i e l d . A f t e r remov-
ing toluene from the f i l t r a t e by vacuum, n-heptane was added to
separate asphaltenes (toluene s o l u b l e , n-heptane i n s o l u b l e ) from
maltenes (n-heptane s o l u b l e ) . Coke and asphaltene f r a c t i o n s were
d r i e d overnight at 100°C i n vacuo. An o v e r a l l m a t e r i a l balance
was obtained by summing the coke, asphaltene, maltene and gas
f r a c t i o n s and f o r lower s e v e r i t y runs averaged between 97-101%.

22. SCHUCKER A N D KEWESHAN Cold Lake Asphaltenes 329
T A B L E I
ANALYSIS O FCOLD L A K E CRUDE ASPHALTENES
C (WT.%) 80.64
H (WT.%) 7.64
0(WT.%) 1.84
N (WT.%) 1.60
S (WT.%) 7.95
Ni (PPM) 310
V (PPM) 815
Mn (VPO, T O L U E N E , 50°C) 6640 ± 120
C A (MOLE %) 47.3
H A ( M O L E % ) 11.4
( H / C ) T 0 T A L 1.14
(H/C) A 0.274
(H/C) s 1.91
T M (°C) 209

F u r t h e r s e p a r a t i o n of maltenes i n t o r e s i n s (polar aromatics) and

o i l s was achieved i n s e l e c t e d cases by adsorption onto Attapulgus
c l a y using a m o d i f i c a t i o n of ASTM D2007 ( c l a y - g e l s e p a r a t i o n ) .
Results And D i s c u s s i o n
The thermal hydroconversion of Cold Lake asphaltenes was

studied i n i t i a l l y to provide a b a s i s f o r e v a l u a t i o n of c a t a l y t i c
e f f e c t i v e n e s s i n subsequent work. S e r i e s of thermal runs were
made at 335°C, 365°C and 400°C and the r e a c t i o n products were
separated as described p r e v i o u s l y . Several k i n e t i c models were
t r i e d , but a f t e r examining the v a r i a b i l i t y of our data, we
decided on the simple f i r s t - o r d e r asphaltene decomposition model
shown below:
A -> aA* + bM (1)
where A = weight f r a c t i o n reactant asphaltenes
A* = weight f r a c t i o n reacted asphaltenes
M = weight f r a c t i o n maltenes
a,b = s t o i c h i o m e t r i c c o e f f i c i e n t s (based on weight)
Rate expressions f o r t o t a l asphaltenes and maltenes were inte-

grated to y i e l d Equations (2) and (3).
k t
A t = a + (l-a)e" (2)
k t
M = b(l-e" ) (3)
Equations (2) and (3) were f i t to experimental data using non-

l i n e a r r e g r e s s i o n to o b t a i n values of the f i r s t - o r d e r r e a c t i o n
rate constants and the s t o i c h i o m e t r i c c o e f f i c i e n t s at each tem-
perature. The conversion data from the 400°C thermal run and the
best f i t of the k i n e t i c model are shown i n F i g u r e 1. It is inter-
e s t i n g to note that at the time of i n c i p i e n t coke formation (^60
minutes) the asphaltene and maltene data deviate from p r e d i c t e d
f i r s t - o r d e r behavior. From t h i s we concluded that both asphal-
tenes and maltenes were p a r t i c i p a t i n g i n secondary coke-forming
r e a c t i o n s . F u r t h e r s e p a r a t i o n of the maltenes i n t o r e s i n s (polar
aromatics) and o i l s confirmed t h i s to be true and showed t h a t i t
was the r e s i n f r a c t i o n t h a t was i n v o l v e d i n coke formation.
The same experiments were run using asphaltenes impregnated
with molybdenum. The conversions and best f i t of the k i n e t i c
model at 400°C are shown i n F i g u r e 2. Previous work (4) had sug-
gested that the molybdenum would s u l f i d e and thus be able to
a c t i v a t e hydrogen r e s u l t i n g i n improved hydrogen t r a n s f e r to
radical fragmentation products. Increased hydrogen transfer


Figure 1. Thermal hydroconversion of Cold Lake asphaltenes at 400 °C and 6 MPa H : 2 asphal-
tenes (A); maltenes (%); coke (H); model ( ).
to
O
r
X
>
r
>
70
>
D

m
r
>
H
m
a

Figure 2. Hydroconversion of Cold Lake crude asphaltenes with 200 ppm molybdenum at 400°C £
t
and 6 MPa H : asphaltenes (J^); maltenes (• ); coke (J^); model ( ). H
>
22. SCHUCKER AND KEWESHAN Cold Lake Asphaltenes 333
above the thermal base case would e x p l a i n the s t a b i l i z a t i o n of

r e s i n fragments shown i n F i g u r e 2 and the lower o l e f i n / p a r a f f i n
r a t i o i n the gas i l l u s t r a t e d i n Table II f o r the C 3 gases.
The temperature dependence of the r e a c t i o n rate constants
obtained f o r the thermal and c a t a l y t i c runs was assumed to f o l l o w
the Arrhenius r e l a t i o n s h i p and the r e s u l t i n g p l o t of these data
i s shown as Figure 3. As we can see, the c a t a l y s t had no r e a l
e f f e c t on the a c t i v a t i o n energy. I t d i d , however, increase the
rate of r e a c t i o n at a l l temperatures. I n t e r p r e t a t i o n of these
data, though, i s at best somewhat s u b j e c t i v e . In complex reac-
t i o n systems l i k e these, the measured rate i s g e n e r a l l y consid-
ered to be that of the slowest or r a t e - l i m i t i n g step i n the
r e a c t i o n sequence. The low values of the a c t i v a t i o n energies
obtained s t r o n g l y suggest that primary bond breaking i s not the
r a t e - l i m i t i n g step and that some other step such as hydrogen

t r a n s f e r might be. This i s supported by the f a c t that the
observed rate increased under improved hydrogen t r a n s f e r condi-
tions .
While the y i e l d of asphaltenes and other products during the
e a r l y stages of r e a c t i o n are s i m i l a r (as shown i n Figures 1 and
2), the thermal asphaltenes e x h i b i t e d lower H/C r a t i o s and higher
number average molecular weight (M ) and r e s u l t e d i n s u b s t a n t i a l
coke formation. The unique behavior of the asphaltenes i n the
presence of molybdenum on the other hand provided us with an
e x c e l l e n t opportunity to look c l o s e r at the s t r u c t u r e of the
reacted asphaltenes. Since these r e a c t i o n s were c a r r i e d out
neat, maltenes could be separated and analyzed d i r e c t l y . There
were no maltenes i n i t i a l l y so these molecules must at one time
have been attached to the reactant asphaltene molecules.
Furthermore, the reacted asphaltenes could a l s o be analyzed to
determine what chemical changes were t a k i n g place during
reaction.
Elemental a n a l y s i s showed some i n t e r e s t i n g r e s u l t s with
regard to H/C, s u l f u r and n i t r o g e n l e v e l s . Figure 4 shows a p l o t
of the (H/C) values i n the reacted asphaltenes and the product
maltenes. As can be seen, the (H/C) r a t i o i n the reacted asphal-
tenes drops continuously while that of the product maltenes
r i s e s continuously. The weighted average of the measured asphal-
tene and maltene f r a c t i o n s r i s e s s l i g h t l y i n d i c a t i n g the a d d i t i o n
of some hydrogen to the system. This i s the kind of behavior
that might be expected of an asphaltene s t r u c t u r e c o n t a i n i n g a
l a r g e , hydrogen d e f i c i e n t core to which are attached smaller,
hydrogen-rich molecules. I t i s not c o n s i s t e n t with the smaller
asphaltene s t r u c t u r e proposed by Ignasiak et a l (2) f o r Athabasca
asphaltenes.
Next the question of s u l f u r d i s t r i b u t i o n was addressed.
S u l f u r i n the asphaltene and maltene f r a c t i o n s was measured
d i r e c t l y and that i n the gas was obtained by d i f f e r e n c e . The
r e s u l t f o r t h i s same s e r i e s of runs i s shown i n Figure 5. What
we found was that approximately 50% of the s u l f u r remained i n

T A B L E II
EFFECT OF HYDROGEN TRANSFER ON OLE FIN/PARAFFIN

R A T I O IN G A S P R O D U C T S
C C
3 ^ 3
REACTION
TEMP. (°C) T I M E (MIN.) THERMAL 200 p p m MOLYBDENUM
365 42 0.18 0.08
87 0.13 0.05
177 0.07 0.03
357 0.04 0.02
335 87 0.26 0.14
177 0.15 0.06
357 0.08 0.03
747 0.04 0.02

Figure 3. Arrhenius plot for hydroconversion of Cold Lake asphaltenes: 200 ppm
molybdenum (A A' thermal (

Figure 4. Hydrogen-to-carbon ratios in reaction products: maltenes (%); total

product (calculated) ( ); asphaltenes (AA

SCHUCKER AND KEWESHAN Cold Lake Asphaltenes 337

the reacted asphaltene, 28% was found i n the maltenes while 22%
wound up i n the gas (presumably as H S ) . 2 Studies with model
s u l f u r compounds ( i n c l u d i n g dibenzothiophene, diphenyl s u l f i d e ,
benzyl phenyl s u l f i d e and d i b e n z y l d i s u l f i d e ) under the same
r e a c t i o n c o n d i t i o n s l e d us to conclude that the m a j o r i t y of the
s u l f u r i n both the asphaltene and maltene products was e i t h e r
h e t e r o c y c l i c or an intermediate r e a c t i o n product from the c l e a v -
age of d i a r y l or a l k y l - a r y l s u l f i d e l i n k a g e s . More e a s i l y
cleaved bonds such as those i n d i a l k y l s u l f i d e s or d i s u l f i d e s
were found to be converted very q u i c k l y .
Nitrogen was a l s o measured i n the asphaltenes and maltenes
and the r e s u l t s are shown i n Table I I I . What we found was t h a t ,
u n l i k e s u l f u r which i s d i s t r i b u t e d p r e t t y evenly between the
asphaltene core and the p e r i p h e r a l groups, n i t r o g e n i s p r i m a r i l y

i n the core s t r u c t u r e . In a d d i t i o n , during r e a c t i o n very l i t t l e
i f any of the n i t r o g e n i s removed from the system. This suggests
that n i t r o g e n i s i n predominantly condensed h e t e r o c y c l i c s t r u c -
tures i n the core with only about 12-14% e x i s t i n g as smaller
condensed n i t r o g e n s t r u c t u r e s on the periphery.
Oxygen was measured only i n the asphaltenes due to sample
size limitations. Combined r e s u l t s i n d i c a t e d that over 50% of
the oxygen was l i b e r a t e d during these r e a c t i o n s as gaseous
species and t h i s i s i n good agreement with r e c e n t l y p u b l i s h e d
work of Moschopedis et a l (5) suggesting the presence of car-
b o x y l i c a c i d and aldehyde f u n c t i o n a l i t y .
In a d d i t i o n to elemental analyses, number average molecular
weights (M ) were obtained on both asphaltene and maltene f r a c -
t i o n s from s e r i e s . The r e s u l t i n g curves are shown i n F i g u r e
6. The s t a r t i n g asphaltenes are observed to have a number aver-
age molecular weight of 6640 ± 120. This decreases monotonically
to an apparent asymptote of 3400. At the same time, maltenes
which are produced e x h i b i t much lower molecular weights s t a r t i n g
at 645 and decreasing to 415. I t i s not unreasonable at t h i s
p o i n t to p o s t u l a t e that the maltenes, once formed, continue to
break down. Here again, the observed v a r i a t i o n i n average
molecular weight i s c o n s i s t e n t with the concept that asphaltenes
have a l a r g e r core s t r u c t u r e to which are attached smaller
(M/10 the s i z e of the core) groups. We are not saying t h a t
3400 represents the molecular weight of the core s t r u c t u r e .
Experimental nmr and other VPO evidence p o i n t s to the contrary.
We are saying that at 400°C we have broken a l l bonds that can be
thermally broken at a reasonable rate and are l e f t with the core
plus p e r i p h e r a l groups attached by much stronger bonds ( i . e .
b i p h e n y l l i n k a g e s , e t c . ) and some a l k y l s i d e chains.
One of the most powerful t o o l s a v a i l a b l e to us f o r charac-
t e r i z a t i o n of these f r a c t i o n s i s nuclear magnetic resonance
1 3
spectroscopy. Proton and C F o u r i e r transform nmr spectra were
run i n deuterochloroform on these same asphaltene and maltene
samples and some of the spectra are shown i n F i g u r e s 7 and 8.
One of the f i r s t i n t e r e s t i n g p o i n t s we f i n d i s t h a t the asphal-

T A B L E III
NITROGEN CONTENT O F REACTION PRODUCTS
REACTION % ASPHALTENE N / N n
T I M E (MIN) CONVERSION ASPHALTENES MALTENES
0 0 1.0 0
27 26.0 0.83 0.12
57 38.3 0.83 0.12
117 42.7 0.76 0.14
4 0 0 ° C , 200 ppm Mo

80001 , , 1 r
7000r-
3001 I I I I I I
0 20 40 60 80 1 00 1 20
TIME a) 400°C (MIN)
Figure 6. Molecular weights of reaction products

SCHUCKER A N D KEWESHAN Cold Lake Asphaltenes
, i • i . i i i •i . i . i • i • i • i • i • i • i . i . i . l
10 9 8 7 6 5 4 3 2 1 0
1 1 1 1 1 1 1
i | i | i | i | i | ' i ' i i i i i ' I • I ' I • I I i I I I I I
i • i . i • i , i , i , i • i • I . I I i i . i • i . i i I . I i I
10 9 8 7 6 5 4 3 2 1 0
6 (PPM FROM TMS)
Figure 7. H-l NMR spectra of (top) crude and (bottom; reacted (400°C, 2 h)
asphaltenes

11
I 1
I I ' I I I | I I I I | ' M II I I | I I I I | I I I I | I I I I | I II I | I I I I | I I I I | I I I I | I I I I | I I I I | I I I I | M M |
6 (PPM FROM TMS)
Figure 8. C-13 NMR spectra of (top) crude and (bottom; reacted (400°C, 2 h)
asphaltenes



22. SCHUCKER A N D KEWESHAN Cold Lake Asphaltenes 345
1 3
tenes with M = 3400 s t i l l have 40% a l i p h a t i c carbon. Both C
X
and H specfra confirm these as predominantly p a r a f f i n i c s i d e
chains although some naphthenic character s t i l l remains. These
side chains need not be connected to the asphaltene core s i n c e
the smaller p e r i p h e r a l groups are a l s o known to be h i g h l y a l k y l
substituted. In general we can say that the increase i n the
f r a c t i o n o f aromatic carbon and hydrogen during r e a c t i o n i s
c o n s i s t e n t with (1) the loss of a l k y l side chains, (2) l o s s o f
h i g h l y s u b s t i t u t e d aromatic and naphthenic groups, and (3) l o s s
of naphthenic hydrogen. We b e l i e v e that to a c e r t a i n degree a l l
of these are o c c u r r i n g but that (2) i s the dominant r e a c t i o n .
We can a l s o say based on subsequent experimental work using
n-decyl benzene as a model a l k y l aromatic that under these condi-
t i o n s (400°C, 120 min, 7 MPa H ) p - s c i s s i o n of a l k y l side chains
i s p r e f e r r e d 20:1 over Of.

One maltene sample generated under somehwat milder condi-
t i o n s (3 h r s . , 365°C, CoMo/y-Al 0 ) to minimize secondary crack-
2 3
ing r e a c t i o n s was analyzed by gas chromatography and the

r e s u l t i n g chromatogram i s shown i n F i g u r e 9. I t i s c l e a r that
while the vast m a j o r i t y o f the area i s contained i n the lower
envelope, a d e f i n i t e p a t t e r n o f r e g u l a r l y - s p a c e d peaks i s observ-
a b l e above the base. These were i d e n t i f i e d by gas chroma-
tography/mass spectrometry as n - p a r a f f i n s ranging i n length from
C11 to C 3 9 . The smaller peaks i n between were i d e n t i f i e d as
p r i m a r i l y i s o - p a r a f f i n s which may have been formed by i s o m e r i z a -
t i o n during hydroconversion over the somewhat a c i d i c CoMo/v-Al 0 2 3
or which may represent the n a t u r a l d i s t r i b u t i o n of i s o p a r a f -

f i n s i n the a l k y l side chains.
In summary, we have presented experimental evidence which
supports the concept that Cold Lake asphaltenes have somewhat
l a r g e , hydrogen-deficient core s t r u c t u r e s to which are attached
a l k y l side chains and h i g h l y s u b s t i t u t e d aromatic groups. We
have shown that s u l f u r tends to be r e l a t i v e l y evenly d i s t r i b u t e d
between the core s t r u c t u r e s and the p e r i p h e r a l groups and that
n i t r o g e n i s concentrated predominantly i n the cores. The o v e r a l l
p i c t u r e of asphaltene r e a c t i v i t y that has emerged from t h i s i s
shown s c h e m a t i c a l l y i n F i g u r e 10. During m i l d hydroconversion,
weaker linkages are thermally broken r e s u l t i n g i n the formation
of maltenes having a higher (H/C) and reacted asphaltenes having
a lower (H/C). Some a l k y l s i d e chains are a l s o l o s t predom-
i n a n t l y by p - s c i s s i o n . In the absence o f e f f e c t i v e hydrogen
t r a n s f e r , some o f these r e a c t i o n fragments can recombine to form
coke. With improved hydrogen t r a n s f e r the coking r e a c t i o n s can
be s i g n i f i c a n t l y delayed. T o t a l conversion o f these asphaltenes
to maltenes would a t t h i s p o i n t seem to be an improbable g o a l ;
however, more research i s needed i n order to see how f a r the
s t r u c t u r a l concepts developed here f o r Cold Lake asphaltenes can
be g e n e r a l i z e d to others.

Literature Cited
1. Speight, J. G., "A Structural Investigation of the Constit-
uents of Athasbaca Bitumen by Proton Magnetic Resonance
Spectroscopy," Fuel, 1970, 49, 76-90.
2. Ignasiak, T., Kemp-Jones, A. V. and Strausz, O. P., "The
Molecular Structure of Athabasca Asphaltenes. Cleavage of
the Carbon-Sulfur Bonds by Radical Ion Electron Transfer
Reactions," J. Org. Chem., 1977, 42(2), 312-320.
3. Bearden, R., Jr. and Aldridge, C. L., U.S. Patent
4,134,825 (1979).
4. Bearden, R., Jr., private communication.

5. Moschopedis, S. E., Parkash, S. and Speight, J. G., "Thermal
Decomposition of Asphaltenes," Fuel, 1978, 57, 431-434.

23
Influence of Thermal Processing on the Properties
of Cold Lake Asphaltenes: The Effect of
Distillation
KENNETH A. GOULD and MARTIN L. GORBATY
Corporate Research Science Laboratories, Exxon Research and Engineering
Company, P.O. Box 45, Linden, NJ 07036
A better understanding of the composition and properties of

heavy feeds such as Cold Lake and Arabian Heavy oils is central
to the development of improved upgrading technology. An impor-
tant question which must be answered is to what extent these
materials are thermally altered during refinery distillation.
These heavy oils already contain large percentages of refractory
materials such as asphaltenes, and it would be highly undesirable
to increase the amount or degrade the quality of these components.
We have, therefore, investigated the effect of heat treatment
during distillation on the quantity and physical and chemical
properties of asphaltenes. Cold Lake crude was chosen for this
study since it is known to be a thermally sensitive material.
Any changes caused by thermal treatment should, therefore, be more
obvious than with a more stable feed. We report here the results
of a variety of measurements made on the asphaltenes isolated
from Cold Lake crude oil and from its vacuum distillation residue.
It should be borne in mind that Cold Lake crude is subjected to
the high temperatures of pressurized steam used in the production
process and may conceivably have already undergone some thermal
alteration. The present study, however, is designed primarily
to learn if any further changes might occur during refining.
Background
The q u e s t i o n o f whether and t o what extent asphaltenes are

formed or a l t e r e d during crude o i l h a n d l i n g and p r o c e s s i n g has
remained unresolved. In one i n v e s t i g a t i o n , samples of a T a r t a r
m i n e r a l o i l d i s t i l l a t i o n r e s i d u e were heated f o r f i v e hours to
163°C and then f o r another f i v e hours to 400°C t o simulate con-
d i t i o n s during d i s t i l l a t i o n . ( 1 ) Both an i n c r e a s e i n asphaltene
content and a decrease i n asphaltene H/C r a t i o were observed. In
a d d i t i o n , d i s t i l l a t i o n r e s i d u e s from v a r i o u s other crudes were
heated to v a r i o u s temperatures f o r three hours and then pentane
deasphaltened. I t was observed that asphaltene H/C r a t i o s
decreased r a p i d l y above gffiftjgfflpfl^nffc^. 6.
O097-6156/8S(HJ«|yOl4^8Py00/O
© 1981 A m p f j j j n ^ i j j c ^ ^ i e t y
Washington, D. C. 20030
These i n v e s t i g a t o r s a l s o heated maltenes i n sealed v i a l s to

v a r i o u s temperatures. The asphaltene y i e l d s obtained a t 350°C,
400°C, and 450°C were 18, 32, and 36%, r e s p e c t i v e l y . Although
the conversions were approximately f i r s t order a t the lower
temperatures, they changed s i g n i f i c a n t l y a t 450°C, the r e g i o n
of t e c h n i c a l i n t e r e s t f o r many r e f i n i n g o p e r a t i o n s . Significant
formation o f new asphaltenes was seen t o occur. Deasphaltened
maltenes were a l s o separated by alumina chromatography i n t o a
non-aromatic " g a s o l i n e " e l u a t e , a s t r o n g l y aromatic benzene
e l u a t e , and a resinous benzene-methanol e l u a t e . Pentane i n s o l -
ubles were obtained from a l l three f r a c t i o n s upon h e a t i n g a t
r e l a t i v e l y low temperatures, although the r a t e s were q u i t e d i f -
f e r e n t . Resins gave the h i g h e s t y i e l d s a t the f a s t e s t r a t e s
while the aromatic o i l s showed about the same y i e l d , but a t a
much slower r a t e . The y i e l d and r a t e were lowest f o r the non-

aromatic o i l s , and t h e i r pentane i n s o l u b l e s were mostly toluene
i n s o l u b l e s and p y r i d i n e i n s o l u b l e s r a t h e r than asphaltenes. The
r e p o r t a l s o claimed that asphaltenes were formed even a t 20°C i n
the absence of a i r a t r e l a t i v e l y slow r a t e s .
A study of the e f f e c t o f heat on asphaltene decomposition a t
350-380°C i n a helium flow system (2) r e s u l t e d i n the f o l l o w i n g
observations:
1. decomposition was found t o be f i r s t order i n asphaltenes
2. the percent coke make expressed as a percent of asphaltenes
decomposed d i d not vary w i t h the extent of c r a c k i n g , implying
that the mechanism i s independent of the percent c r a c k i n g .
11
3. a "20,000-fold i n c r e a s e i n s u r f a c e area of the asphaltenes
v i a i n t r o d u c t i o n of carbon b l a c k (manner not s p e c i f i e d ) d i d
not change the r e a c t i o n r a t e
4. toluene i n s o l u b l e s were formed i n amounts that decreased
with i n c r e a s i n g r e a c t i o n time, implying t h a t these products
are intermediates i n p y r i d i n e i n s o l u b l e formation.
These observations l e d to the p r o p o s a l o f a f r e e r a d i c a l , c h a i n
r e a c t i o n mechanism. Aspects of the mechanism i n c l u d e : (1)
formation o f s m a l l r a d i c a l fragments which could a b s t r a c t hydro-
gen and leave as l i g h t products, (2) r e a c t i o n of s t a b i l i z e d f r e e
r a d i c a l s (formed by hydrogen a b s t r a c t i o n ) which could i n t e r a c t
w i t h asphaltenes to form l a r g e r and l a r g e r condensation products,
and (3) formation of toluene i n s o l u b l e s , i . e . l i n e a r condensation
products, and p y r i d i n e i n s o l u b l e s , i . e . c r o s s - l i n k e d products.
These c h a i n r e a c t i o n s could be terminated by formation of very
s t a b l e r a d i c a l s that could not r e a c t f u r t h e r . ( 2 ) T h i s mechanism
i s i n accord with the c o n c l u s i o n s of Speight, who has s t a t e d
that formation of p a r a f f i n s d u r i n g p y r o l y s i s of Athabasca
asphaltenes probably occurs v i a i n t e r a c t i o n of a l k y l r a d i c a l s
with hydrogen produced during a r o m a t i z a t i o n and condensation o f
p o l y c y c l i c s t r u c t u r e s . ( 3 ) Carbon-carbon bond breaking i n these
asphaltenes was found to occur p r i m a r i l y $ to aromatic r i n g s .

23. GOULD A N D GORBATY Thermal Processing 349
In other work (4), x-ray a n a l y s i s l e d to the c o n c l u s i o n

that not only d i d asphaltene m e l t i n g p o i n t i n c r e a s e w i t h i n c r e a s -
i n g f r a c t i o n a l a r o m a t i c i t y , f , but thermal s e n s i t i v i t y i n c r e a s e d
a
i n the same d i r e c t i o n . Thus, asphaltenes with f 0.32 were more a
s e n s i t i v e and were transformed to a l a r g e extent to toluene

i n s o l u b l e s a f t e r one hour at 375°C. When f was 0.17 and 0.24,
a
only 18-32% conversion to toluene i n s o l u b l e s was observed.
Experimental
P r e p a r a t i o n of Asphaltenes. Asphaltenes were obtained by

n-heptane p r e c i p i t a t i o n from e i t h e r Cold Lake crude or vacuum
residuum using t y p i c a l deasphaltening procedures. ( i . e . One p a r t
of residuum was r e f l u x e d f o r one hour with 10 p a r t s of heptane.

The mixture was then f i l t e r e d and the i n s o l u b l e asphaltenes
washed s e v e r a l times with heptane and pentane and d r i e d i n vacuo
at 80°C.)
P y r o l y s i s of Asphaltenes. Pyrolyses were performed u s i n g

the apparatus shown i n Figure 1.(5) The a p p r o p r i a t e m a t e r i a l was
placed i n a quartz tube w i t h 24/40 ground j o i n t s and a dry i c e
condenser was attached. A f t e r a l t e r n a t e l y evacuating and f l u s h -
i n g with n i t r o g e n s e v e r a l times, the m a t e r i a l was pyrolyzed at
the a p p r o p r i a t e temperature f o r 10 min. Char and l i q u i d y i e l d s
were c a l c u l a t e d from the weights of the p y r o l y s i s tubes and con-
densers before and a f t e r r e a c t i o n .
A n a l y t i c a l Data. Instrumental analyses and s p e c t r a were made

on the f o l l o w i n g equipment: i n f r a r e d spectroscopy, D i g i l a b FTS-
14 F o u r i e r transform spectrophotometer; vapor pressure osmometry,
H i t a c h i - P e r k i n Elmer 115; g e l permeation chromatography, Waters
Assoc. 200; nuclear magnetic resonance spectrometry, V a r i a n
Assoc. A60 and XL100; thermogravimetric a n a l y s i s , modified Stanton
thermobalance; d i f f e r e n t i a l scanning c a l o r i m e t r y , P e r k i n Elmer DSC
2; and e l e c t r o n s p i n resonance spectrometry, V a r i a n Assoc. Century
spectrometer with E102 X band microwave b r i d g e o p e r a t i n g at 9.5
GHz.
The f i n d i n g s discussed above (1-4) i n d i c a t e that changes i n

asphaltene q u a l i t y and q u a n t i t y during thermal treatment depend
s t r o n g l y on both the o r i g i n of the o i l and the s e v e r i t y of the
treatment. This means that s p e c i f i c questions concerning s t a b i l i t y
can only be answered v i a s t u d i e s on the p a r t i c u l a r o i l at the
p a r t i c u l a r c o n d i t i o n s of i n t e r e s t .

Figure 1. Rapid heat-up pyrolysis unit

To provide raw m a t e r i a l f o r t h i s comparative study of

untreated and h e a t - t r e a t e d o i l s , asphaltenes from Cold Lake
crude (crude asphaltenes) and from Cold Lake vacuum residuum
(residuum asphaltenes) were prepared by n-heptane p r e c i p i t a t i o n
as d e s c r i b e d i n the Experimental s e c t i o n . The Cold Lake residuum
f r a c t i o n was prepared by Imperial O i l E n t e r p r i s e s , L t d . a t S a r n i a ,
Ontario, Canada. The d i s t i l l a t i o n h i s t o r y of t h i s bottoms
f r a c t i o n i n d i c a t e s that the pot m a t e r i a l was subjected to temp-
eratures as h i g h as 314-318°C d u r i n g atmospheric and vacuum
distillation. The length of time at 300°C or higher was about
two hours. T h i s i s w e l l i n excess of what would be experienced
i n a p i p e s t i l l and should have provided ample time f o r any decom-
position. I t should be noted, however, that s i n c e i t was pos-
s i b l e to maintain the system vacuum a t 0.35 mm, the maximum
temperature experienced by the residuum was not q u i t e as h i g h

as i t might be during r e f i n e r y d i s t i l l a t i o n (e.g. ca 350°C).
Table I shows the y i e l d s of asphaltenes obtained from s e v e r a l
deasphaltening operations on crude o i l and bottoms. The y i e l d s
on bottoms were normalized to y i e l d s on crude by c o r r e c t i n g f o r
the q u a n t i t y of d i s t i l l a t e s i n the crude.
Table I
Asphaltene Y i e l d s from Cold Lake Crude and Residuum
Source % Asphaltenes (On Crude)
Residuum 10.6
Residuum 10.9
Crude 9.9
Crude 9.8
Crude 10.8
The average percentage of asphaltenes i n the bottoms i s

10.8% (based on crude) and i s thus s l i g h t l y higher than the
average value of 10.2% f o r the crude o i l . The 0.6% d i f f e r e n c e
i s , however, w i t h i n the observed experimental v a r i a t i o n of 1.0%
and i s t h e r e f o r e not considered s i g n i f i c a n t .
The average elemental compositions f o r s e v e r a l p r e p a r a t i o n s
of crude and residuum asphaltenes are shown i n Table I I . As
can be seen, the two asphaltenes are q u i t e s i m i l a r with the d i f -
ferences between them being l e s s than the t y p i c a l e r r o r s from
a n a l y s i s to a n a l y s i s . The H/C r a t i o s are almost i d e n t i c a l .

Table I I
Average Elemental Analyses f o r Crude and Residuum Asphaltenes
Asphaltene Ni V
Source % C % H % N % S (ppm) (ppm) H/C
Residuum 81.81 7.75 1.42 8.01 329 893 1.14

Crude 82.14 7.65 1.28 7.78 345 935 1.12
Both the number average molecular weights as determined by

vapor pressure osmometry and e x t r a p o l a t e d to zero c o n c e n t r a t i o n
and the g e l permeation chromatographic molecular weight d i s -
t r i b u t i o n s i n d i c a t e that the crude and residuum asphaltenes do

d i f f e r i n molecular weight. The VPO r e s u l t s are summarized i n
Table I I I and comparative GPC t r a c e s are shown i n F i g u r e 2. As
can be seen from these data, both techniques i n d i c a t e that the
crude asphaltenes have a s i g n i f i c a n t l y higher molecular weight
than the residuum asphaltenes. T h i s r e s u l t i s somewhat s u r -
p r i s i n g s i n c e one would not a. p r i o r i expect thermal c r a c k i n g a t
such low temperatures, ^320°C, even w i t h a thermally s e n s i t i v e
crude such as Cold Lake. T h i s e x p l a n a t i o n , however, cannot be
r u l e d out. Another p o s s i b i l i t y which could account f o r lower
molecular weights i n the residuum asphaltenes, s i d e c h a i n
d e a l k y l a t i o n , can be e l i m i n a t e d on the b a s i s of n u c l e a r magnetic
resonance r e s u l t s (vide i n f r a ) . Another p o s s i b l e cause of the
molecular weight r e d u c t i o n i s thermally induced d i s s o c i a t i o n of
II- II complexes which may help to hold the asphaltene macro-
s t r u c t u r e together. Deasphaltening done at higher s o l v e n t - t o -
o i l r a t i o s , i . e . from 20:1 to 40:1, showed s i m i l a r molecular
weight d i f f e r e n c e s between crude and residuum asphaltenes,
implying that the r a t i o used here, 10:1, d i d not cause the obser-
ved d i f f e r e n c e s . ( 6 )
Table I I I
Number Average Molecular Weights

(M^) f o r Crude and Residuum Asphaltenes
Asphaltene Source Average

Residuum 5120
4400
5850 5305
5850
Crude 8250
6120 6955
6850
6600

The two asphaltenes were a l s o examined by i n f r a r e d ,

n u c l e a r magnetic resonance, and e l e c t r o n s p i n resonance
techniques. Figures 3, 4, and 5 show the r e s u l t s of the IR
analysis. I t i s immediately apparent that the two asphaltene
s p e c t r a (Figures 3 and 4) are q u i t e s i m i l a r , showing no obvious
q u a l i t a t i v e d i f f e r e n c e s . To l e a r n i f more s u b t l e d i f f e r e n c e s
e x i s t e d , a d i f f e r e n c e spectrum (Figure 5) was generated by com-
puter u s i n g the data accumulated f o r Figures 3 and 4. T h i s
demonstrates that v i r t u a l l y complete c a n c e l l a t i o n can be obtained.
The only r e s i d u a l a b s o r p t i o n of any s i g n i f i c a n c e i n t h i s h i g h l y
magnified spectrum i s the s m a l l peak at 2950 cm~l. T h i s may
r e s u l t from t r a c e s of r e s i d u a l s o l v e n t or i t may represent a very
minor d i f f e r e n c e between the two asphaltenes.
In the case of the magnetic resonance c h a r a c t e r i z a t i o n , both

! 3 c NMR and proton NMR were employed to o b t a i n the percentages
of aromatic carbon and hydrogen. The r e s u l t s are shown i n
Table IV. Although the measured l e v e l s o f aromatic hydrogen are
w i t h i n experimental u n c e r t a i n t y of each other, the d i f f e r e n c e i n
aromatic carbon i s probably s i g n i f i c a n t . Nevertheless, t h i s
d i f f e r e n c e i s s m a l l and i n d i c a t e s that the aromatic carbon con-
tents are q u i t e s i m i l a r . In a d d i t i o n , attempts to d i s c e r n
q u a l i t a t i v e d i f f e r e n c e s i n the 13C NMR were i n v a i n . These
r e s u l t s imply that very l i t t l e , i f any, d e a l k y l a t i o n or aromatiza-
t i o n has occurred d u r i n g the crude d i s t i l l a t i o n procedure.
Table IV
Aromatic Carbon and Hydrogen

Contents of Cold Lake Asphaltenes
Asphaltene Source %__C^ % H^
Crude 52.0 + 1 13.7 + 0.5

Residuum 50.4 + 1 14.2 + 0.5
Petroleum asphaltenes e x h i b i t two general types of s i g n a l s

when examined by e l e c t r o n s p i n resonance techniques. One i s the
1 6 - l i n e , a n i s o t r o p i c , vanadyl (V=CH"2) resonance of the s o l i d
s t a t e while the other a r i s e s from unpaired e l e c t r o n s which are
present i n the form of r e l a t i v e l y s t a b l e f r e e r a d i c a l s . The crude
and residuum asphaltenes were examined by ESR, and the r e l e v a n t
data are summarized i n Table V.

700
1 l
? 600
•o
c Resid
| 500 - Asphaltenes Crude
Asphaltenes
y
100 1000 10000 100000
Molecular weight (Polystyrene)
Figure 2. Molecular-weight distributions of Cold Lake crude and residuum

asphaltenes
W A V E L E N G T H (jim)
u
r i i i i 1 i i 1 i
4000 3500 3000 2500 2000 1800 1400 1200 1000 800 600
WAVENUMBER (CM ) - 1
Figure 3. IR spectrum of Cold Lake crude asphaltenes

W A V E L E N G T H (jim)
2.5 3 3.5 4 4.5 5 5.5 7 8 9 10 12 15

4000 3500 3000 2500 2000 1800 1400 1200 1000 800 600
WAVENUMBER (CM" ) 1
Figure 4. 1R spectrum of Cold Lake residuum asphaltenes
W A V E L E N G T H (\im)
4000 3500 3000 2500 2000 1800 1400 1200 1000 800 600
WAVENUMBER (CM ) - 1
Figure 5. Differential IR spectrum of crude and residuum asphaltenes

Table V
ESR Parameters f o r Cold Lake Asphaltenes
Parameter Crude Asphaltenes Residuum Asphaltenes
Vanadyl:
(G) 174.0 174.4

Ml
A, (G) 56.3 56.7
1.9632 1.9629
g| 1.9837 1.9813
Free R a d i c a l :
g 2.00308 2.00307
linewidth (G) 6.4 6.6
I t i s apparent from the chemical s h i f t s ( g - v a l u e s ) , the

h y p e r f i n e c o u p l i n g constants (A-values), and the l i n e w i d t h s t h a t
the f r e e r a d i c a l s and vanadyl species are i n very s i m i l a r e n v i r o n -
ments i n both samples. I t was not p o s s i b l e to o b t a i n meaningful
values f o r the absolute numbers of spins per gram f o r e i t h e r
s p e c i e s , but estimates of the r e l a t i v e concentrations obtained by
measuring peak h e i g h t s i n d i c a t e that the vanadyl and f r e e - r a d i c a l
concentrations do not d i f f e r s i g n i f i c a n t l y between the two
asphaltenes. I t thus appears that heat treatment of Cold Lake
asphaltenes to 320°C does not a l t e r the nature or abundance of
paramagnetic c e n t e r s .
Since most of the p h y s i c a l p r o p e r t i e s of the asphaltenes
d i d not show any major d i f f e r e n c e s , thermal r e a c t i v i t y was i n v e s t i -
gated to d i s c e r n any d i f f e r e n c e s which might e x i s t i n chemical
r e a c t i v i t y . D i f f e r e n t i a l scanning c a l o r i m e t r y and thermogravi-
metric a n a l y s i s as w e l l as r a p i d p y r o l y s i s were employed. The
only n o t a b l e f e a t u r e s of the DSC analyses were what appeared to
be g l a s s t r a n s i t i o n s o c c u r r i n g at 175°C and 172°C f o r the crude
and residuum asphaltenes, r e s p e c t i v e l y . The TGA curves f o r the
two m a t e r i a l s were a l s o v i r t u a l l y i d e n t i c a l , d i f f e r i n g by l e s s
than one percent v o l a t i l e matter at any temperature. Both of
these techniques thus i n d i c a t e e s s e n t i a l l y no d i s c e r n a b l e d i f f e r -
ences i n the two asphaltenes.
S i m i l a r l y , when the p y r o l y s i s behavior was s t u d i e d i n a
r a p i d h e a t i n g u n i t w i t h a heatup time of one to two minutes,
v i r t u a l l y i d e n t i c a l r e s i d u e y i e l d s were obtained.
Summary and Conclusions
The c h a r a c t e r i s t i c s of Cold Lake crude and residuum a s p h a l t -

enes have been compared by a number of i n s t r u m e n t a l and p h y s i c a l
techniques. The asphaltenes were e s s e n t i a l l y i d e n t i c a l i n q u a l i t y

and q u a n t i t y except that the crude asphaltenes e x h i b i t e d higher

average molecular weights as w e l l as molecular weight d i s t r i b u -
t i o n s peaking a t higher molecular weights than d i d the residuum
asphaltenes.
The thermal h i s t o r y of these p a r t i c u l a r residuum asphaltenes
i s much more severe i n terms of h e a t i n g time than would o r d i n a r i l y
be the case f o r a r e f i n e r y product from a p i p e s t i l l s i n c e , i n
the present i n s t a n c e , a pot d i s t i l l a t i o n was used. I t t h e r e f o r e
seems l i k e l y that r e f i n e r y asphaltenes should be even l e s s
d i f f e r e n t from t h e i r r e s p e c t i v e crude asphaltenes than i n t h i s
i n v e s t i g a t i o n , assuming that p i p e s t i l l temperatures would be
kept below the decomposition temperatures f o r the asphaltenes,
i . e . l e s s than about 350°C. Furthermore, any d i f f e r e n c e s should
be f u r t h e r diminished i n the event that a crude which i s l e s s

thermally s e n s i t i v e than Cold Lake i s i n v o l v e d .
Since the Cold Lake crude used i n t h i s i n v e s t i g a t i o n has
been exposed to the temperature of the p r e s s u i z e d steam used
i n the o i l p r o d u c t i o n , one cannot be c e r t a i n that some thermal
changes had not a l r e a d y occurred i n the crude o i l . To study
t h i s p o s s i b i l i t y the p r o p e r t i e s of c o l d b a i l e d ( i . e . recovered
without steam i n j e c t i o n ) Cold Lake crude asphaltenes are being
i n v e s t i g a t e d by many of these same techniques and w i l l be
described i n a f u t u r e r e p o r t .
Acknowled gments
We would l i k e to thank R. B. Long f o r h i s a s s i s t a n c e i n

the p r e p a r a t i o n of t h i s manuscript, R. R i f f o r help with the
experimental work, and the f o l l o w i n g i n d i v i d u a l s f o r t h e i r a s s i s t -
ance i n the v a r i o u s a n a l y t i c a l measurements: L. Ebert, J . E l l i o t t ,
B. Hager, B. Hudson, M. M e l c h i o r , E. P r e s t r i d g e , W. Schulz, and
B. S i l b e r n a g e l .
Literature Cited
1. Hrapia, H. Meyer, D., and Prause, M., Chem. Tech., 1964, 16,
(12), 733.
2. Magaril, R. Z., and Aksenova, E. J., Khim. Technol. Top.
Masel, 1970, 15, (7), 22.
3. Speight, J. G., Am. Chem. Soc., Div. Fuel Chem. Prepr., 1971,
15, (1), 57.
4. Bestougeff, M. A., and Genderel, P., Am. Chem. Soc., Div.
Petrol. Chem. Prepr., 1964, 9, (2), B51.
5. Design supplied by R. J. Lang, Exxon Res. and Eng. Co.,
Baytown, Texas.
6. R. C. Schucker, private communication from these laboratories.

24
Thermal Recovery of Oil from Tar Sands by an
Energy-Efficient Process
2
K. M.JAYAKAR1,J. D. SEADER, A. G. OBLAD, and K. C. HANKS
Departments of Chemical and Fuels Engineering, University of Utah,
Salt Lake City, UT 84112
Oil-impregnated rock d e p o s i t s , more commonly r e f e r r e d to as

tar sands, are found on every continent except A u s t r a l i a and
A n t a r c t i c a (1). The l a r g e s t known d e p o s i t s occur in northern
A l b e r t a , Canada, where two full-scale commercial p l a n t s f o r pro-
ducing s y n t h e t i c crude oil a r e in o p e r a t i o n and two more p l a n t s
have been approved f o r c o n s t r u c t i o n . Of the 24 s t a t e s that con-
t a i n t a r sands in the United S t a t e s , Ritzma (2) estimates that
about 90-95 percent o f these t a r sands lie in Utah. Although the
Utah deposits c o n t a i n only about 25 billion b a r r e l s of i n - p l a c e
bitumen, compared t o 900 billion b a r r e l s in Canada, as d i s c u s s e d
by Oblad et al. (3), the Utah d e p o s i t s represent an important
p o t e n t i a l domestic source o f s y n t h e t i c petroleum.
Operating p l a n t s in Canada employ a hot-water process f o r
r e c o v e r i n g bitumen from t a r sands. Although Utah t a r sands can be
c o n s i d e r a b l y d i f f e r e n t from Canadian t a r sands w i t h respect t o
p h y s i c a l and chemical p r o p e r t i e s (4), Sepulveda and Miller (5)
have s u c c e s s f u l y processed t a r sands from high-grade Utah d e p o s i t s
with a m o d i f i e d hot-water process that uses high-shear c o n d i t i o n s
to overcome the higher v i s c o s i t y of Utah tar-sand bitumens. More
recent work by M i s r a and Miller (6) has been s u c c e s s f u l in pro-
cessing medium-grade Utah d e p o s i t s . Other methods f o r p r o c e s s i n g
tar sands that have been s t u d i e d e x t e n s i v e l y (1) i n c l u d e v a r i o u s
in-situ techniques and mining followed by d i r e c t coking, s o l v e n t
e x t r a c t i o n , or cold-water s e p a r a t i o n . Of the other methods that
use mined m a t e r i a l as the feed stock, d i r e c t coking processes,
g e n e r a l l y r e f e r r e d to as thermal recovery methods, appear t o exhi-
b i t the most promise as a l t e r n a t i v e s to hot-water processing
because thermal recovery methods avoid handling of v i s c o u s bitumen,
recovery of sediment from s o l u t i o n s , and recovery and r e c y c l e of
water and/or s o l v e n t s . In the work presented here, a new energy-
e f f i c i e n t thermal process was developed and a p p l i e d to t a r sands
from three Utah d e p o s i t s .
1
Current address: Eastman Kodak Company, Rochester, NY, 14605.
2
Current address: Celanese Chemical Company, Pampa, TX, 78408.
0097-6156/81/0163-0359$05.00/0

Thermal Recovery Process

The concept of r e c o v e r i n g l i q u i d and/or gaseous hydrocarbons
from s o l i d hydrocarbon-bearing m a t e r i a l s by thermal treatment has
been known f o r s e v e r a l c e n t u r i e s (7). Thermal treatment essen-
t i a l l y e n t a i l s p r o c e s s i n g at high temperature. In most thermal
processes, the feed m a t e r i a l i s heated i n an i n e r t or non-
o x i d i z i n g atmosphere. The mode of h e a t i n g and the operating
temperature l a r g e l y determine the type of changes o c c u r r i n g to the
feed, which can i n c l u d e : 1) v o l a t i l i z a t i o n of any low-molecular-
weight components i n the feed, 2) generation of vapors by c r a c k i n g
r e a c t i o n s , and 3) conversion of part of the m a t e r i a l i n t o coke,
by r e a c t i o n s such as p o l y m e r i z a t i o n . In the case of feed m a t e r i -
a l s such as t a r sand, which c o n t a i n a s i g n i f i c a n t amount of s i l i c a
sand or other i n o r g a n i c i n e r t matter that remains s u b s t a n t i a l l y

unchanged through the thermal treatment, coke i s obtained as a
deposit on the i n o r g a n i c matter.
Thermal p r o c e s s i n g can r e q u i r e a s u b s t a n t i a l input of energy
to provide the necessary s e n s i b l e , l a t e n t , and r e a c t i o n h e a t s .
However, as d i s c u s s e d by Oblad et a l . (3), coke, when produced as
above and subsequently combusted, can g e n e r a l l y provide much or
a l l of t h i s energy requirement. Combustion, r e f e r r e d to some
authors as decoking or burning, i s t h e r e f o r e an important aspect
of thermal-recovery methods.
Moore et a l . (8) c l a s s i f y thermal processes i n t o two general
groups, d i r e c t heated and i n d i r e c t heated, depending on whether
p y r o l y s i s and combustion steps are c a r r i e d out i n one or two
r e a c t i o n v e s s e l s . The processes f u r t h e r d i f f e r from each other
with r e s p e c t to f l u i d i z e d - b e d or moving-bed s t a t e of s o l i d s i n
each of the two s t e p s . Table I shows a general process c l a s s i -
f i c a t i o n scheme that f i t s most known thermal processes. Refer-
ences are i n c l u d e d i n that t a b l e . Regardless of the thermal
process used, as d i s c u s s e d i n d e t a i l by Bunger (4), the s y n t h e t i c
crude o i l product obtained cannot, i n general, be used as a sub-
s t i t u t e f o r crude petroleum but must be upgraded to reduce s u l f u r
and n i t r o g e n contents, average molecular weight, and C/H r a t i o .
In a l l thermal recovery processes, t a r sand i s subjected to
high p r o c e s s i n g temperatures, about 450-550°C f o r p y r o l y s i s , and
the r e s i d u a l coked sand i s f u r t h e r heated to about 550-650°C during
the combustion s t e p . At these c o n d i t i o n s , an acceptable thermal
e f f i c i e n c y can only be obtained i f a s i g n i f i c a n t p o r t i o n of the
s e n s i b l e heat i n the spent sand i s recovered and introduced back
i n t o the process. Almost a l l the processes i n Table I provide f o r
heat recovery from spent sand before i t i s d i s c a r d e d .
Perhaps the best-known f l u i d i z e d - b e d process i s the one
developed by G i s h l e r and Peterson (17, 24-, 25) i n Canada. The
process scheme resembles that of c a t a l y t i c c r a c k i n g as used i n the
petroleum i n d u s t r y . Tar sand i s fed to the p y r o l y s i s or coker bed,
where the o i l vapor produced i s c a r r i e d by the f l u i d i z i n g gas to
the product c o l l e c t i o n system. Coked sand i s withdrawn from the
coker and blown by preheated a i r i n t o the burner where the coke

24. JAYAKAR ET AL. Thermal Recovery of Oil 361
i s burned. A p o r t i o n of the hot sand i s r e c y c l e d to the coker to

supply heat f o r the p y r o l y s i s step, with the remainder d i s c a r d e d
through an overflow pipe i n the burner bed. Two s e r i o u s drawbacks
of t h i s process, as noted by Camp (1), are the l a r g e r e c y c l e of
hot sand r e q u i r e d and the high energy content of the net spent
sand. Rammler (23) has d e s c r i b e d the a p p l i c a t i o n of the L u r g i -
Ruhrgas process to t a r sands. L i k e the G i s h l e r and Peterson pro-
cess, i t uses sand as the heat c a r r i e r .
Development of an E n e r g y - E f f i c i e n t Thermal Process
The p a r t i c u l a t e nature of the m i n e r a l matter i n most t a r

sands permits f l u i d i z e d p r o c e s s i n g with s e v e r a l advantages: 1)
d i s i n t e g r a t i o n of lumps of t a r sand to i n d i v i d u a l p a r t i c l e s upon
the p y r o l y s i s of the bitumen; hence such feeds do not have to be

reduced to a s m a l l s i z e p r i o r to entry i n t o the p y r o l y s i s reactor;
2) r e l a t i v e ease of handling s o l i d s because f l u i d i z e d s o l i d s flow
through pipes l i k e l i q u i d ; 3) h i g h h e a t - t r a n s f e r r a t e s between
f l u i d i z i n g medium and s o l i d p a r t i c l e s ; 4) n e a r l y i s o t h e r m a l opera-
t i o n , which permits c l o s e c o n t r o l of the temperature of p y r o l y s i s ,
a v a r i a b l e a f f e c t i n g product y i e l d s , q u a l i t y and energy r e q u i r e -
ments; 5) high r a t e s f o r mass t r a n s f e r between p a r t i c l e s u r f a c e
and f l u i d i z i n g medium, which i s important f o r a h i g h r a t e of feed
per u n i t area without forming agglomerates; 6) accommodation of
v a r i a t i o n s i n bitumen content of feed by r e g u l a t i n g the flow of
f l u i d i z i n g gas; and 7) ease of immersion of heat t r a n s f e r tubes
or heat exchangers i n the f l u i d i z e d beds w i t h accompanying h i g h
h e a t - t r a n s f e r c o e f f i c i e n t s . The l a s t f a c t o r i s p a r t i c u l a r l y
important f o r the type of process developed i n t h i s study and
c o n s t i t u t e s the primary reason f o r the choice here of f l u i d i z e d
p y r o l y s i s . A f l u i d i z e d bed recommends i t s e l f f o r burning coke
f o r e s s e n t i a l l y the same reasons as f o r p y r o l y s i s and was used,
t h e r e f o r e , f o r the process developed here.
P r e v i o u s l y developed processes employ v a r i o u s f e a t u r e s to
accomplish heat t r a n s f e r f o r preheat and p y r o l y s i s . These i n -
clude 1) preheating the tar-sand feed, s e p a r a t e l y from the p y r o l y -
s i s step, g e n e r a l l y to recover heat from outgoing hot gaseous
streams; 2) preheating the incoming process gas streams, gener-
a l l y to recover heat from spent sand or s o l i d s r e s i d u e l e a v i n g
the process; 3) t r a n s f e r of heat from the burner to the p y r o l y s i s
r e a c t o r i n the form of s e n s i b l e heat of gases l e a v i n g the burner,
g e n e r a l l y by d i r e c t heat exchange with the contents of the p y r o l y -
s i s zone; and 4) i n t e r n a l combustion of coke i n the p y r o l y s i s
r e a c t o r i t s e l f with a c o n t r o l l e d amount of o x i d i z i n g gas so that
only a p o r t i o n of the hydrocarbons i n the p y r o l y s i s zone, p r e f e r -
ably coke, i s combusted; 5) t r a n s f e r from the burner to the
p y r o l y s i s step by r e c y c l e of hot, spent sand as a heat c a r r i e r .
Feature 1 has not been shown to be p r a c t i c a l because, when
preheated, t a r sand becomes s o f t and s t i c k y , making i t impossible

to feed by common feeding devices such as a screw conveyor.

Feature 2 can be and g e n e r a l l y i s incorporated i n t o most thermal
processes. However, a maximum of only about 25 percent of the
energy i n the hot, spent sand can be recovered by preheating the
o x i d i z i n g g^s f o r coke combustion. In Feature 3, the amount of
energy that can be c a r r i e d by gases from the combustion zone to
the p y r o l y s i s zone i s r e l a t i v e l y s m a l l . Feature 4 r e q u i r e s a
means f o r d i r e c t heat t r a n s f e r between the two zones by conduc-
t i o n , convection, and/or r a d i a t i o n . Unless t h i s can be accom-
p l i s h e d on a l a r g e s c a l e w i t h l i t t l e or no combustion of bitumen,
Feature 4 i s not p r a c t i c a l . Feature 5 i s p r a c t i c a l , but excessive
r e c y c l e of hot, spent sand i s r e q u i r e d , thus g r e a t l y i n c r e a s i n g
the r e q u i r e d s i z e s of p y r o l y s i s and combustion r e a c t o r s and
n e c e s s i t a t i n g l a r g e devices to convey the sand.
Another p o s s i b l e means of t r a n s f e r r i n g heat from the coke-

combustion stage to the p y r o l y s i s stage i s by the use of i n d i r e c t
heat exchange not i n v o l v i n g sand or gas. In the process developed
i n t h i s work, t h i s means was implemented by i n c o r p o r a t i n g heat
pipes to t r a n s f e r the bulk of the energy r e q u i r e d f o r s o l i d pre-
heat and p y r o l y s i s from the coke-combustion stage. A heat pipe,
f o r the purpose here, may be d e f i n e d simply as a completely
enclosed tubular device w i t h very high e f f e c t i v e thermal conduc-
tance, which t r a n s f e r s heat by two-phase c i r c u l a t i o n of a working
f l u i d (28).
In o p e r a t i o n , heat i s t r a n s f e r r e d to one end of the heat
pipe, causing the working f l u i d to v a p o r i z e . The vapor flows to
the other, c o o l e r end due to the pressure g r a d i e n t s e t up i n s i d e
the c e n t r a l vapor core of the heat p i p e . There, the vapor con-
denses on the tube w a l l and i n s i d e a wick, t r a n s f e r r i n g heat to
the surroundings. The condensate then returns to the warmer end,
thus completing the c y c l i c flow of the f l u i d . Because a l a r g e
amount of heat can be t r a n s f e r r e d by a heat pipe, i t s s o - c a l l e d
e f f e c t i v e thermal c o n d u c t i v i t y can be extremely h i g h . For a p p l i -
c a t i o n to thermal processing of t a r sands, potassium was s e l e c t e d
as the working f l u i d .
The e s s e n t i a l f e a t u r e s of the r e a c t o r system f o r the new
thermal process developed i n the work reported here are i l l u s -
t r a t e d i n the s i m p l i f i e d process scheme of F i g u r e 1. F r e s h l y
mined and s i z e d t a r sand i s dropped i n t o the upper bed of a m u l t i -
staged f l u i d i z e d - b e d column. The upper bed i s a p y r o l y s i s r e a c -
t o r , which i s maintained a t a temperature of g e n e r a l l y between
400° and 550°C. Here, bitumen i n the feed i s cracked and/or
v o l a t i l i z e d , l e a v i n g a coke deposit on the sand p a r t i c l e s . The
o i l vapors and l i g h t hydrocarbon gases produced are c a r r i e d o f f
by the i n e r t f l u i d i z i n g gas to f i n e s - s e p a r a t i o n and product-
recovery s e c t i o n s , w h i l e coked sand flows down by g r a v i t y through
a c o n t r o l v a l v e to the burner s e c t i o n of the column where the
coke i s burned to generate heat. The burner i s maintained at a
temperature of g e n e r a l l y between 550° and 650°C. Preheated a i r
i s used to f l u i d i z e the s o l i d s i n the combustion bed and to pro-

24. JAYAKAR E TAL. Thermal Recovery of Oil 363
T a r Sand Products to
Recovery
Pyrolysis
Heat P i p e - tit
Combustion
Heat Recovery
Air .
*Sc
'Spent Sand
Figure 1. University of Utah process

v i d e oxygen f o r combustion. Gaseous products of combustion,

mostly n i t r o g e n and carbon d i o x i d e , then flow upwards to f l u i d i z e
s o l i d s i n the upper bed as noted above.
A number of heat pipes, as r e q u i r e d by the h e a t - t r a n s f e r load,
are placed v e r t i c a l l y i n the f l u i d i z e d - b e d column such that they
extend i n t o the p y r o l y s i s and combustion beds as d e p i c t e d i n
F i g u r e 1. The heat pipes t r a n s f e r excess heat generated i n the
burner to the p y r o l y s i s r e a c t o r , thus m a i n t a i n i n g the r e a c t o r and
burner at proper temperatures.
Hot, spent sand l e a v i n g the burner flows down through a con-
t r o l v a l v e to a heat-recovery s e c t i o n , where process a i r recovers
heat from the spent sand. A d d i t i o n a l energy can be recovered from
the sand by heat exchange to produce steam. A more d e t a i l e d
d e s c r i p t i o n of the process i s given by Seader and Jayakar (26).
The new process r e t a i n s most of the s i m p l i c i t y of d i r e c t -

heated processes. S o l i d s move only downwards by g r a v i t y , the
equipment i s e s s e n t i a l l y a s i n g l e v e s s e l , and there i s no r e c y c l e
of s o l i d s . Most importantly, the h e a t - t r a n s f e r f e a t u r e s u s e d —
heat p i p e s , heat recovery from spent sand to preheat process a i r ,
t r a n s f e r of some heat by combustion gases, and some r a d i a t i v e heat
t r a n s f e r from coke-combustion stage to the p y r o l y s i s r e a c t o r —
permit e f f i c i e n t management of the energy that i s w i t h i n t a r sand
i t s e l f to h e l p achieve high energy e f f i c i e n c y . The heat pipes
e f f e c t i v e l y l i n k the p y r o l y s i s r e a c t o r and the coke-combustion
stage thermally without n e c e s s a r i l y imposing any other c o n s t r a i n t s
on the process such as flow p a t t e r n s , r e a c t o r c o n f i g u r a t i o n , or
dimensions of the column (except f o r the volume of heat pipes,
which i s a s m a l l f r a c t i o n of bed volumes).
The b a s i c process as o u t l i n e d above i s very f l e x i b l e , and
m o d i f i c a t i o n s and v a r i a t i o n s can be e a s i l y i n c o r p o r a t e d i n t o i t to
f u r t h e r improve the o v e r a l l e f f i c i e n c y and/or to make i t more
s u i t a b l e f o r s p e c i f i c types of feeds. Thus, e x t e r n a l f u e l , r e c y c l e
gas, or l i q u i d f u e l s can be e a s i l y introduced i n t o the burner i n
the case of l e a n t a r sands. By p r o v i d i n g f o r a purge gas stream
o f f the top of the combustion bed, one can adjust the flow r a t e
of f l u i d i z i n g gas to the p y r o l y s i s bed. I f desired, after
recovery, gas produced i n the p y r o l y s i s bed can be r e c y c l e d back
to that bed and used i n s t e a d of combustion gases to f l u i d i z e i t .
This i s very important f o r l e a n t a r sands which would otherwise
have very low product c o n c e n t r a t i o n i n the combined e x i t gas
stream, making product recovery d i f f i c u l t .
Laboratory T e s t i n g of New Process
A l a b o r a t o r y apparatus was used to demonstrate the new t h e r -

mal process. I t c o n s i s t e d of a 10-foot-high by nominal 2-inch
diameter, two-staged, f l u i d i z e d - b e d column, a screw feeder f o r
feeding t a r sand, a hot cyclone and f i l t e r system f o r s e p a r a t i o n
of f i n e s from the products, and a product-recovery s e c t i o n c o n s i s t -
ing of condensers, phase s e p a r a t o r s , cyclones, and an e l e c t r o -

24. JAYAKAR E TAL. Thermal Recovery of Oil 365
s t a t i c p r e c i p i t a t o r . A s i n g l e 0.75-inch-diameter by 7-foot-long
heat pipe extended i n t o the p y r o l y s i s and coke-combustion beds.
The apparatus was completely i n s u l a t e d and instrumented with
thermocouples, pressure taps, flow meters, and sampling taps.
E l e c t r i c a l heaters and a propane burner were used to provide
heat during s t a r t u p c o n d i t i o n s . The equipment was designed
to handle a nominal feed r a t e of 5 l b / h r of t a r sands c o n t a i n i n g
up to 14 weight percent bitumen. F u r t h e r d e t a i l s of the apparatus
are given by Jayakar (27).
Several problems i n s o l i d s handling were encountered i n

operating the l a b o r a t o r y apparatus. O r i g i n a l l y s o l i d s were trans-
f e r r e d from the p y r o l y s i s bed to the combustion bed by means of a
weir and d i p l e g . Because gas tended to flow up through the d i p

l e g , t h i s system was abandoned i n favor of a simple s o l i d s down-
comer with a s p e c i a l l y designed s o l i d s f l o w - c o n t r o l v a l v e .
Although t h i s v a l v e permitted proper o p e r a t i o n of the bed, i t was
a r e c u r r e n t source of o p e r a t i n g d i f f i c u l t y as i t tended to s t i c k
a f t e r a few runs and had to be dismantled and cleaned every two
to f o u r runs. Flow of s o l i d s from the combustion bed was con-
t r o l l e d by a s i m i l a r v a l v e , which presented no o p e r a t i n g problems.
Tar-sand feed m a t e r i a l s were ground to p a r t i c l e s or p i e c e s
no l a r g e r than about 1/4-inch i n s i z e . M a t e r i a l s tending to be
s t i c k y were dusted with f i n e s o r c o a l dust p r i o r to f e e d i n g . The
screw feeder d i d not plug as long as i t was kept a t a near-
ambient temperature. Run d u r a t i o n s were t y p i c a l l y one hour a f t e r
spending s e v e r a l hours to reach e s s e n t i a l l y s t e a d y - s t a t e
conditions.
The experimental work was d i v i d e d i n t o three p a r t s : f l u i d i z a -
t i o n s t u d i e s a t elevated temperatures, p r o c e s s i n g of t a r sands i n
the p y r o l y s i s s e c t i o n without use of the heat pipe, and o p e r a t i o n
of the complete heat-piped apparatus. Only t y p i c a l r e s u l t s o f
some of the l a t t e r t e s t s are reported here.
A t o t a l of 75 runs was made under thermal p r o c e s s i n g c o n d i -
t i o n s a t near-ambient pressure with t a r sands from three d i f f e r -
ent d e p o s i t s : Tar Sand T r i a n g l e , Sunnyside, and Asphalt Ridge.
Data from r e p r e s e n t a t i v e runs f o r feed m a t e r i a l s from each o f the
three d e p o s i t s a r e given i n Table I I . A complete accounting of
a l l the bitumen i n the feed m a t e r i a l was g e n e r a l l y not achieved
mainly because of d i f f i c u l t i e s i n removing o i l product from the
product recovery equipment. Thus, values reported f o r o i l y i e l d
are b e l i e v e d to be low. Based on the best runs, i t i s estimated
that f o r Sunnyside and Asphalt Ridge m a t e r i a l s , a t y p i c a l y i e l d
s t r u c t u r e f o r near-optimal operating conditions would be: 70 wt%
o i l , 10 wt% gas, and 20 wt% coke.
Conclusions
1. The b a s i c concept of a thermal process using p y r o l y s i s

and combustion stages coupled by heat pipes i s workable and
e l i m i n a t e s the need to r e c y c l e l a r g e amounts o f sand.

Table I . C l a s s i f i c a t i o n o f and References f o r Thermal Recovery

Processes
D i r e c t Heated I n d i r e c t Heated
Moving-bed p y r o l y s i s Cheney et a l . (9) Bennett (12)

and combustion Dannanberg and Berg (13)
Matzick (10) F i t c h (14)
Saunders (11)
Fluidized-bed pyrolysis G i f f o r d (15) G i s h l e r and

and combustion Peck et a l . (16) Peterson (17)
Nathan e t a l . (18)
R o e t h e l i (19)
Murphree (20)
Alleman (21)
Fluidized-bed pyrolysis Donnelly et a l . (22) No examples

and moving-bed combus- known
tion
Moving-bed p y r o l y s i s No examples known Rambler (23)

f l u i d i z e d - b e d combus-
tion
Table I I . Laboratory R e s u l t s f o r Processing of Utah

Tar Sands
Deposit
Tar Sand T r i a n g l e Asphalt Ridge Sunnyside
Run No. 58 67 74
Bitumen Content of 4.70
Feed, wt% 11.67 10.56
Tar-Sand Feed Rate, 3.85
lb/hr 3.90 4.41
P y r o l y s i s Bed Temper- 475
ature, °C 482 449
Combustion Bed Temp- 603
erature, °C 649 604
O i l Y i e l d , wt% 49.5 52.7 45.4
Gas Y i e l d , wt% 20.6 15.7 6.2
Coke Y i e l d , wt% 22.0 7.8 17.2
T o t a l Y i e l d , wt% 92.1 76.2 68.8
API G r a v i t y of O i l ,
20 °C 13.1 15.2 18.2
V i s c o s i t y of O i l ,
cps, 25°C 142 102 291

24. JAYAKAR ET AL. Thermal Recovery of Oil 367
2. Tar sands c o n t a i n i n g as low as 8 percent bitumen can be

thermally processed without e x t e r n a l energy input to get s a t i s -
f a c t o r y y i e l d s of o i l . Tar sand with even lower bitumen content
can be processed with good o i l y i e l d i f a p o r t i o n o f the gas or
o i l products or some cheaper e x t e r n a l f u e l , such as c o a l , can
be added to the combustion stage to provide energy.
3. M o d i f i c a t i o n s of the process, such as i n t r o d u c i n g recycle
of gas and o i l , a l l o w i n g f o r purge o f some combustion gas, e t c . ,
can improve the energy e f f i c i e n c y o f the process and the y i e l d s
of o i l and gas.
4. The process developed during the course of t h i s work i s
simple, d i r e c t , and e f f i c i e n t . I t i s capable of wide a p p l i c a t i o n
to processing o f t a r sands i n Utah, Canada, and perhaps other
d e p o s i t s . Moreover, the concept of using heat pipes i s o f even
broader a p p l i c a b i l i t y i n the process i n d u s t r i e s i n general and

i n e n e r g y - r e l a t e d i n d u s t r i e s i n p a r t i c u l a r . For example, the
b a s i c processing concepts i n v e s t i g a t e d here may have p o t e n t i a l f o r
a p p l i c a t i o n i n the processing of o i l shale and c o a l .
ABSTRACT
Tar sands from the Asphalt Ridge, Sunnyside, and Tar Sand
Triangle deposits in Utah were processed in a small-scale, two-
-stagefluidized reactor system operating under continuous, steady-
-flow conditions. The oil products obtained were analyzed for
viscosity, refractive index, density, sulfur content, distillation
yield, and proton nmr spectra.
In the first stage of the reactor, mined and suitably sized
tar sand is pyrolyzed at temperatures of 450 to 500°C in an inert
atmosphere to crack and volatilize most of the contained bitumen,
which is then condensed and collected to give a synthetic crude
oil. In the second stage, coke formed as a by-product in the
first stage is combined with air at temperatures of 550 to 650°C.
The energy released during combustion in the second stage is
transferred by a heat pipe to the first stage where the heat is
utilized to provide for preheat and heat of pyrolysis of tar-sand
feeds. Gaseous combustion products from the second stage, contain-
ing very little oxygen, are used to fluidize the pyrolysis bed.
The process permits recovery of oil from tar sands with high
energy efficiency in a once-through operation with respect to sand.
References
1. Camp, F. W., "Tar Sands" in Kirk-Othmer Encyclopedia of
Chemical Technology, 2nd Edition, Vol. 19, John Wiley and
Sons, New York, pp. 682-732 (1969).
2. Ritzma, H. R., AIChE Symposium Series No. 155, 72, 47 (197
3. Oblad, A. G., J. D. Seader, J. D. Miller, and J. W. Bunger,
AIChE Symposium Series No. 155, 72, 69 (1976).

4. Bunger, J. W., K. P. Thomas, S. M. Dorrance, Fuel 58, 183

(1979).
5. Spulveda, J. E., and J. D. Miller, Mining Engineering, 30,
1311 (1978).
6. Misra, M., and J. D. Miller, Mining Engineering, 32, 302
(1980).
7. Gustafson, R. E., "Shale Oil" in Kirk-Othmer Encyclopedia of
Chemical Technology, 2nd Edition, Vol. 18, John Wiley and
Sons, New York, pp 1-20 (1969).
8. Moore, R. G., D. W. Bennion, J. K. Donnelly, "Anhydrous
Extraction of Hydrocarbons from Tar Sands," Paper presented
at local ISA Meeting, Calgary Section, April 1975.
9. Cheney, P. E., R. W. Ince, and C. M. Mason, U. S. Patent
3,487,002, December 30, 1969.
10. Dannanberg, R. O., and A. Matzick, "Bureau of Mines Gas-Com-

bustion Retort for Oil Shale," U. S. Bureau of Mines Report
of Investigation 5545 (1960).
11. Saunders, F. J., U. S. Patent 3,130,132, April 21, 1964.
12. Bennett, J. D., U. S. Patent 3,623,972, November 1971.
13. Berg, C. H. O., U. S. Patent 3,905,595, September 22, 1959.
14. Fitch, C. M., U. S. Patent 3,267,019, August 16, 1966.
15. Gifford, P. H., II. U. S. Patent 4,094,767, June 1978.
16. Peck, E. B., E. Tomkins, and D. G. Tomkins, U. S. Patent
2,471,119, May 1949.
17. Gishler, P. E., and W. S. Peterson, Treatment of Bituminous
Sand. Canadian Patent 530,920, September 25, 1956.
18. Nathan, M. F., G. T. Skaperdas and G. C. Grubb, U. S. Patent
3,320,152, May 16, 1967.
19. Roetheli, B. E., U. S. Patent 2,579,398, December 18, 1951.
20. Murphree, E. V., U. S. Patent 2,980,617, October 13, 1959.
21. Alleman, C. E., U.S. Patent 2,647,077, July 28, 1953.
22. Donnelly, J. K., R. G. Moore, D. W. Bennion, and A. E.
Trenkwalkder, "A Fluidized Bed Retort for Oil Sands," Paper
presented at the AIChE Meeting, Florida, 1978.
23. Rammler, A. W., "The Production of Synthetic Crude Oil from
Oil Sand by Application of the Lurgi-Ruhrgas Process,"
Canadian Journal of Chemical Engineering, 48 (October 1970):
552-560.
24. Peterson, W. S., and P. E. Gishler, "A Small Fluidized Solids
Pilot Plant for the Direct Distillation of Oil from Alberta
Bituminous Sands," Canadian Journal of Research, 28 (January
1950): 62-70.
25. Peterson, W. S., and P. E. Gishler, "Oil from Alberta
Bituminous Sand," Petroleum Engineer, 23 (April 1951): 553-
561.
26. Seader, J. D., and K. M. Jayakar, Process and Apparatus to
Produce Synthetic Crude Oil from Tar Sands, U. S. Patent
4,160,720, July 10, 1979.
27. Jayakar, K. M., "Thermal Recovery of Oil from Tar Sands,"
Ph.D. Thesis in Chemical Engineering, University of Utah (1979).
28. Dunn, P., and D. Reay,HeatPipes,2nd., Pergamon Press, 1978.

25
Hydropyrolysis: The Potential for Primary
Upgrading of Tar Sand Bitumen
J. W. BUNGER, D. E. COGSWELL, R. E. WOOD, and A. G. OBLAD
Department of Mining and Fuels Engineering, 320 WBB, University of Utah,
Salt Lake City, UT 84112
Upgrading of high molecular weight, residual materials is

becoming increasingly important as a result of decreasing availa-
bility of lighter feedstocks. Conversion processes for residual
materials must contend with high heteroatom content, high molecu-
lar weight (low volatility), high aromaticity and high metals
content not encountered to the same degree in lighter feedstocks.
These characteristics result in higher process costs and typically
lower conversion and yield of desired products. But as production
recovery and processing costs rise, yield and conversion effi-
ciency become increasingly important. As a result, conventional
techniques for primary conversion of residual materials such as
tar sand bitumen, e.g. coking, may prove economically unacceptable.
A possible alternative for the primary conversion of residual
material is hydropyrolysis. Hydropyrolysis (HP) is a process for
thermal cracking in the presence of hydrogen. This process has
been shown to dramatically improve the yields of liquid and
gaseous products compared to coking (1,2,3,4,5). Hydropyrolysis
does not require the introduction of heterogeneous catalysts but
requires elevated pressures. Through model compound work (5) and
characterization (6) and processing (7) of high molecular weight
tar sand bitumen, an understanding of the chemistry of this
reaction is beginning to emerge. This paper reports our latest
results and discusses the chemical changes effected by hydro-
pyrolysis. The implication of the possible reactions to the
suitability of various feedstocks for processing by hydropyrolysis
is also discussed.
Experimental
Feedstock Source. Three feedstocks were used i n t h i s study.

A l l were derived from U i n t a Basin, Utah Tar Sand d e p o s i t s . A
Sunnyside bitumen was solvent extracted by procedures p r e v i o u s l y
reported (6) from a f r e s h l y mined sample obtained from the o l d
Asphalt Quarry northeast of Sunnyside, Utah. An Asphalt Ridge
bitumen was extracted s i m i l a r l y from a sample f r e s h l y mined from
0097-6156/8l/0163-0369$05.00/0

the U i n t a County Quarry southwest of V e r n a l , Utah. The TS-IIC

o i l was used as r e c e i v e d from the U.S. Department of Energy,
Laramie Energy Technology Center (LETC). The TS-IIC o i l i s
r e p r e s e n t a t i v e of the o i l produced during an echoing i n - s i t u
combustion o i l recovery p r o j e c t conducted at Northwest Asphalt
Ridge by the LETC l a b o r a t o r i e s (8).
Elemental A n a l y s i s and P h y s i c a l P r o p e r t i e s . Elemental

a n a l y s i s was accomplished by conventional m i c r o a n a l y t i c a l tech-
niques i n a commercial t e s t i n g l a b o r a t o r y . D e n s i t i e s were
measured on a Mettler/Paar d i g i t a l d e n s i t y meter, model D.M. 40.
Number average molecular weights were determined by VPO i n
benzene. Simulated d i s t i l l a t i o n was accomplished using a 1/4" by
18" column of 3% d e x s i l 300 on chromosorb W, programmed from -30°
to 350°C at 10°/minute with a 4 minute hold at 350°C. The

detector was a flame i o n i z a t i o n detector maintained at 400°C.
The percent n o n d i s t i l l a b l e m a t e r i a l was determined by using as an
i n t e r n a l standard, an equal volume^mixture of C^ to C ^ n - a l k y l -
benzenes (See a l s o reference 9). C-NMR spectra data were
obtained as reported i n reference (_3) .
Hydropyrolysis Process. Two h y d r o p y r o l y s i s r e a c t o r s were

used i n t h i s study. The Sunnyside and Asphalt Ridge bitumen were
processed i n a r e a c t o r c o n s i s t i n g of a c o i l e d s t a i n l e s s s t e e l tube
3/16" i . d . x 236" long. T h i s r e a c t o r has been p r e v i o u s l y
described by Ramakrishnan (1). The TS-IIC o i l was processed i n a
r e a c t o r o r i g i n a l l y developed f o r short residence time c o a l l i q u e -
faction. T h i s r e a c t o r a l s o c o n s i s t s of c o i l e d s t a i n l e s s s t e e l
tubes 3/16" i . d . The length of t h i s tube system can be v a r i e d
from 20 to 120 f e e t , and has been p r e v i o u s l y described by Wood,
et a l . (10). The length of the r e a c t o r f o r runs reported i n t h i s
paper was 100 f e e t . Average residence times were c a l c u l a t e d from
the volumetric flow r a t e s and the r e a c t o r volume at process c o n d i -
t i o n s . The r e a c t i o n mixture, which i s predominantly H^, was
assumed f o r purposes of t h i s c a l c u l a t i o n to behave as an i d e a l
gas. The r e a c t o r s were p r e - s u l f i d e d with H^S to i n h i b i t c a t a l y t i c
r e a c t i o n s from w a l l s u r f a c e s .
Results
The elemental a n a l y s i s and p h y s i c a l p r o p e r t i e s f o r the U i n t a

Basin d e r i v e d feedstocks are given i n Table I. The elemental
analyses r e v e a l compositions t y p i c a l of U i n t a Basin bitumens (11)
i n that H/C r a t i o s f a l l between 1.53 and 1.66, n i t r o g e n contents
are a p p r e c i a b l e (~1%) and s u l f u r content i s low (<0.5%). The
p h y s i c a l property data r e v e a l s i g n i f i c a n t d i f f e r e n c e s between the
three samples i n that the Sunnyside bitumen e x h i b i t s the highest
molecular weight and, hence, the h i g h e s t v i s c o s i t y and lowest
volatility. The Asphalt Ridge TS-IIC o i l e x h i b i t s the lowest
molecular weight with corresponding higher v o l a t i l i t y and lower

25. BUNGER ET AL. Hydropyrolysis 371
TABLE I
Elemental A n a l y s i s and P h y s i c a l P r o p e r t i e s of Feedstocks
Asphalt
Sunnyside Ridge Asphalt
(virgin (virgin Ridge
Property bitumen) bitumen) (TS-IIC o:
Carbon (wt.%) 86.3 86.2 86.7

Hydrogen 11.1 11.3 11.6
Nitrogen 0.8 1.1 0.7
Sulfur 0.35 0.4 0.5
Oxygen 1.4 0.9 <0.5
H/C atomic r a t i o 1.53 1.56 1.59
S p e c i f i c g r a v i t y 20/20 1.003 0.981 0.959

API g r a v i t y 9.6 12.7 16
Average M.W. (VPO benzene) 778 713 410
Conradson Carbon Residue 14.1 9.1 6.8
% D i s t i l l a b l e below 530°C 34 44 69
V i s c o s i t y kP 77°F, 200 sec 1500* 69.3* 3.9
*Shear = .05 sec
v i s c o s i t y and d e n s i t y . An i n t e r e s t i n g property of the TS-IIC o i l

i s the a p p r e c i a b l e carbon r e s i d u e e x h i b i t e d c o n s i d e r i n g t h i s o i l
has been thermally produced i n - s i t u . A greater p o r t i o n of the
h e a v i e s t and most carbonaceous m a t e r i a l might have been expected
to remain i n the r e s e r v o i r .
The three feedstocks were processed by h y d r o p y r o l y s i s at
s e l e c t e d process c o n d i t i o n s . Previous r e s u l t s (1,7) have shown
that gas to l i q u i d r a t i o s i n c r e a s e s e n s i t i v e l y with i n c r e a s i n g
temperature. T h i s e f f e c t can be o f f s e t somewhat by decreasing
the residence time. A v a r i a t i o n i n pressure does not have a major
e f f e c t on product y i e l d s or gross p r o p e r t i e s , but pressures above
about 1200 p s i g H^ are r e q u i r e d to i n h i b i t coke formation.
Representative r e s u l t s f o r h y d r o p y r o l y s i s of the study
feedstocks are given i n Table I I . The Sunnyside bitumen was pro-
cessed at more moderate temperatures and longer residence times
as a r e s u l t of a s i g n i f i c a n t propensity to coke at 525°C. The
e x t r a o r d i n a r i l y high v e l o c i t i e s of gas used were r e q u i r e d to
prevent coking i n the c o i l e d tube r e a c t o r ; however, more recent
r e s u l t s with other r e a c t o r c o n f i g u r a t i o n s i n d i c a t e that a two-
order of magnitude improvement on the r e c y c l e gas to feed r a t i o s
can be accomplished without s i g n i f i c a n t l y a f f e c t i n g the y i e l d s
and without major coking problems. Run times f o r r e s u l t s shown i n
Table I I were f o r one to two hours i n l e n g t h .
R e s u l t s given i n Table I I show v i r t u a l l y 100% conversion of
feedstocks to l i q u i d s and gases. R e s i d u a l m a t e r i a l shown f o r

TABLE I I
Representative R e s u l t s of Hydropyrolysis
Process Conditions
Asphalt

bitumen) bitumen) (TS-IIC o i :
Temperature °C 500 525 525

Pressure (psig) 1800 1500 1800
Average residence time (sec ) 30 18 5
Space v e l o c i t y (LHSV) 1 1 1
Gas hourly space v e l o c i t y
( r e c y c l e and makeup) 1000 1000 - 1000
(approximate s c f / b b l ) 7 x 10^ 6 x 10^ 7 x 10^
Yields
Weight % gases 27.3 27.3 12.8

liquid 73.9 73.7 85.6
residue * * 2.1
NH 0.38 0.61 0.1
H S 0.13 0.21 0.3
H^O 1.15 0.79 negligible
Total yield 102.9 102.6 100.9
Hydrogen consumption
(weight %) 2.9 2.6 0.9
(scf/bbl) 1800 1600 600
* R e s i d u a l m a t e r i a l f o r these runs were counted as l i q u i d s .

25. BUNGER E T A L . Hydropyrolysis 373
TS-IIC represents the m a t e r i a l r e t a i n e d i n a hot (350-400°C) catch

tank and i s b e l i e v e d to be i n d i c a t i v e of the amount of m a t e r i a l
which i s not v o l a t i l i z e d during r e a c t i o n . E x t e n s i v e experimenta-
t i o n with h y d r o p y r o l y s i s has shown that a c t u a l coke p r o d u c t i o n of
much l e s s than 1% i s achieved. D e t a i l s of minor coke buildup over
extended runs have not yet been determined. The optimum c o n d i -
t i o n s to o b t a i n the d e s i r e d y i e l d s and to prevent e x t r a o r d i n a r y
coke formation w i l l depend upon the feedstock p r o p e r t i e s and
composition. Q u a n t i t a t i v e r e l a t i o n s h i p s between feedstock
composition and optimum process c o n d i t i o n s have not yet been
conducted.
The amount of ammonia, hydrogen s u l f i d e and water shown i n
Table I I i s i n f e r r e d from the m a t e r i a l balance on the r e s p e c t i v e
heteroatoms; d i r e c t a n a l y s i s of these compounds was not conducted.
The values shown i n Table I I , along with the elemental a n a l y s i s

of condensable products and the gas a n a l y s i s , were used to c a l c u -
l a t e the hydrogen consumption. Hydrogen consumption i s not under-
estimated by the method of c a l c u l a t i o n (7) which f i r s t accounts
f o r a l l of the carbon and heteroatoms fed and then sums the
hydrogen content of the v a r i o u s components. The r e s u l t s of t h i s
study and those p r e v i o u s l y reported (7) i n d i c a t e that hydrogen
consumption v a r i e s i n rough proportions to the non-condensable gas
yield. C a l c u l a t i o n s of hydrogen requirements r e v e a l that a
h y d r o p y r o l y s i s p l a n t could operate i n hydrogen balance by steam-
reforming the methane produced.
The C--C^ gas a n a l y s i s i s given i n Table I I I along w i t h a
coker gas from Asphalt Ridge bitumen ( c a l c u l a t e d from r e f e r e n c e 7)
f o r comparison. While the t o t a l amount of gas produced i n hydro-
p y r o l y s i s i s s e v e r a l times as high as with coking (-5 weight
percent gas i s produced i n coking), i t i s apparent that hydropyro-
l y s i s reduces o l e f i n formation r e l a t i v e to p a r a f f i n formation and
that C^'s and C^'s are h i g h l y favored r e l a t i v e to methane. The
rather e r r a t i c r e s u l t s of o l e f i n s to the p a r a f f i n s r a t i o and C,.
production f o r the h y d r o p y r o l y s i s runs suggest the p o s s i b i l i t y of
v a r i a b l e w a l l - e f f e c t s ( c a t a l y t i c ) or s i g n i f i c a n t d i f f e r e n c e s i n
molecular s t r u c t u r e of one feed to another. A l s o , v a r i a t i o n s i n
r e a c t o r c o n t r o l (±6°C, ±100 p s i g , ±20% of r e s i d e n c e time) may
a l s o i n f l u e n c e these r e s u l t s .
C h a r a c t e r i s t i c s of h y d r o p y r o l y s i s l i q u i d products are given
i n Table IV. Only modest improvement has been made i n the H/C
r a t i o s and heteroatom removal, but notable improvements have been
made i n p h y s i c a l p r o p e r t i e s compared to the feed m a t e r i a l .
Average molecular weights of the v i r g i n bitumens have been reduced
i n h a l f and v i s c o s i t i e s have been reduced by about 4 to 5 orders
of magnitude. The r e d u c t i o n i n molecular weight i s s i g n i f i c a n t
i n that the products w i l l be much more amenable to c a t a l y t i c
hydroprocessing than the o r i g i n a l m a t e r i a l s . The low API g r a v i t y
and high r e s i d u e content of the Sunnyside products suggest a
h i g h l y condensed m a t e r i a l , probably unconverted from the o r i g i n a l
bitumen.

TABLE I I I
Gas A n a l y s i s
Coke
\7)
Hydropyrolysis Gas Gas
Asphalt Asphalt
Sunnyside Ridge Asphalt Ridge
(virgin (virgin Ridge (virgin
Compound bitumen) bitumen) (TS-IIC o i l ) bitumen)
weight percent of 0^-C^ gases
Methane 29.7 25.9 27.8 45.4
Ethane 12.8 17.2 15.8 13.8

Ethylene 2.9 5.1 2.9 6.8
Propane 14.6 22.0 18.7 14.2

Propylene 13.8 5.1 6.7 13.5
Butanes 9.8 16.9 14.2 3.3

Butenes 5.9 5.0 1.6 2.4
f
C 5 s 10.5 2.8 12.3 0.6
Total 100.0 100.0 100.0 100.0

25. BUNGER E T AL. Hydropyrolysis 375
TABLE IV
C h a r a c t e r i s t i c s of H y d r o p y r o l y s i s L i q u i d Products
Asphalt
bitumen) bitumen) (TS-IIC o:
Product C h a r a c t e r i s t i c s —
Carbon (weight percent) 86.9 86.8 86.2

Hydrogen 11.4 11.4 11.6
Nitrogen 0.7 0.8 0.7
Sulfur 0.3 0.3 0.2
Oxygen 0.5 0.3 1.2
H/C atomic 1.56 1.56 1.61
S p e c i f i c g r a v i t y 20/20 0.967 0.903 0.920

API g r a v i t y 14.8 25.2 22.3
Average MW (VPO) 352 321 312
% d i s t i l l a b l e below 530°C 68 85 97
V i s c o s i t y 77°J cp, 7000 8.1 246
(shear sec ) * (77) (230) (6)
R e f r a c t i v e index too dark 1.52 1.503
*A11 products appear to e x h i b i t Newtonian behavior i n the shear

ranges s t u d i e d .

^^The o r i g i n a l Sunnyside bitumen and the products were examined

by C-NMR spectroscopy and found to possess a s a t u r a t e s to aroma-
t i c carbon r a t i o of 4.3 and 2.3, r e s p e c t i v e l y . While these r a t i o s
i n d i c a t e a s i g n i f i c a n t l y more aromatic product has been formed,
the t o t a l aromatic carbon has increased only s l i g h t l y , from 19%
i n the o r i g i n a l bitumen to 22% i n the o v e r a l l products, when gases
are taken i n t o account. T h i s r e s u l t suggests that the molecular
weight r e d u c t i o n i s o c c u r r i n g through c r a c k i n g of s a t u r a t e s and
a l k y l s u b s t i t u e n t s , that the remaining l i q u i d s are r e l a t i v e l y more
condensed, but that dehydrogenation to form aromatics has a l s o
been i n h i b i t e d .
To f u r t h e r compare HP products with more c o n v e n t i o n a l
m a t e r i a l s , the smoothed b o i l i n g point d i s t r i b u t i o n f o r the Asphalt
Ridge bitumen HP product was p l o t t e d a g a i n s t a s i m i l a r curve f o r
the A s p h a l t Ridge coker d i s t i l l a t e and a Wilmington, C a l i f o r n i a

crude o i l . R e s u l t s given i n F i g u r e 1 show that HP products are
q u i t e s i m i l a r i n b o i l i n g p o i n t d i s t r i b u t i o n to a v i r g i n heavy
crude o i l . By comparison, the coker d i s t i l l a t e possesses a
r e l a t i v e l y high c o n c e n t r a t i o n of m a t e r i a l i n the heavy and vacuum
gas o i l r e g i o n . The Wilmington, C a l i f o r n i a crude o i l was chosen
f o r comparison because t h i s crude i s being c o n v e n t i o n a l l y r e f i n e d
and has been shown to resemble U i n t a Basin t a r sand bitumen i n
terms of the heteroatom and hydrocarbon compound types present (6).
A f u r t h e r d i f f e r e n c e between HP products and coker d i s t i l l a t e
i s noted i n the o l e f i n s content. I n f r a r e d s p e c t r a l data taken
neat on these twcj> products r e v e a l o l e f i n bonds at 1638, 988, 960,
904, and 880 cm about 1.5 to 2.0 times as i n t e n s e f o r coker
d i s t i l l a t e compared to HP condensables. Based on a n a l y s i s of
gases produced and on model compound work (5) which both show
h y d r o p y r o l y s i s i n h i b i t s o l e f i n production, i t i s a n t i c i p a t e d that
h y d r o p y r o l y s i s products w i l l be more s t a b l e f o r storage, t r a n s p o r -
t a t i o n , or d i s t i l l a t i o n than coker d i s t i l l a t e s from the same
source.
Discussion
The r e a c t i o n s taking p l a c e during h y d r o p y r o l y s i s are probably

dominated by f r e e r a d i c a l chemistry. C a t a l y t i c e f f e c t s from
r e a c t o r components or t r a c e minerals found i n the feedstocks
cannot, however, be discounted. Cracking r e a c t i o n s are probably
i n i t i a t e d through thermally induced unimolecular bond s c i s s i o n .
The subsequent r e a c t i o n s i n v o l v i n g the f r e e r a d i c a l s are those
which d i s t i n g u i s h h y d r o p y r o l y s i s from thermal r e a c t i o n s i n the
absence of high hydrogen pressure. Shabtai, et a l . (5) have
p o s t u l a t e d the r e a c t i o n
R- + H 2 • RH + H-
as a s i g n i f i c a n t r e a c t i o n i n the h y d r o p y r o l y s i s of n-decane. A
very modest a c t i v a t i o n energy of 14-15 K cal/mol i s estimated f o r

25. BUNGER E T AL. Hydropyrolysis 377
Ll • w
I I I I | | | | I 1 1
- 50 100 150 200 250 300 350 400 450 500 550
NOMINAL BOILING POINT °C
Figure 1. Distillation curves for selected tar sand products and Wilmington crude
oil: Asphalt Ridge coker distillate (97% distillable, 27° API) ( ); Asphalt
Ridge hydropyrolysis condensables (85% distillable, 25° API) ( ); Wilming-
ton, CA crude oil (65% distillable, 20° API) (- • -).

t h i s r e a c t i o n on the b a s i s of thermochemical data (5,12,13).

Considering the dominant p a r t i a l pressure of hydrogen and
favorable a c t i v a t i o n energy, i t i s h i g h l y probable that many f r e e
r a d i c a l s present undergo the above r e a c t i o n during h y d r o p y r o l y s i s .
T h i s r e a c t i o n has c o n s i d e r a b l e s i g n i f i c a n c e . F i r s t , f r e e r a d i c a l s
present have an e a r l y opportunity to become s a t u r a t e d before other
bimolecular r e a c t i o n s can occur. Such processes as p o l y m e r i z a t i o n
or condensation which u l t i m a t e l y lead to high molecular weight
species or coke are i n h i b i t e d . The r e s u l t s of both model compound
work (5) and those presented i n t h i s paper i n d i c a t e that such
r e a c t i o n s are indeed i n h i b i t e d . There i s no evidence from the
model work and l i t t l e i n the work with t a r sand bitumen to i n d i -
cate that any products of a molecular weight higher than the
r e a c t a n t s are formed.
Second, the p r o d u c t i o n of a f r e e hydrogen atom poses some

interesting implications. Should the hydrogen atom a b s t r a c t a
hydrogen atom from a saturated carbon, the r e s u l t a n t f r e e r a d i c a l
may 1) undergo 3 - e l i m i n a t i o n to produce another hydrogen atom and
an o l e f i n or 2) undergo B - s c i s s i o n to crack the molecule forming
an o l e f i n p l u s a hydrocarbon f r e e r a d i c a l . Should the hydrogen
atom a t t a c k an unsaturated carbon such as our aromatic r i n g , a
d i e n y l r a d i c a l i s formed which 1) may r a p i d l y undergo r i n g opening
w i t h subsequent d e s t r u c t i o n of the aromatic r i n g or 2) become
saturated by a hydrogen from H^, thus reducing the resonance
s t a b i l i z a t i o n of the r i n g making i t s u s c e p t i b l e to f u r t h e r r e a c -
t i o n . The p o s s i b i l i t y that t h i s l a t t e r r e a c t i o n i s o c c u r r i n g i s
supported, however weakly, by an i n c r e a s e i n monoaromatics at the
apparent expense of polyaromatics. Previous work (7) has shown
that a monoaromatic/polyaromatic r a t i o of 0.3 i s observed f o r
coker products (assuming coke as polyaromatics) but the r a t i o i s
0.5 f o r h y d r o p y r o l y s i s products d e r i v e d from the same feedstock.
There are, admittedly, molecular weight f a c t o r s and dehydrogena-
t i o n r e a c t i o n s i n coking which could a l s o i n f l u e n c e t h i s r a t i o .
As a consequence of the reduced p a r t i a l pressure of hydro-
carbons, bimolecular r e a c t i o n s which r e s u l t i n hydrogen t r a n s f e r
are i n h i b i t e d . Such r e a c t i o n s which are h i g h l y s i g n i f i c a n t i n
l i q u i d phase thermal r e a c t i o n s such as coking r e s u l t i n appre-
c i a b l e dehydrogenation of naphthenic r i n g s with a corresponding
i n c r e a s e i n aromatics content. R e s u l t s from h y d r o p y r o l y s i s i n d i -
cate that dehydrogenation of naphthenes occurs to some extent but
not n e a r l y as much as with coking where the percentage of aromatic
carbon i n c r e a s e s from l e s s than 20% i n the bitumen to over 30% i n
the t o t a l products (assuming the coke contains p r i n c i p a l l y aroma-
t i c carbon) (7). The i n h i b i t i o n of hydrogen t r a n s f e r r e a c t i o n s
may be e s p e c i a l l y important f o r conversion of very high molecular
weight, naphthenic feedstocks such as t a r sand bitumen.
The e f f e c t s of hydrogen on the thermal c r a c k i n g of bitumen
are obvious i n the r e s u l t s . Most d r a m a t i c a l l y , high carbon
r e s i d u e m a t e r i a l i s converted i n v i r t u a l l y 100% y i e l d s to l i q u i d
and gaseous products. The e f f e c t i s most pronounced f o r the

25. BUNGER ET AL. Hydropyrolysis 379
v i r g i n bitumens; however, the e f f e c t f o r TS-IIC o i l i n which

v o l a t i l i t y i s improved from 69% to 97% f o r a modest a d d i t i o n of
600 s c f I ^ / b b l i s a l s o a p p r e c i a b l e . The l i q u i d products formed
from h y d r o p y r o l y s i s more c l o s e l y resemble n a t u r a l l y o c c u r r i n g
crude o i l s i n terms of b o i l i n g p o i n t d i s t r i b u t i o n than do coker
distillates.
U i n t a Basin bitumen e x h i b i t s a high n i t r o g e n content which
p e r s i s t s i n the h y d r o p y r o l y s i s products. T h i s i s expected as the
highest molecular weight s p e c i e s present i n the o r i g i n a l bitumen
where the n i t r o g e n i s concentrated are converted to l i q u i d s . The
high n i t r o g e n content of HP products suggests that c a t a l y t i c
h y d r o t r e a t i n g may be r e q u i r e d p r i o r to use of these l i q u i d s as a
c a t a l y t i c c r a c k i n g feedstock. However, u n l i k e the s i t u a t i o n with
shale o i l which may contain 2% n i t r o g e n and s u b s t a n t i a l q u a n t i t i e s
of p y r o l l i c n i t r o g e n ( a c i d i c ) not commonly found i n crude o i l s ,

the l e v e l of n i t r o g e n i n bitumen products i s not above that which
i s handled by conventional r e f i n e r i e s designed f o r high n i t r o g e n
crudes.
H y d r o p y r o l y s i s p r o c e s s i n g i s probably best s u i t e d f o r those
feedstocks which can best u t i l i z e the i n h i b i t i o n e f f e c t s of hydro-
gen on p o l y m e r i z a t i o n , condensation, and a r o m a t i z a t i o n r e a c t i o n s .
Such feedstocks are high molecular weight naphthenic m a t e r i a l s
which are s u s c e p t i b l e to c r a c k i n g but are e a s i l y converted to
coke by l i q u i d - p h a s e bimolecular r e a c t i o n s .
O v e r a l l , process c o n d i t i o n s f o r h y d r o p y r o l y s i s are no more
severe than p r a c t i c e d now i n c a t a l y t i c hydrogenation processes.
C o n s i d e r i n g the s i g n i f i c a n t l y increased y i e l d s of v a l u a b l e l i q u i d
and gaseous products (compared to coking) and the r a t h e r simple
process c o n f i g u r a t i o n , the economics of h y d r o p y r o l y s i s look
promising.
Summary
H y d r o p y r o l y s i s promises to be a process f o r reducing the

molecular weight of r e s i d u a l m a t e r i a l s without the formation of
coke, without the i n t r o d u c t i o n of heterogeneous c a t a l y s t s and
without an i n o r d i n a t e l y high consumption of hydrogen. Hydropyro-
l y s i s gains i t s a t t r a c t i v e n e s s by t r a d i n g o f f coke production f o r
gas production. T h i s i s accomplished by the presence of hydrogen
which i s thought to i n h i b i t u n d e s i r a b l e bimolecular hydrocarbon-
hydrocarbon r e a c t i o n s . L i q u i d products from h y d r o p y r o l y s i s more
c l o s e l y resemble v i r g i n crude o i l s than do coker d i s t i l l a t e s i n
terms of b o i l i n g p o i n t d i s t r i b u t i o n . H y d r o p y r o l y s i s i s expected
to be most u s e f u l f o r the primary conversion of h i g h molecular
weight, moderate- to low-aromatic feedstocks, e s p e c i a l l y where
high recovery c o s t s place a premium value on improved y i e l d s i n
the conversion process.

Literature Cited
1. Ramakrishnan, R. "Hydropyrolysis of Coal Derived Liquids and
Related Model Compounds," Ph.D. Dissertation, University of
Utah, 1978.
2. Bunger, J.W.; Cogswell, D.E.; Oblad, A.G. Am. Chem. Soc., Div.
Fuel Chem., Prepr. 1978, 23(4), 98-109.
3. Bunger, J.W.; Cogswell, D.E. In "Chemistry of Asphaltenes,"
Adv. Chem. Ser., accepted for publication, 1981.
4. Pruden, B.B.; Denis, J.M. Can. Chem. Proc. 1977, 61, 37-38.
5. Shabtai, J.; Ramakrishnan, R.; Oblad, A.G. "Hydropyrolysis of
Model Compounds," Adv. Chem. Ser. 1979, 183, 297-328.
6. Bunger, J.W.; Thomas, K.P.; Dorrence, S.M. Fuel 1979, 58(3),
183.
7. Bunger, J.W. "Processing Utah Tar Sand Bitumen," Ph.D. Disser-

tation, University of Utah, 1979.
8. Johnson, L.A.; Fahy, L.J.; Romanowski, L.J.; Barbour, R.O.;
Thomas, K.P. "An Echoing In-Situ Combustion Oil Recovery
Project in a Utah Tar Sand," J. Petr. Tech. Feb. 1980,
295-304.
9. Poulson, R.E.; Jensen, H.B.; Duvall, J.J.; Harris, F.L.;
Morandi, J.R. Analysis Instrumentation, Instrument Society
of America, 1972, 10, 193-200.
10. Wood, R.E.; Wiser, W.H. "Coal Liquefaction in Coiled Tube
Reactors," I & EC, Process Res. Dev. 1976, 15, 144.
11. Bunger, J.W. Amer. Chem. Soc., Div. Petr. Chem., Prepr. 1977,
22(2), 716.
12. Bensen, S.W. "Thermochemical Kinetics"; Wiley: New York, 1976.
13. Rosenstock, H.M.; Draxl, K.; Steiner, B.W.; Herron, J.T. J.
Phys. Chem. Ref. Data, 1977, 6 (suppl. 1), I-774-I-783.

INDEX
A AP61 oil shale in argon atmosphere,

rate of H S evolution from a
Acid/clay treating, net fuels produced
2
powdered sample of 61-gal/ton .. 65/

after 230/
Agglomeration and defluidization of Arbitrary Lagrangian-Eulerian (ALE) 14
the SPHER process 178 Argon 63-65
A L E (Arbitrary Lagrangian- atmosphere
Publication Date: September 3, 1981 | doi: 10.1021/bk-1981-0163.ix001
Eulerian) 14 apparatus used to measure the

Alkane by the free-radical mechanism, rate of H S evolution from
2
formation of 85-90 oil shale in 64/

Alkanes, pyrolysis of 80 effect of added pyrite on the H S 2
w-Alkane(s) evolution from Sample

content, shale oil 239 AP22 heated at 4.8°C/min
in Shale-II fuels 242/ in 67/
yield from various residual fractions H S evolution in
2 73
of Paraho shale oil, potential .. 294/ rate of H S evolution from a
2
Alkene/alkane 19-gal/ton Tract C-a

ratios 79 sample of oil shale heated
ratios produced during kerogen at4.8°C/min in 65/
pyrolysis, ethene/ethane rate of H S evolution from a
2
ratio and 85 powdered sample of 61-gal/

production in oil shale retorting, ton AP61 oil shale in 65/
possible mechanism of 79-91 and autogenous atmospheres,
1-Alkene/rt-alkane ratio(s) 51 H S evolved in
2 72
effect of cracking on 50/ Arrhenius plot
in shale oil 226 for C 0 gasification
2 119/
effect of inert sweep gas during for hydroconversion of Cold
retorting on 86/ Lake asphaltenes 335/
ANFO of shale oil cracking data 45/
comparison between calculations for the time and temperature
and field experiments for 17 dependence of [H ][C H ]/ 2 2 4
in oil shale, explosivefieldtests using 17 [C H ] evolved from 22-gal/

2 6
in various diameters, behavior of .... 15/ ton oil shale heated at 1.5°C/
Antrim oil shale, IR spectra of 34/ min under an autogenous
Anvil points (AP) 63, 140 atmosphere 84/
mine, distribution of organic matter Asphaltene(s)
in Mahogany Zone oil shale C-13NMR data for 133-136
lower zone 152/ C-13 NMR spectra of crude and
middle zone 151/ reacted 342/
upper zone 151/ Cold Lake
mine, Rifle, CO, core intervals and aromatic carbon and hydrogen
mineable beds at 141/ contents of 353/
samples of varying grades, rate of Arrhenius plot for hydroconver-
H S evolution from
2 67/ sion of 335/
AP22 heated in argon and 40% steam ESR parameters for 356/
atmospheres, comparison of H S 2 at 400°C and 6 MPa H , thermal 2
evolution from Sample 68/ hydroconversion of 331/

AP61 heated in argon and 40% steam influence of thermal processing
atmosphere, comparison of H S 2 on the properties of 347-357
evolution rate from Sample 69/ reactivity of 327-346
383

Asphaltene(s) (continued) Autoignition temperatures for shale

crude and residuum jet fuels 260
average elemental analyses for .... 352/
differential IR spectrum of 355/ B
molecular-weight distributions Ball loop, properties and circulation
of Cold Lake 354/ rates of candidate materials for outer .. 180/
number average molecular Ball SPHER process
weights for 352/
choice of material for 179
yields from Cold Lake 351/ heater of 176
elemental composition of 131/
separation and recovery in 178-179
Green River
Beneficiation cycles, recovery of
average structural parameters Marathon lease kerogen as a
of 136/, 137/ function of number of 159/
by C-13 NMR, percentage Beneficiation of oil shale
carbon group distributions .. 135/ Dow-Colony 160/
elemental compositions of 131/ steps of, mineral distribution
by H - l NMR, fractional proton
following 162/
distributions of 135/ Green River, by density

H - l NMR data for 133 methods 139-154
H - l NMR spectrum(a) of
Green River, by pelletization ... 155-166
crude and reacted 341/
reasons for 139
from shale bitumen 134/
Bitumen(s) 129
from shale oil retorted at 425 °C 134/
from Dow-Colony oil shale,
from shale oil retorted at 500°C 134/
extraction of 163/
hydroconversion, reaction mecha-
feedstock sources of tar sand 369
nism for 344/
hydropyrolysis primary upgrading
IR spectrum(a) of
of tar sand 369-380
Cold Lake crude 354/
Brittle/ductile transition pressure 16
Cold Lake residuum 355/
samples 131-133
of shale oil 132/ C
isolation of 130 C-13 NMR (see Carbon-13 NMR)
with 200 ppm molybdenum at data for asphaltenes 133-136
400°C and 6 MPa H , hydro- 2 percentage carbon group distribu-
conversion of Cold Lake crude 332/ tions of Green River
from naturally occurring shale asphaltenes by 135/
bitumen and retorted shale shale oil fraction(s)
oils 129-138 analysis of Paraho 287
physical and chemical analysis of .. 130 examination of residual 289/
preparation of 349 spectrum of residual polar 289/
pyrolysis of 349 C 0 gasification
2 118-120
structure, influence of temperature 129 Arrhenius plot for 119/
Autogenous atmosphere rates of 120/
with added pyrite, the increase in and steam of the char 115
H S evolution in
2 68/ CA19 in argon and 40% steam
apparatus used to measure the rate atmospheres, comparison of the
of H S evolution from oil
2 H S evolution from sample
2 70/
shale in 64/ CA36, increase in H S evolution in
2
Arrhenius plot for the time and the presence of steam for sample 69/
temperature dependence of CaO, mixed gasification-no 124/
[H ][C H4]/[C H ] evolved
2 2 2 6 CaO present, mixed gasification- 124/
from 22-gal/ton oil shale Carbon-13 NMR (see C-13 NMR)
heated at 1.5°C/min under .... 84/ Carbon dioxide (see C 0 ) 2
and H S evolved in argon

2 72 CDM (Continuum damage model)
product measurements for oil shale Char
heated at 1.5°C/min under .... 83/ C 0 and steam gasification of
2 115
propene/propane ratios for oil shale consumption, reaction rate expres-
heated at l°C/min under 83/ sion for 115
rate of H S evolution in
2 66 gasification, kinetics of oil shale .115-127

INDEX 385
Chromatogram of basic nitrogen Computer simulation of explosive

fraction from Shale-I jet fuel, fracture of oil shale 13-14
total ion 271/ Continuum damage model (CDM) .... 16
Chromatogram of shale oil from Copper corrosion 262-264
Rock Springs No. 9 54/ strip tests—Shale-II fuels 263/
Coal vs. kerogen 317/ Core intervals and mineable beds at
Coal liquids 319/ Anvil Points Mine, Rifle, CO .... 141/
Coke yield and retorting temperature 97 Cost uncertainties and break-even
Coking costs 219/
on the H / C atomic ratio and nitro- Cracking
gen content of the shale oil, on l-alkene//i-alkane ratios,
effect of shale oil 47/ effect of 50/
oil 46 on the ethene/ethane ratios of the
rate constants for 109/ total evolved gases, as a func-
heavy oil production and 113/ tion of cracking losses and
Cold Lake asphaltenes cracking temperature 88/
aromatic carbon and hydrogen free radical 80
contents of 353/ on the H / C atomic ratio and

crude nitrogen content of the shale
IR spectrum of 354/ oil, effect of 45/
and residuum, molecular-weight on naphthalene/Cn + C i , effect
2
distributions of 354/ of 50/

and residuum, yields from 351/ reaction, kinetics of 107
ESR parameters for 356/ shale oil
hydroconversion of chemistry of 39-60
Arrhenius plot for 335/ conversion limit for 44
crude, with 200-ppm molyb- data, Arrhenius plot of 45/
denum at 400°C and 6 product(s) from 46/
MPa H 2 332/ distribution for thermal 44
thermal at 400°C and 6 over shale, apparatus used in
MPa H 2 331/ the gas-phase 41/
influence of thermal processing on over shale, kinetics for the
the properties of 347-357 thermal 39
reactivity of 327-346
residuum, IR spectrum of 355/ D
Colorado oil shale, H S evolution
2
from 61-77 Damage distribution and mean stress

Combustion retorting 53 contour plot, in computer
Commercial-scale refining of Paraho simulation
crude shale oil into military at 0.2, 0.6, 1.0, and 2.0 ms 20/-22/
specification fuels 223-235 Defluidization of the SPHER process,
Commercialization and the process of agglomeration and 178
technological change 215/ Density methods, beneficiation of
Commercialization and the process of Green River oil shale by 139-154
technological change 215/ Department of Energy (DOE) 1
Compaction 188-193 alternative retorting procedures 6
area, field 187/ chemical kinetics 5
studies during the Paraho research, development of
field 186 compliance plans 9
test results for Paraho retorted oil emissions control strategy 8
shale 189/ environmentally acceptable retort
Compliance plans, DOE's develop- abandonment strategy 7
ment of 9 solid waste management systems 7
Compression test results for Paraho water treatment systems 8
retorted oil shale 189/ environmental R&D needs 6
Computer simulation, damage distri- guidelines to ensure health and
bution and mean stress contour safety of workers and general
plot public 7
at 0.2, 0.6, 1.0, and 2.0 ms in ... 20/-22/ implementation plan 12

Department of Energy £
(DOE) (continued)
methods for controlling or prevent- Ecological impacts, DOE's mitiga-
ing subsidence 9 tion of 9
mitigation of ecological impacts .... 9 Economy-of-scale saving in the shale
mitigation of social and community oil production industry, examples
economic impacts 9 of 200
oil shale 2 Elastic constants 17
program Electrostatic properties of shale jet
goal and objectives 2 fuels 260-262,261/
mining systems 5 Emissions control strategy, DOE's
operating plans 11 development of 8
R,D,&D 1-12 Energy-efficient thermal recovery
key technical and environ- process, development of 361-364
mental needs in 3-11 EPA extraction, leachate data— 193/
strategy 2 ESR parameters for Cold Lake
process (ing) asphaltenes 356/
in situ 10 Ethene
novel techniques 11 /ethane ratio(s) 80
-specific R,D,&D 10 and alkene/alkane ratios pro-
surface 10 duced during kerogen
retorting mechanisms 6 pyrolysis 85
shaft sinking technology 5 effect of
strategic plan 11 for oil shale heated at 1.5°C/
Diesel fuel(s) min under autogenous
GC-simulated distillation of 256/ conditions, inert sweep
marine 231 gas on the time-dependent 86/
analyses 233/ from retorting oil shale, tem-
L C Fractions 5 and 7 244/-245/ perature and inert sweep
No. 2 gas on 89/
Arrhenius plot of DMP in 307/ of the total evolved gases, as
at 110°F, interaction between a function of cracking
DMP and aromatic thiols in 305/ losses and cracking
sediment increase due to inter- temperature 88/
action between DMP and as a function of Fischer assay,
isoquinoline in 301/ and heating rate 88/
shale oil products vs. petroleum from steam retort 87
products 324/ formation 80
2,5-Dimethylpyrrole (DMP) 306/ -hydrogen-ethane system 81
in No. 2 Diesel fuel Experience cost reduction 218
and aromatic thiols, at 110°F, Experience curve 213/
interaction between 305/ Explosive
Arrhenius plot of 307/ behavior 14
and isoquinoline, sediment increases field tests using ANFO in oil shale 17
due to interaction between . . . 301/ fracture of oil shale, computer
in JP-8, Arrhenius plot of 308/ simulation 13-24
sediment, proposed partial
structures for 300/ F
Distillation curves for tar sand
products and Wilmington crude Feedstocks, elemental analysis and
oil 377/ physical properties of 371/
DMP (see 2,5-Dimethylpyrrole) Ferroan during normal retorting
DOE (see Department of Energy) conditions 190
Dow-Colony oil shale FID (see Flame ionization detector)
beneficiation of 160/ Field ionization mass spectrometry
mineral distribution following .... 162/ (FIMS) 239
extraction of bitumen from 163/ base fraction from Shale-I JP-5 276/
samples, mineral constituents of of DFM, L C Fractions 5
Marathon lease and 163/ and 7 244/-245/

INDEX 387
Field ionization mass spectrometry Fuel(s) (continued)

(FIMS) (continued) samples
fingerprint 239 GC analyses of 238
hydrocarbon classes in JP-5 fuel L C separation of 238
samples by 246/ MS of 238
of Shale-I and Shale-II JP-5 NMR examination of 238
jet fuels 240/ system icing inhibitor (FSII) 254
Fischer assay
of Marathon lease oil shale 164/ G
particle size and 110
results for separated fractions 148/ Gas
retort 110 analysis 374/
vs. the TOSCO-II process 51 atmosphere, dependence of total
yield 97 evolved, on H S
2 72/
Flame ionization detector (FID) 94 chromatogram
chromatogram(s) of shale oil 48/-49/ of maltene fraction 343/
from Rock Springs No. 9 53 -MS peaks, tentative structural
chromatogram of TOSCO-II oil .... 52/ assignments of 272/-276/

response curve 100 -simulated distillation, fuels
Flammability and ignition properties DFM 256/
of shale jet fuels 258/, 259 JP-5 254/
Flash point of shale jet fuels 259-260 Shale-II jet 254
Flash points, Pensky-Martens 259 hydropyrolysis 374/
Flotation depressants 163 -phase cracking of shale oil over
Flow regimes and the SPHER process 177 shale, apparatus used in 41/
Fluidized-bed reactor system for oil and C 0 2 118-120
shale retorting 95/ Arrhenius plot for 119/
Fluidized-bed techniques, particle-size of the char, and steam 115
distributions of oil shale retorted rates of 120/
by 180/ kinetics of oil shale char 115-127
Fractional proton distributions of steam 121-122
Green River asphaltenes by H - l rates of 121/
NMR 135/ for leached and unleached
Fracture model development 15 shale, 123/
Fracture toughness of oil shale 17 Gasification-CaO present, mixed 124/
Fracturing Gasification-no CaO, mixed 124/
mechanisms 35 Gasoline stock(s), product analyses
of model minerals 35 of 228-230,230/
of oil shale(s) 27 GC (see Gas chromatogram)
by liquid S 0
2 29/ Gradation data for Paraho retorted
treatment with 25-37 oil shale 191/
by various fluids 30/ Green River asphaltenes
Free-radical cracking 80 average structural parameters of ... 137/
Free-radical mechanism, formation of by C-13 NMR, percentage carbon
an alkane by 85-90 group distributions of 135/
Freezing point of shale jet fuels 254 elemental compositions of 131/
FSII (Fuel system icing inhibitor) 262 by H - l NMR, fractional proton
Fuel(s) distributions of 135/
analyses, residual 234/ beneficiation
distribution, product 231-235 by density methods 139-154
FIMS of Shale-I and Shale-II by pelletization 155-166
JP-5 jet 240/ products of 158/
hydrocarbon content on synfuel geochemical basis 146-147
degradation mechanisms, IR spectra of 32/
effects of base 303 typical composition of 317/
physical properties of U.S. Navy Griffith criterion 16
Shale-II 253-266
properties and chemical composi- H
tion, relation between 237-251,
253-283 H - l NMR, asphaltenes

H - l NMR, asphaltenes (continued) Hydroconversion, reaction mechanism

data for 133 for asphaltene 344/
fractional proton distributions of Hydrogen
Green River 135/ -to-carbon ratios in reaction
spectra of crude and reacted 341/ products 336/
spectrum of, from shale requirement to hydrotreat shale oil. 321/
bitumen 134/ sulfide (H S)
2 61
oil retorted at 425°C 134/ evolution
oil retorted at 500°C 134/ from AP samples of varying
[H ][C H ]/[C H ] evolved from 22
2 2 4 2 6 grades 67/
gal/ton oil shale heated at in argon atmosphere 73
1.5°C/min under an autogenous from a 19-gal/ton Tract
atmosphere, Arrhenius plot for C-a sample of oil shale
the time and temperature de- treated at 4.8°C/min
pendence of 84/ in 65/
Health and safety of workers and from powdered sample of
general public, DOE's guide- 61-gal/ton AP61 oil
lines to ensure 7 shale in an 65/

Heat in an autogenous atmosphere .. 66
exchange retorting shell pellet ...167-181 with added pyrite 68/
media test flowsheet 144/ from Colorado oil shale 61-77
oil production, primary 103/ from oil shale, apparatus used
oil production, rate constants 109/ to measure the rate of
and coking 113/ argon atmosphere 64/
recovery section of the SPHER autogenous atmosphere 64/
process 176 in steam atmosphere 64/
transfer rates and the SPHER in the presence of steam for
process 177 Sample CA36 increase in 69/
High-temperature (thermal) stability from Sample AP22 heated at
of shale jet fuels 269, 278/ 4.8°C/min in an argon
atmosphere, effect of
Hydrocarbon (H/C)
atomic ratio and nitrogen content added pyrite on 67/
from sample in argon and
of the shale oil, effect of
40% steam atmos-
cracking on 45/
phere (s), comparison of
atomic ratio and nitrogen content
AP22 68/
of the shale oil, effect of shale
AP61 69/
oil coking on 47/
CA19 70/
classes in JP-5 fuel samples by
in a steam environment 66
FIMS 246/
evolved in argon and autogenous
effect(s)
atmospheres 72
types on sediment formation
on gas atmospheres, dependence
with DMP 306/
of total evolved 72/
yields at 930°F, particle-size 98/
reactions producing 72-75
yields for 0.4-mm particles,
total evolved 66-95
temperature 99/
Hydropyrolysis
fraction, light 106/
gas 374/
production from kerogen, rate
liquid products, characteristics of .. 375/
expressions for 103/
primary upgrading of tar sand
production, light 103/ bitumen 369-380
ratio of shale oil 44 process 370
series in Shale-II D F M 247/ representative results of 372/
series in Shale-II JP-5 248/ Hydrotreating yields, shale oil 230/
Hydroconversion of Cold Lake
asphaltenes
Arrhenius plot for 335/ I
at 400°C and 6 MPa H with 200 2 Ignition properties of shale jet fuels,
ppm molybdenum 332/ flammability 258/, 259
at 400°C and 6 MPa H , thermal .. 331/ In situ processing, DOE's
2 10

INDEX 389
In situ retorting 25 JP-5 (continued)

Infiltration 188-190 fuel(s) (continued)
field samples by FIMS, hydrocarbon
analysis 188/ classes in 246/
area 187/ stability properties, refinery 233/
studies during the Paraho process 186 hydrocarbon series in Shale-II 248/
Intraparticle coking 103/ results of storage stability of
liquid-phase 103 treated Shale-I 279/
IR spectra of oil shale yield, product yield of 294/
Antrim 34/ JP-8, Arrhenius plot of DMP in 308/
Green River 32/
Morrocan 33/ K
IR spectrum(a) of asphaltenes
Cold Lake crude 354/ Kerogen 198
Cold Lake residuum 355/ vs. coal 317/
crude and residuum, differential ... 355/ decomposition products, relative
samples 131-133 yields of 106/
shale oil 132/ decomposition, rate constants for .. 109/

Iron, first-order rate constants for the as a function of number of benefi-
oxidation/reduction of 125/ ciation cycles, recovery of
Iron on WGSR, catalytic effects of 125-126 Marathon lease 159/
Isoquinoline in No. 2 Diesel, and pyrolysis, ethene/ethane ratio and
sediment increase due to inter- alkene/alkane ratios produced
action between DMP 301/ during 85
pyrolysis model(s) 103-106
proposed 93, 105/
J rate expressions for hydrocarbon
production from 103/
Jetfuel(s) 231 Kinetic
high-temperature stability of 278/ curves 100
JP-5 285 measurements of shale oil cracking
nitrogen compounds of Shale-I 269 experiments 42
shale results 100-109
autoignition temperatures for .... 260
electrostatic properties of 261/
flammability and ignition L
properties of 258/ Lawrence Livermore National
flash point 259-260 Laboratory (LLNL) 39, 56/, 93
high-temperature (thermal) mechanism for shale oil generation
stability of 269 and degradation developed at 56/
miscellaneous physical proper- L C (see Liquid chromatography)
ties of 257/ Leachate(s)
oil, upgrading effect on compo- composition, initial 192/
sition and stability of 309/ data—EPA extraction 193/
Shale-II from Paraho retorted oil shale,
freezing point of 254 analysis of 192
GC-simulated distillation of 254 Liquid chromatography (LC)
specific gravity of 254 fractions, MS of 243-250
stability of oil shale-derived 267-283 separation of fuels, yields from 246t
JETOT evaluations by ASTM test separation of Shale-II DFM,
method D3241 conducted for preparative-scale 241/
2.5h at 260°C control tem- Liquid-phase (intraparticle) coking . . . 103
perature 311/
JP-5 M
fuel(s)
analyses 232/ Mahogany Zone
GC-simulated distillation of 254/ oil shale, Anvil Points Mine distri-
jet 285 bution of organic matter in
FIMS of Shale-I and Shale-II 240/ lower zone 152/

Mahogany Zone (continued) Oil (continued)

oil shale, Anvil Points Mine distribution shale (continued)
of organic matter in (continued) apparatus used to measure the
middle zone 151/ rate of H S evolution from
2
upper zone 151/ heated autogenous atmos-

oil shale, biomodal nature of 149 phere 64/
shale 140 at 1.5°C/min, Arrhenius plot
Marathon lease for the time and tempera-
and Dow-Colony oil shale samples, ture dependence of [H ]- 2
mineral constituents of 163/ [C H ]/[Q>H ] evolved

2 4 6
kerogen as a function of number of from 22-gal/ton 84/

beneficiation cycles, recovery .. 159/ at 1.5°C/min, effect of inert
oil shale, Fischer assays of 164/ sweep gas on the time-
Military specification fuels, commer- dependent ethene/ethane
cial-scale refining of Paraho ratio for 86/
crude shale oil into 223-235 at 1.5°C/min, product meas-
Mineral distribution following benefi- urements for 83/
ciation steps of Dow-Colony at l°C/min, propene/propane

oil shale 162/ ratios for 83/
Mine-run composite, weight recovery bimodal nature of Mahogany
vs. specific gravity for 144/ Zone 149
Mining opportunities 201-202 blasting experiments, data for .... 18/
MS of L C fractions 243-250 char gasification 115-127
computer simulation of explosive
N fracture of 13-24
Naphtha, shale oil products vs. dependence of thefinaldistribu-
petroleum products 322/ tion of sulfur in solid, gas,
Naphthalene/(Cii + C i ) , effect of
2
and liquid products as a
cracking on 50/ function of organic carbon in 71/
Naphthalene/2-methylnaphthalene deposits, bimodal nature of ... 149-153
ratio, effect of pyrolysis condi- -derived jet fuel, stability of ... 267-283
tions on 55/ disposal research, retorted 183-194
Nitrogen DOE's program
content in shale oil 44, 238-250 goal and objectives 2
and effect of cracking on the operating plans 11
H / C atomic ratio 45/ R,D,&D 1-12
content, Shale-II refining 242/ key technical and environ-
Shale-I mental needs in 3-11
compounds, fuels 269 strategy 2
compounds, G C basic 270/ Dow-Colony
fraction, total ion chromatogram beneficiation of 160/
of basic 271/ extraction of bitumen from .... 163/
mineral distribution following
O beneficiation steps of 162/
Oil samples, mineral constituents
coking 46 of Marathon lease and .... 163/
composition as a function of effect of inert sweep gas during
retorting temperature 99/ retorting on the 1-alkene/n-
crude 319/ alkane ratios in 86/
distillation curves for tar sand explosive field tests using ANFO
products and Wilmington .. 377/ in 17
production kinetics at 930°F 102/ feed preparation 172
shale 39 Fischer assays of Marathon lease 164/
Anvil Points Mine, distribution fracture toughness of 17
of organic matter in Mahog- fracturing of 27
any Zone by liquid SO, 25-27, 29/
lower zone 152/ by various fluids 30/
middle zone 151/ generation offinesand entrain-
upper zone 151/ ment of 179

INDEX 391
Oil (continued) Oil (continued)

shale (continued) shale (continued)
grade, relative distribution of .... 152/ retorting (continued)
grade with specific gravity, effect of temperature and
correlation of 147-149 inert sweep gas on the
Green River ethene/ethane ratio
geochemical basis of 146-147 from 89/
IR spectra of 32/ fluidized-bed reactor system
by pelletization, beneficiation for 95/
of 155-166 kinetics 93-113
typical composition 317/ possible mechanism of alkene/
heated at 5.5°C/min in a 40% alkane production 79-91
steam, 60% argon atmos- SPHER energy-efficient
phere, demonstration of the process for 167-181
importance of the pyrite- sample preparation 62
steam reaction for 70/ samples, properties of 62/
H2S evolution from Colorado ...61-77 sampling 140
IR spectra of Antrim 34/ strength of 17

Paraho retorted triaxial testing data for 17
analysis of leachates from 192 typical composition of 28/
chemical and physical proper- yield and oil composition, correla-
ties of 190-193 tion between 98/
compaction test results for ... 189/ from tar sands by an energy-effi-
compression test results 189/ cient process, thermal re-
gradation data for 191/ covery of 359-368
particle size Overheating and ignition of the
cumulative distribution of SPHER process 178
mineral constituents of .... 161/ Oxidation/reduction of iron, first-
on product yields at 930°F, order rate constants for 125/
the effect of 97-100
retorted byfluidized-bedtech-
niques, distributions of .. 180/ P
process, SPHER 168-172, 169/
processing 198 Paraho
technology 198 crude shale oil into military specifi-
recovery, systems approach cation fuels, commercial-scale
to 205-207 refining 223-235
pyrolysis scheme, raining ball .... 173/ direct mode operation 184/
rate of H S evolution from
2
process 167, 185
in an argon atmosphere field infiltration studies during .... 186
apparatus used to measure .. 64/ research, field compaction studies
heated at 4.8°C/min, a 19- during 186
gallon Tract C-a sam- retorted oil shale
ple of 65/ analysis of leachates from 192
a powdered sample of chemical and physical properties
61-gal/ton AP61 65/ of 190-193
in an autogenous atmosphere, compaction test results for 189/
apparatus used to compression test results for 189/
measure 64/ gradation data for 191/
in steam atmosphere, appara- semiworks retort 183
tus used to measure 64/ shale oil 223-225
reason for the beneficiation of .... 139 fractions (of)
retorting 61 C-13 NMR analysis of 287
above-ground 167 potential n-alkane yield from
processes 93-113 various residual 294/
at constant heating rate, appa- pyrolysis of 288
ratus used to measure the separation of a residue from .286-287
rate of evolution of gases and West Texas sour crude,
from 82/ properties of 224/

Particle-size Refinery JP-5 fuels stability

distributions of oil shale retorted by properties 233/
fluidized-bed techniques 180/ Refinery, shale oil
effect on hydrocarbon yields at logistics and process flow 226-227
930°F 98/ modifications 226
effect on retorting kinetics at 930°F 101/ run 227-228
Pelletization, beneficiation of Green Refining
River oil shale by 155-166 nitrogen content, Shale-II 242/
Pensky-Martens flash points 259 of Paraho crude shale oil into
Preheat section of the raining pellet military specification fuels,
process 174 commercial-scale 223-235
Pressure balance of the SPHER process, shale oil 225-226
process 178 Residual fuel 231
Product fuels distribution 231-235 analyses 234/
Propene/propane ratios for oil shale Retort
heated at l°C/min under an abandonment strategy, DOE's
autogenous atmosphere 83/ development of environ-
Pyrite mentally acceptable 7

H S evolution in an autogenous
2 Fischer assay 110
atmosphere with added 68/ Paraho semiworks 183
on the H S evolution from Sample
2 section of the raining-pellet process 175
AP22 heated at 4.8°C/min in shale oil to refinery feedstock,
an argon atmosphere, effect upgrading raw 204-205
of added 67/ shale oil samples, pilot and field .... 51
reactions involving steam and 74 Retorted oil shale disposal research 183-194
-steam reaction for oil shale heated Retorted oil shale, Paraho
at 5.5°C/min in a 40% steam, analysis of leachates from 192
60% argon atmosphere, dem- chemical and physical properties
onstration of the importance of 190-193
of 70/ compaction test results for 189/
of alkanes 80 compression test results for 189/
of asphaltenes 349 gradation data for 191/
conditions on the naphthalene/2- Retorted shale oils, and asphaltenes
methylnaphthalene ratio, from naturally occurring shale
effect of 55/ bitumen 129-138
mechanisms 286 Retorting
model(s), kerogen 93, 103-106, 105/ on the 1-alkene/n-alkane ratios in
of Paraho 288 shale oil, effect of inert sweep
rate constants 108/ gas during 86/
scheme, raining-ball oil shale 173/ combustion 53
of shale oil residual fraction(s) ...285-296 conditions, ferroan during normal .. 190
at 450°C in situ 25
polar 293/ kinetics at 930°F, particle size
saturate 292/ effect on 101/
for 30 min 291/ oil shale 61
unit, rapid heat-up 350/ above-ground 167
process 93-113
R at constant heating rate, appara-
tus used to measure the rate
Raining of evolution of gases during 82/
-ball oil shale pyrolysis scheme 173/ effect of temperature and inert
-pellet process, preheat section of .. 174 sweep gas on the ethene/
-pellet process, retort section of .... 175 ethane ratio from 89/
Raw retort shale oil to refinery feed- fluidized-bed systems for 95/
stock, upgrading 204-205 kinetics 93-113
Reaction products possible mechanism of alkene/
hydrogen-to-carbon ratios in 336/ alkane production 79-91
molecular weights of 340/ SPHER energy-efficient process
sulfur distribution in 337/ for 167-181

INDEX 393
Retorting (continued) Shale (continued)

opportunities 202-204 oil (continued)
shale 130 cracking
temperature chemistry of 39-60
and coke yield 97 conversion limit for 44
effect on kinetics for 1-mm data, Arrhenius plot of 45/
particles 104/ effects of retorting of tempera-
oil composition as a function of .. 99/ ture on 53
on shale oil cracking, effects of .. 53 experiments, kinetic measure-
Rifle Mine composite ments of 42
hand-picked, 0-+20 ft 145* products from 46*
mined, — A \n.-V4 in
3
143* over shale, apparatus used in
mined, —3 m-V4 in 143* gas-phase 41/
Rock Springs No. 9, chromatogram of over shale, kinetics for the
shale oil from 54/ thermal 39
FID 53 crude 319*
FID chromatograms of 48/-49/
from Rock Springs No. 9 53, 54/

S fractions, C-13
examination 289*
S0 (Sulfur dioxide)
2 25 NMR analysis of Paraho 287
fracturing of oil shales by NMR spectrum of polar 289/
liquid 25-37,29/ H / C ratio of 44
Safety of workers and general public, hydrogen requirement to hydro-
DOE's guidelines to ensure treat 321*
health and 7 hydrotreating yields 230*
SCM (see Statistical crack mechanics) nitrogen content 44,238-250
Sediment coking effect on H / C atomic
formation with DMP effects of ratio, effect of 47/
hydrocarbon types on 306* Paraho 223-225
formation, structural effects of syn- into military specification
fuel degradation mechanisms fuels, commercial-scale
on 298/ refining of crude 223-235
increase due to interaction between potentialrc-alkaneyield from
DMP and isoquinoline in No. various fractions residual 294*
2 Diesel 301/ separation of a residue
Shakedown 219/ from 286-287
period 217 and West Texas sour crude,
Shale properties of 224*
bitumen, H - l NMR spectrum of preparative-scale L C 239
asphaltene from 134/ processing blockflowdiagram . . . 229/
bitumen and retorted shale oils, production
asphaltenes from naturally economics of large-scale ... 195-221
occurring 129-138 industry, examples of econ-
jet fuels omy-of-scale savings in .. 200
autoignition temperatures for .... 260 technological changes 200-201
flash point of 259-260 products vs. petroleum products
high-temperature (thermal) diesel fuel 324*
stability of 269 naphtha 322*
properties of turbine fuel 323*
electrostatic 260-262, 261 * properties of laboratory samples 44
flammability and ignition .258*, 259 and its refined products, the
miscellaneous physical 257* chemistry of 315-325
Mahogany Zone 140 refinery
oil feedstock, upgrading raw
H-alkane content 239 retort 204-205
1-alkene/n-alkane ratios in 85 logistics and process flow .226-227
asphaltenes, IR spectra of 132/ modifications 226
characteristics of 223 run 227-228

Shale (continued) Shell pellet heat exchange retorting

oil (continued) (SPHER) (continued)
refining process 225-226 process (continued)
residual fractions, pyrolysis of 285-296 and flow regimes 177
at 450°C 292/ heat recovery section of 176
polar 293/ and heat transfer rates 177
of Paraho 288 oil shale 169/
saturate for 30 min 291/ applied to 168-172
retorted overheating and ignition of 178
at 425°C, H - l NMR spectrum pressure balance of 178
of asphaltene from 134/ problem areas of 177-179
at 500°C, H - l NMR spectrum staging of .177-178
of 134/ retort(ing) 167-181,171/
samples, pilot and field 51 vs. TOSCO-II 172
samples, conditions for prepara- Social and community economic
tion of laboratory 43/ impacts, DOE's mitigation of ... 9
upgrading effect on composition Sodium bicarbonate 164
and stability of jet fuel from 309/ Solid waste management systems,
retorting 130 DOE's development of 7
Shale-I Solvent extraction 129
fuel, storage stability of 277 Specific gravity
JP-5 correlation of oil shale grade
FIMS base fraction from 276/ with 147-149
results of storage stability of dependence of calculated organic
treated 279/ volume on organic and mineral 150/
and Shale-II jet fuels, FIMS of .. 240/ for mine-run composites, weight
nitrogen recovery vs 144/
basic compounds, GC of 270/ of Shale-II jet fuels 254
jet fuel, total ion chromatogram SPHER (see Shell pellet heat exchange
of basic fraction from 271/ retorting)
jet fuels, compounds of 269 Statistical crack mechanics (SCM) .... 15
Shale-II theory in stress wave codes 16
DFM, hydrocarbon series in 247/ Steam
DFM, preparative-scale L C separa- atmosphere, apparatus used to
tion of 241/ measure the rate of H S evolu-
distillation temperature data 254
2
tion from oil shale in 64/

fuels environment, H S evolution in 66
n-alkanes in 242/
2
gasification 121-122
chemical characterization of of the char, and C 0 115
U.S. Naval 237-251
2
rates of 121/
copper strip corrosion tests 263/ for leached and unleached shale 123/
jet and pyrite, reactions involving 74
GC-simulated distillation of .. 254 reaction for oil shale heated at
JP-5, FIMS of Shale-I 240/ 5.5°C/min in a 40% steam,
specific gravity of 254 60% argon atmosphere, dem-
JP-5, hydrocarbon series in 248/ onstrated of the importance of
refining nitrogen content 242/ the pyrite- 70/
Shell pellet heat exchange retorting retort, ethene/ethane ratios from .. 87
(SPHER) 168 for Sample CA36, increase in H S
preheater 170/
2
evolution in the presence of .... 69/

process
Storage stability of Shale-I fuel 277
agglomeration and defluidization
of 178 tests of treated JP-5, results of 279/
ball heater of 176 Stress wave codes, SCM theory in 16
ball separation and recovery Subsidence, DOE's methods for con-
in 178-179 trolling or preventing 9
choice of ball material for 179 Surface processing, DOE's 10
description, detailed 172-179 Sulfur dioxide (see S0 ) 2
energy-efficient, for retorting oil Sulfur distribution in reaction

shale 167-181 products 337/

INDEX 395
Sulfur in solid, gas, and liquid prod- Torbanite 156

ucts as a function of organic TOSCO (see The Oil Shale Company)
carbon in the oil shale, depend- TOSCO-II
ence on the final distribution of .. 71/ oil, FID chromatogram of 52/
Surfactants 164 process 167
Synfuel vs. Fischer assay 51
degradation mechanisms 297 semiworks, FID chromatogram of
compound interactions of 299-303 oil shale of 51
effects of base fuel hydrocarbon Tract C- a sample of oil shale heated
content on 303 at 4.8°C/min in an argon atmos-
structural effects of 297-299 phere, rate of H S evolution from
2
on sediment formation 298/ a 19-gal/ton 65/

stability 297-313 Triaxial testing data for oil shale 17
test results 303-312 Tube deposit ratings (TDR) 277
Turbine fuel, shale oil products vs.
T petroleum products 323*
Tag closed cup 259

U
Tar sand(s)
bitumen, hydropyrolysis primary Union process 167
upgrading of 369-380 U.S. Navy Shale-II fuels, physical
bitumens, feedstock sources of . ...369-370 properties of 253-266
by an energy-efficient process, Utah tar sands, laboratory results for
thermal recovery of oil processing of 366*
from 359-368 Utah thermal recovery process,
laboratory results for processing University of 363/
of Utah 366*
products and Wilmington crude oil,
V
distillation curves for 377/
TBP distillation comparison of pilot Varves 146
plant and refinery whole hydro-
treated product 229/
W
TDR (Tube deposit ratings) 277
Technological change, process of 209 Water-gas shift reaction (WGSR) .122-125
The Oil Shale Company (TOSCO) .... 167 catalytic effects of iron on 125-126
material-balanced assay (TMBA) .. 66 rate 116
Thermal Water treatment systems, DOE's
cracking of shale oil, product development of 8
distribution for 44 West Texas sour crude, properties of
cracking of shale oil over shale, Paraho shale oil and 224*
kinetics for 39 Wilmington crude oil, distillation
recovery 364-365 curves for tar sand products and 377/
process(es) 360-361
classification of and references X
for 366/
development of an energy- X-ray diffraction 162
efficient 361-364
of oil from tar sands by an Y
energy-efficient 359-368
University of Utah 363/ YAOUI 17
TMBA (TOSCO material-balanced calculations 18
assay) 66 code 13
Jacket design by Carol Conway.

Production by CandaceA. Deren and V. J. Deveaux.
Elements typeset by Service Composition Co., Baltimore, MD.

The book was printed and bound by The Maple Press Co., York, PA.


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Publication Date: September 3, 1981 | doi: 10.1021/bk-1981-0163.

Oil Shale, Tar Sands, and

In Oil Shale, Tar Sands, and Related Materials; Stauffer, H.;

In Oil Shale, Tar Sands, and Related Materials; Stauffer, H.;

Gulf Research & Development Company

Division of Fuel Chemistry

at the Second Chemical Congress

of the North American Continent,

Las Vegas, Nevada

August 25-29, 1980.

ACS SYMPOSIUM S E R I E S 163

AMERICAN CHEMICAL SOCIETY

In Oil Shale, Tar Sands, and Related Materials; Stauffer, H.;

In Oil Shale, Tar Sands, and Related Materials; Stauffer, H.;

M . Joan Comstock, Series Editor

David L. Allara James P. Lodge

Kenneth B. Bischoff Marvin Margoshes

Donald D . Dollberg Leon Petrakis

Robert E. Feeney Theodore Provder

Jack Halpern F. Sherwood Rowland

Brian M . Harney Dennis Schuetzle

W . Jeffrey Howe Davis L. Temple, Jr.

James D . Idol, Jr. Gunter Zweig

In Oil Shale, Tar Sands, and Related Materials; Stauffer, H.;

The ACS SYMPOSIUM SERIES was founded in 1974 to provide

In Oil Shale, Tar Sands, and Related Materials; Stauffer, H.;

heard or read at least one paper enthusiastically suggesting the general

In Oil Shale, Tar Sands, and Related Materials; Stauffer, H.;

Gulf Research & Development Company

April 10, 1981

In Oil Shale, Tar Sands, and Related Materials; Stauffer, H.;

The largest untapped fossil fuel resource in the United

This chapter not subject to U.S. copyright.

In Oil Shale, Tar Sands, and Related Materials; Stauffer, H.;

Program Goal and Objectives

The Department o f Energy's R,D&D o i l shale goal i s t o permit

o To overcome t e c h n o l o g i c a l b a r r i e r s to o i l shale commer-

o To f o s t e r development o f innovative processes for a l l

shales that reduce environmental impact

o To obtain accurate environmental data and demonstrate

The a n a l y s i s o f commercialization i n c e n t i v e s and m i t i g a t i o n

In essence, the DOE program goal i s t o develop the techno-

o Research and Development

o Development and Demonstration Support

Through the existence o f these p a r a l l e l a c t i v i t i e s , the

In Oil Shale, Tar Sands, and Related Materials; Stauffer, H.;

i n the i n d u s t r i a l d e c i s i o n process and f a c i l i t a t e o i l shale

environment and socioeconomic impacts before committing to a

Key T e c h n i c a l and Environmental Needs i n R,D&D

T e c h n i c a l . The O i l Shale R,D&D Program i s d i r e c t e d toward

o E f f i c i e n t O i l Shale Rock Breakage and Retort Bed Pre-

o Development o f Retort Diagnostics and Instrumentation,

o Development o f Retort Control Procedures,

o Systems Engineering Methods f o r T o t a l O i l Shale Process

o E f f i c i e n t and E f f e c t i v e O i l Shale Mining Systems,

In Oil Shale, Tar Sands, and Related Materials; Stauffer, H.;

o Advanced Shaft Sinking Technology,

o Chemical K i n e t i c s o f the T o t a l P y r o l y s i s Process,

o Understanding Retorting Mechanisms and Developing a

Rock Breakage and Retort Bed P r e p a r a t i o n . Efficient

sweep e f f i c i e n c y w i l l be poor, and s i g n i f i c a n t amounts o f o i l

Retort Diagnosis and Instrumentation. The development o f

Retort C o n t r o l Procedures. The development o f r e t o r t con-