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33.OJ.0
PYROLYSIS OF SUNNYSIDE (UTAH)
TAR SAND: CHARACTERIZATION OF VOLATILE
COMPOUND EVOLUTION
John G. Reynolds and Richard W. Crawford
University of California
Lawrence Livermore National Laboratory
Livermore, California 94550
ABSTRACT
Sunnyside (Utah) tar sand was subjected to programmed
temperature pyrolysis and the volatile products were
detected by tandem on-line mass spectrometry (MS/MS) in
real time analyses. A heating rate of 4°C/min from room
temperature to 900°C was employed.
Evolution of hydrogen, light hydrocarbons, nitrogen-,
sulfur- and oxygen-containing compounds was monitored by
MS or MS/MS detection. Evolution of volatile organic
compounds occurred in two regimes: 1) low_temperature
(maximum evolution at 150 to 175°C) f corresponding to
entrained organics, and 2) high temperature (maximum
evolution at 440 to 460°C), corresponding to cracking of
large organic components. The pyrolysis yields were
dominated by the evolution of light hydrocarbons.
Alkanes and alkenes of two carbons and higher had
temperatures of maximum evolution at approximately
440°C, and methane at approximately 474°C. Aromatic
hydrocarbons had temperatures of maximum evolution
slightly higher, at approximately 450°C.
Comparing the Sunnyside pyrolysis to the pyrolysis of
other domestic tar sands indicated the following for
hydrocarbon evolution: 1) the evolution of entrained
organics relative to the total evolution was much less
for Sunnyside tar sand, 2) the temperatures of maximum
evolution of hydrocarbons due to cracking reactions were
at slightly lower, and 3) the temperatures of maximum
evolution for benzene and toluene are slightly higher
than observed for other tar sands.
In general, the noncondensible gases, H2, CO, and CO2,
exhibited evolution associated with hydrocarbon cracking
reactions, and high temperature evolution associated
with mineral decomposition, the water-gas shift
reaction, and gasification reactions. Compared to other
domestic tar sands, the gas evolution reflected more
mineral decomposition character for Sunnyside tar sand.
INTRODUCTION
Tar sand is defined as any sand or rock which is
impregnated with heavy oil or bitumen. (This excludes
coal, oil shale,, and Gilsonite.) In the United-States
alone, there are "an estimated 60 billion barrels of
bitumen in tar sand, some of which is recoverable.(1)
The Sunnyside deposit in Utah accounts for approximately
4.4 billion barrels of recoverable bitumen,(2) making it
an attractive deposit for recovery processing. Several
commercial concerns have had financial interest in the
development of recovery processing, including in situ
thermal (Shell Oil),(2) steam flooding (Signal Oil and
Gas), (2) and solvent extraction (AMOCO). (3)
Laboratory pyrolysis of a given tar sand is useful in
pyrolysis type recovery research, both in situ and
surface. Several laboratory studies have been performed
on Sunnyside tar sand, to elucidate its performance —
fluidized-bed(4)
and
fixed-bed(5)
pyrolysis,
hydropyrolysis, (6)
hot water(7)
and solvent
extraction.(3,7)
3
This paper summarizes our initial efforts in the
laboratory pyrolysis of Sunnyside tar sand, and compares
the results to the pyrolysis of other domestic tar sands
(Asphalt Ridge from Utah and Big Clifty from Kentucky)
studied under the same conditions.
EXPERIMENTAL
The techniques and equipment utilized have been
described in detail elsewhere, as applied to oil shale
pyrolysis,(8) and tar sand pyrolysis.(9)
Briefly: the tar sands were" pyrolyzed under argon
carrier gas from room temperature to 900°C at a heating
rate of 4°C/min, in a quartz reactor. The argon flow
was approximately 200 cc/min.
The 150°C volatile
material was examined by on-line, real time mass
spectrometry (MS) and MS/MS detection. Gas evolution
profiles were monitored as a function of temperature.
When possible, quantitation was performed by calibrating
the instrument with the appropriate standard diluted in
the carrier gas.
The Sunnyside tar sand was a gift from Tom 0'Grady of
AMOCO, Naperville, IL, and was ground to a 3/8 inch
minus I.D.
It contains 6.2 wt% toluene extractable
bitumen.
RESULTS
Two pyrolysis experiments were performed on Sunnyside
tar sand.
The results generally agreed, but the
temperatures of maximum evolution of species evolving at
higher temperatures differed by 3°C to 4°C. This was
due to the temperature controlling thermocouple. -The
position was as close to the center of the reactor as
possible, but this placement is not perfectly
reproducible. For these results, however, this is not a
critical parameter. In addition there is a temperature
gradient across the diameter of the reactor, which is
approximately 12°C from wall to center.
Hydrocarbon Evolution. Figure 1 shows the evolution of
hexanes as a function of pyrolysis temperature for
Sunnyside tar sand.
This profile is typical of the
hydrocarbon evolution profiles for Sunnyside, Asphalt
Ridge, and Big Clifty tar sands.(9)
In general, the
generation of volatile hydrocarbons occurs in two
distinct temperature ranges: 1) a low temperature range
which is close to the distillation temperatures of
various lower molecular weight alkane, alkene, and
aromatic species, and 2) a higher temperature range
which is close to the cracking temperatures of high
molecular weight hydrocarbons, heteroatomic species, and
salts of organic compounds. "
Table 1 shows the hydrocarbon evolution data for
Sunnyside tar sand.
Included are the temperatures of
maximum evolution of each species, and the relative
percentage of the total evolution is given in
parentheses. A bimodal distribution is seen for all
hydrocarbons other than propane.
These results are
similar to those of Asphalt Ridge and Big Clifty tar
sands. The only differences are : 1) the temperatures
of maximum evolution in the cracking evolution range are
slightly lower, and 2) the relative distribution of
release of hydrocarbon is weighted to the cracking
regime for the Sunnyside tar sand. In addition, no low
temperature release of methane and ethene is observed
for Asphalt Ridge and Big Clifty tar sands.
5
Methane exhibits the highest temperature for maximum
evolution in the cracking regime (474°C). This behavior
has been seen before in tar sand (9) and oil shale
pyrolysis.(10) The other alkyl hydrocarbons appear to
have cracking evolution maxima which slightly decrease
in temperature as the length of the carbon chain
increases.
Hexanes have an evolution maximum due to
cracking 13°C lower in temperature than ethane.
The
same appears to be true for the alkenes. This has been
observed in Asphalt Ridge and Big Clifty tar sands, (9)
and Devonian oil shale pyrolysis.(11)
Small amounts of methane and longer hydrocarbons evolve
in the low temperature region. This behavior has been
observed for Asphalt Ridge and Big Clifty tar sands.(9)
This evolution temperature is much higher than the
distillation temperature of low molecular weight
hydrocarbons, and has been attributed to a weak
interaction between the sand matrix and the bitumen
breaking down, allowing entrained or adsorbed methane
(as well as other hydrocarbons) to evolve.
This evolution at low temperature is much more obvious
for Asphalt Ridge and Big Clifty tar sands, and has been
attributed to: 1) the boiling point distribution of the
bitumen, and/or 2) sample handling, mining conditions,
or diagenetic maturation or migration. Boiling point
distribution of the extracted bitumens shows Sunnyside
tar sand has the highest temperature distillation range,
and has the lowest percentages of hydrocarbons evolving
in the low temperature range.(12,13) The second point
is more difficult to analyze for, because, except for
laboratory handling, the other variables are difficult
to measure. As of this time, however, it is thought
that the differences are due to both boiling point
distribution and different diagenetic conditions,
because a l l samples were carefully r e t r i e v e d , s t o r e d in
closed c o n t a i n e r s , and handled under n i t r o g e n in t h e
laboratory.
Table 1 a l s o shows an i n c r e a s e in t h e r e l a t i v e
proportion of entrained hydrocarbons evolving at the low
temperature with i n c r e a s i n g carbon chain l e n g t h .
This
is c o n s i s t e n t with t h e l a r g e r hydrocarbons being l e s s
v o l a t i l e than the l i g h t e r hydrocarbons, and t h e r e f o r e
d i s s i p a t e l e s s rapidly with time. It is also c o n s i s t e n t
with t h e behavior of Asphalt Ridge and Big C l i f t y t a r
sands.
Methane.
Figure 2 shows the methane evolution p r o f i l e
of Sunnyside t a r sand.
The y-axis has been c a l i b r a t e d
with a methane s t a n d a r d , and is the volume of gas
evolved per minute per gram of whole t a r sand.
Obvious
is the maximum at cracking evolution, accounting for 68%
of t h e methane evolved.
Obvious also is a shoulder on
t h e high temperature side of the prominent maximum.
This shoulder has a defined maximum at approximately
538°C, and accounts for 29% of the methane evolved.
In
Asphalt Ridge and Big Clifty t a r sands(9) and o i l shale
p y r o l y s i s , t h i s s h o u l d e r has been a t t r i b u t e d t o
secondary
reactions
of l a r g e h y d r o c a r b o n s
and
h e t e r o a t o m i c compounds producing char or coke and
l i b e r a t i n g methane. (14)
Also seen in the p r o f i l e is
the low temperature evolving methane.
Aromatic Hydrocarbons. Table 2 shows the temperatures
of maximum e v o l u t i o n for benzene and t o l u e n e for
Sunnyside, Asphalt Ridge, and Big Clifty t a r sands. The
evolution behavior is similar to the alkanes and alkenes
— a low temperature maximum of evolution around 150°C,
and a high temperature maximum of evolution at cracking
temperatures.
7
Both benzene and toluene have pyrolysis evolution
profiles which are similar to but have temperatures of
maximum evolution slightly above those for the other tar
sands. The benzene maximum for cracking evolution
occurring approximately 8 degrees lower in temperature
than the toluene.
This latter observation has been
attributed to benzene being formed by different
mechanisms than toluene.
The principal difference among the three sands is the
relative distribution of aromatic compounds which shows
the Sunnyside tar sand has much less material evolved at
low temperature. This suggests a difference in the
handling or diagenetic conditions.
Hydrogen. Figure 3 shows the hydrogen evolution profile
as a function of pyrolysis temperature for Sunnyside tar
sand. The profile shows no hydrogen evolution before
approximately 350°C. Five (or six) evolution maxima are
seen above this temperature. The best defined maximum
occurs at 438°C, and accounts for approximately 35% of
the total hydrogen evolved. This maximum occurs in the
same temperature range as the maximum for hydrocarbon
evolution
(see above),
and is attributed to
aromatization, cracking, and dehydrogenation reactions
of nonvolatile organic compounds.
These types of
reactions have been observed when heavy oils are
subjected to high temperature conversion processes. (15)
This maximum has been also observed in the pyrolysis of
Asphalt Ridge and Big Clifty tar sands, (9) and oil
shale. (14) A sharp, well defined maximum is also seen
at 500°C, accounting for 8% of the hydrogen evolved.
This maximum has not been observed before in the
pyrolysis profiles of the other tar sands. The reasons
are not clear, but could be due to: 1) the low intensity
8
of hydrogen evolution at cracking temperatures in the
Asphalt Ridge and Big Clifty tar sands not
allowing
resolution of this peak, or 2) mineral dehydration or
compound
decomposition,
unique to
Sunnyside.
This
produces water which is then gasified into hydrogen by
the char on the sand surface (see Discussion section).
A much less defined maximum is observed about
645°C.
The nature of this peak is not certain, but possibly can
be attributed to secondary charring reactions,
also.
The evolution maxima at high temperature, approximately
717°C
and
798°C,
decomposition
component
of
are
in
and mineral
Sunnyside
the
region
transformation.
is primarily SiC>2
of
mineral
The
sand
in various
hydration forms,(16) and has batch dependent impurities
which could be decomposing to liberate water promoting
gasification reactions.
In addition, the hydrogen at
these temperatures could be controlled by the water-gas
shift
reaction
These
maxima
(-see
occur
Discussion
at
section below) . (17)
approximately
the
temperatures as observed in oil shale pyrolysis,
same
and
have been attributed to the same types of reactions.
The principal difference of Sunnyside compared to
Asphalt Ridge and Big Clifty tar sands is the relative
amount of hydrogen evolving during hydrocarbon cracking.
For Asphalt Ridge, Big Clifty, and Sunnyside tar sands,
the bitumen contents are:
15%,
5%,
and 6.2%,
respectively; the hydrogen evolutions are: 0.82, 0.38,
and 1.73 cc of hydrogen/min-gram, respectively.
The
much higher absolute amount of hydrogen evolving for
Sunnyside is unexpected when considering the extractable
bitumen contents. This suggests the Sunnyside tar sand
contains some pyrobitumen or even kerogen in the sand
formation, which is not solvent extractable.
In
addition, the profile looks more like oil shale hydrogen
9
evolution profiles(14) than Asphalt Ridge or Big Clifty
tar sand profiles.
Carbon Monoxide.
Figure 4 shows the CO evolution
profile as a function of pyrolysis temperature for
Sunnyside tar sand. No evolution of CO is seen below
300°C, after which evolution begins. A small maximum is
evident at 438°C and falls in the range of hydrocarbon
evolution due to cracking reactions. This maximum
accounts for approximately 2% of the CO formed. The
chemical species responsible for this evolution are not
certain, but may be the decarbonylation of carboxylic
acids and salts (see Discussion section) or perhaps
ketones.(18)
The evolution at high temperature shows two defined
maxima at 74 9°C and 815°C, corresponding to 98% of the
CO evolved.
This is similar ,to the behavior of Big
Clifty tar sand and indicates CO production'chemistry,
not related directly to hydrocarbon generation, is more
prominent for both of these tar sands than for Asphalt
Ridge tar sand. This higher temperature CO could have a
variety of origins,(19) including the water-gas shift
reaction, the Boudouard reaction, carbonate mineral
decomposition, and char gasification.
The difference among the Sunnyside, Asphalt Ridge, and
Big Clifty tar sands is in the relative percentage of
total CO evolved at cracking temperatures.
For Big
Clifty and Asphalt Ridge tar sands, the maximum
associated with hydrocarbon evolution accounts for 10%
and 29% of the CO evolved, relatively. This peak is
much smaller for Sunnyside tar sand.
However, when
considering the quantitative yields, the Big Clifty tar
sand (0.15 cc of CO evolved/g tar sand) produces
approximately one third the amount of CO during
hydrocarbon generation produced by Asphalt Ridge tar
sand (0.38 cc of CO evolved/g tar sand), and Sunnyside
falls into the middle (0.23 cc of CO evolved/g of tar
sand). This is consistent with the bitumen yields for
the three tar sands (see above). This relationship, of
course, would only have significance if the reactions
and species producing CO in this temperature regime are
the same in all three tar sands. Model compound studies
suggest some of the carbon oxide formation could be due
to decomposition of carboxylic acids and salts (see
below).
Carbon Dioxide.
Figure 5 shows the CO2 evolution
profile as a function of temperature for Sunnyside tar
sand. Unlike the hydrogen and CO profiles, evolution is
evident at the onset of heating, below 300°C. This has
been seen for other tar sands.(9) This is probably due
to desorption_ ofCO2 on the quartz filler used in the
reactor, and the Si02 of the sand matrix. This type of
desorption has been shown to be important in the water
evolution profiles discussed below.
Above 300°C, the evolution of CO2 increases, with a
small, but defined, evolution maximum at 4 64°C. This is
in the temperature range of hydrocarbon evolution due to
cracking reactions. This maximum accounts for
approximately 6% of the CO2 evolved, and may be
associated with organic decarboxylation reactions (see
Discussion section). The prominent maximum is at 751°C,
and accounts, for 94% of the CO2 evolved. This peak
accounts for" approximately one third the CO2 which
should be evolved due to carbonate decomposition as
measured by acid carbonate determinations.
This
indicates CO2 is consumed by other reactions. In this
evolution range for Big Clifty tar sand, carbonate
mineral decomposition appears to dominate, while for
11
Asphalt Ridge tar sand, the water-gas shift reaction
appears important.
Water. Figure 6 shows the water evolution profile for
Sunnyside tar sand.
Quantitatively, the profile
corresponds to a total evolution which is in the range
of the other tar sands, and has a profile shape which is
similar to Big Clifty tar sand.
However, the fine
structure of the profile is unique. Evident is a sharp
peak at 115°C, which accounts for 17% of the evolved
water.
This corresponds to free water.
Evident at
370°C is a broad peak due to the quartz filler. This
accounts for approximately 25% of the evolved water.
Differences in Sunnyside, Asphalt Ridge, and Big Clifty
tar sands water evolution profiles are seen in regions
above 400°C. For Sunnyside and Big Clifty tar sands,
evolution is occurring at temperatures of hydrocarbon
evolution *due to cracking reactions, but there is no
maximum. The closest maximum is at 513°C for both tar
sands, which is well above the temperature range for
hydrocarbon evolution, except for methane.
A broad
maximum is also seen at approximately 64 0°C. This is
coincident with the maximum in the carbon dioxide
profile, which, along with the acid carbonate
determination, indicates at least some of this water is
due to carbonate mineral decomposition.
The balance
could have different sources, for example, some
dehydration of hydrated forms of SiC-2.
The behavior of water during pyrolysis of tar sands is
more clearly defined when comparing water evolution
profiles at several different conditions.
There are
roughly six evolution ranges: 1) free water (at
approximately 100°C) , 2) entrained water (150 to 250°C) ,
3) quartz desorbed water (temperature of maximum at
12
approximately
(temperature
to beta
6)
340°C),
4)
hydrocarbon
o f maximum a r o u n d 475°C),
t r a n s i t i o n water
cracking
5)
quartz
( s h a r p maximum a t
m i n e r a l decomposition water
water
alpha
560°C),
and
(600 to 680°C) .
DISCUSSION
Hydrocarbon
figures,
evolution.
As seen in the t a b l e s
and t h e
hydrocarbon evolution i s e s s e n t i a l l y bimodal
distribution,
evolution
at
with
a
low
approximately
temperature
150°C t o
maximum
175°C,
and
in
of
a high
t e m p e r a t u r e maximum o f e v o l u t i o n a t a p p r o x i m a t e l y 450°C.
The
high
pyrolysis
are
to
or
char.
cracking
light
evolution
reactions.(20)
known
coke
for
temperature
crack
to
reactions
are
due
the
light
data
hydrocarbons
listed
are:primarily
above,
responsible
process
performance
and
these
for
h y d r o c a r b o n y i e l d i n p y r o l y s i s and s u g g e s t
possible
to
L a r g e h e t e r o a t o m compounds
produce
From
maxima
the
areas
enhancement.
An
o b v i o u s e x a m p l e i s p y r o l y s i s u n d e r H 2 which h a s shown t o
enhance
l i q u i d y i e l d s in t h e h y d r o p y r o l y s i s of Sunnyside
b i t u m e n . (6)
primarily
The
incremental
through
the
hydrogen a v a i l a b i l i t y .
also
important
gain
reduction
liquid
yield
of
coking
by
is
the
The m e a s u r e o f c r a c k i n g y i e l d s i s
because
several
refinery
dependent
on cracking type r e a c t i o n s
example
catalytic
cracking,(21)
in
cracking,
practices
are
for upgrading,
for
fluidized
catalytic
and residuum h y d r o c o n v e r s i o n . ( 1 5 , 2 2 )
CC>2r CO. H2O. a n d H2 •
S e v e r a l r e a c t i o n s m u s t be
c o n s i d e r e d when a c c o u n t i n g f o r t h e e v o l u t i o n of CO2, CO,
H2O,
and H2 in t h e Sunnyside t a r sand p y r o l y s i s .
have been
s t u d i e d i n more d e t a i l
elsewhere,(9)
These
and w i l l
13
only be mentioned briefly here because the mechanism(s)
have not been unequivocally discerned.
The cause of the CO and CO2 evolution in the temperature
range of hydrocarbon evolution has been examined by
model compound studies. The obvious candidate is the
decomposition of carboxylic acids and salts which are
known in tar sand bitumen.(23) Ketones, which have been
observed in tar sands, (12) have also been considered to
produce CO in oil shale pyrolysis.(18) Depending upon
the carboxylic acid, the decomposition pathway is
through reactions (1) and/or (2) . (24) Even though the
reaction chemistry appears applicable, the evolution
temperatures for CO and CO2 from the model compound are
almost 100°C below that of the evolution temperatures
for those compounds for the tar sands. The cause of
this is not clear, but makes the model suspect.
However, carboxylic acid compounds have been found to
have varying decomposition temperatures depending on
carbon structure.(25)
RCH2CH2COOH
RCH2CH2COOH
=
CO2
CO
+
+
H20
RCH2CH3
+
(1)
RCH=CH2
(2)
All tar sands show temperatures of maximum evolution for
water which are above the maximum assigned to
hydrocarbon evolution. This water and CO evolution may
be accounted for by the water-gas shift reaction shown
in reaction (3).
CO
+
H20
=
C0 2
+
H2
(3)
Enough CO2 can be generated by the carbonate mineral
decomposition to make r e a c t i o n s l i k e (3) p o s s i b l y
relevant.
Pyrolysis experiments on o i l shales(14,17)
under c e r t a i n conditions have shown gas s h i f t r e a c t i o n s
are in effect above 550 C, and the rapid decrease in
detected water may be a result of reaction (3) .
Comparison of calculated and theoretical log Keq values
for reaction (3) for Asphalt Ridge and Big Clifty tar
sands show similar behavior, close to water-gas shift
values, but not matching exactly.
CO2
+
CHX =
2CO
+
X/2H2
(4)
The Boudouard reaction, reaction (4), depends upon the
deposition of organic char or coke on the sand during
hydrocarbon generation. Some char formation is evident
based upon the secondary evolution behavior of methane.
Independent studies on the pyrolysis of Asphalt Ridge
tar sand show very low coke formation, (5,26) but much
higher for Sunnyside tar sand.
In the pyrolysis of
Colorado oil shale, however, this has been shown not to
be important.(14)
H20- +
C =
CO
+ H2
(5)
Char gasification^ reaction (5), also depends upon char
formation, and the evolution of water by some secondary
reactions, primarily through mineral dehydration.
(Several silica based minerals are highly hydrated, and
could liberate water upon heating.)
As stated above,
char formation is low for Asphalt Ridge tar sand, but
much higher for Sunnyside tar sand.
In addition,
pyrolysis of the extracted Asphalt Ridge tar sand also
shows no water evolution above approximately 500°C,
indicating this reaction may have little consequence
here. However, other sources of water can not: be ruled
out, such as pyrolysis of the coke itself.
MCO3
= MO
+
C0 2
(6)
15
Carbonate mineral decomposition, reaction (6), is
important for all three tar sands, as evidenced by the
independent acid carbonate determinations, shown in
Table 3, and appears to dominate the high temperature
gas evolution behavior, particularly for Big Clifty and
Sunnyside tar sands.
CONCLUSIONS
Several conclusions can be made about the comparison of
Sunnyside, Asphalt Ridge, and Big Clifty tar sands:
1) Hydrocarbon evolution occurs at approximately the
same cracking temperatures for Asphalt Ridge and Big
Clifty, but is slightly lower for Sunnyside tar sands.
In addition, methane evolves at a higher temperature
than the longer chained hydrocarbons .2) Hydrocarbon evolution due to entrainment occurs
approximately at the same temperature in all three tar
r
sands. However, Big Clifty has, relatively, a much
higher percentage of total hydrocarbons evolving in
this range.
3) CO evolution appears similar for all three tar
sands, with a maximum associated with hydrocarbon
evolution, and a high temperature maximum associated
with mineral decomposition or water-gas shift
chemistry. This latter maximum is relatively larger
in Sunnyside and Big Clifty tar sands.
4) CO2 evolution profiles are substantially different,
with Asphalt Ridge tar sand exhibiting, clearly, CO2
evolution associated with hydrocarbon evolution, but
the Sunnyside and Big Clifty tar sands dominated by
higher temperature evolution which is due, in part, to
mineral decomposition.
1
5)
Water evolution profiles are also substantially
different,
with,
after
subtracting
all
exogenous
sources of water, the Asphalt Ridge exhibiting a sharp
maximum associated with hydrocarbon evolution, but Big
Clifty
and
Sunnyside
tar
probably due to mineral
sands
showing
evolution
decomposition overwhelming
this peak.
Other
gases
have
been
examined,
including
hydrogen
sulfide, ammonia, volatile organo-sulfur, nitrogen, and
oxygen compounds,
publications.
and will be presented in subsequent
In addition, other tar sands and heavy
oils have been examined and will be reported elsewhere.
ACKNOWLEDGMENTS
We thank Rosalind
determinations,
assistance,
Swansiger
Armando
and Art
for the
Alcarez
Lewis
for
acid carbonate
for
experimental
funding.
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.
REFERENCES
(1) Westhoff, J. D.,
Eastern Oil Shale Symposium,
KECL86-158, 65 (1986).
(2) Kuuskra, V. A., Hammershaimb, E. C, and Paque, M.,
DOE/METC DE85 001994, 35 (1985).
(3) Graham, R. J.,
Eastern Oil shale Symposium.
KECL87-XXX (1987).
(4) Venkatesan, V. N., Hanson, F. V., and Oblad, A.
G., AIChE Symp. Ser., 2&(216), 42 (1982)
(5) Barbour, R. V., Dorrence, S. M., Vollmer, T. L., and
Harris, J. D.,
ACS Div. Fuel Chem., Preprints, 2JL(6),
278 (1976).
17
(6) Bunger, J. W., ACS Div. Petrol. Chem., Preprints,
^ ( 4 ) , 658 (1985) .
(7) Oblad, A. G., Bunger, J. W., Hanson, F. V., Miller,
J. D., and Seader, J. D., DOE METC85-6026, DE85013717,
73 (1985).
(8) Wong, C. M., and Crawford, R. W.,
Int. J. Mass
Spec, and Ion Processes, £H, 107 (1984) .
(9) Reynolds, J. G., Crawford, R. W., and Coburn, T.
T., Eastern Oil Shale Symp., KECL87-YYY (1987).
(10) Wong, C. M., Crawford, R. W., Barton, V. C, Brand,
H. R., Neufeld, K. W., and Bowman, J. W., Rev. Sci.
Instr., 5_i, 996 (1985) .
(11) Coburn, T. T., Energy Sources, 2, 121 (1983).
(12) Bunger, J. W., Thomas, K. P., and Dorrence, S. M.,
Fuel, 58, 183 (1979).
(13) Personal Communication, Martin C. Noger.
(14) Campbell, J. H., Koskinas, G. J., Gallegos, G., and
Gregg, M., Fuel, £2, 718 (1980).
(15) Beret, S., and Reynolds, J. G., ACS Div. Petrol.
Chem., Preprints, 3JH4), 664 (1985).
(16) Altringer, P. B., McDonough, P. J., and Brooks, P.
T., US Bur. Mines, OFR 11-85, PB85-185791 (1982).
(17) Coburn, T. T., Crawford, R. W., Gregg, H. R., and
Oh, M. S., Eastern Oil Shale Symposium, KECL86-158, 291
(1986) .
(18) Singleton, M. F., Burnham, A. K., Richardson, J.
H., and Clarkson, J. E., UCRL-88128 (1983).
(19) Campbell, J. H., and Burnham, A. K., Proceedings
of the 11th Shale Oil Symposium, Colorado School of
Mines, 242 (1978).
(20) Satterfield, C. N., Heterogeneous Catalysis.
McGraw-Hill Book Co., New York (1980).
(21) Gary, J. H., and Handwerk, G. E., Petroleum
Refining. Marcel Dekker, Inc., New York (1984).
(22) Reynolds, J. G., and Beret, S., AIChE Annual
Meeting, New York, paper 9072 (1987).
(23) Barbour, F. A., Guffey, F. D., and Dorrence, S. M.,
Oil Sands, 743 (1977).
(24) March, J., J. Chem. Ed., A£(4), 212 (1963).
(25) Bigley, D. B., and May, R. W., J. Chem. S o c , B,
557 (1967).
(26) Lechner, C. A., Liapis, A. I., and Findley, M. E.,
Proc. AIChE 1984 Spring National Meet., V 57A. paper
9383 (1984).
Figure 1. Evolution of Hexanes as a Function of
Pyrolysis Temperature for Sunnyside Tar Sand.
Quartz Reactor at a 4°C/min Heating Rate.
Figure 2. Evolution of Methane as a Function of
Pyrolysis Temperature for Sunnyside Tar Sand.
Quartz Reactor at a 4°C/min Heating Rate.
Figure 3. Evolution of Hydrogen as a Function of
Pyrolysis Temperature for Sunnyside Tar Sand.
Quartz Reactor at a 4°C/min Heating Rate.
Figure 4. Evolution of Carbon Monoxide as a Function of
Pyrolysis Temperature for Sunnyside Tar Sand.,
Quartz Reactor at a 4°C/min Heating Rate.
Figure 5. Evolution of Carbon Dioxide as a Function of
Pyrolysis Temperature for Sunnyside Tar Sand.
Quartz Reactor at a 4°C/min Heating Rate."
Figure 6. Evolution of Water as a Function of Pyrolysis
Temperature for Sunnyside Tar Sand. Quartz
Reactor at a 4°C/min Heating Rate.
Table 1. Hydrocarbon Evolution Data for
Sunnyside Tar Sands, 4°C/min Heating
Rate, Quartz Reactor
Species
Peak 1
°C (%)
Peak 2
°C (%>
CH4
C2H4
C2H6
C3H6
C3H8
C4H8
C4H10
C5H10
C5H12
C6H12
C6H14
C7H10
110 (3)
tr
171 (4)
193 (5)
474
445
451
443
440
441
437
441
438
434
438
446
-
167
190
163
181
180
177
177
(6)
(9)
(8)
(11)
(11)
(17)
(25)
(96)
(100)
(96)
(95)
(100)
(94)
(91)
(92)
(89)
(89)
(95)
(75)
Table 2. Aromatic Hydrocarbon Evolution
Data for Asphalt Ridge, Big Clifty,
and Sunnyside Tar Sands, 4°C/min
Heating Rate, Quartz Reactors
Tar Sand
Peak 1
°C (%)
Peak 2
°C (%)
Benzene
Asphalt Ridge
Big Clifty
Sunnyside
163 (26)
147 (39)
173 (8)
438 (74)
440 (61)
447 (92)
Asphalt Ridge
Big Clifty
Sunny
side
167 (27)
153 (41)
173 (4)
441 (73>
448 (59)
454 (96)
Table 3.
Acid Carbonate Determinations of
Sunnyside, Big Clifty, and Asphalt
Ridge Tar Sands
Tar Sand
Sunnyside
Big Clifty
Asphalt Ridge
Acid Carbonate, wt%
Figure 1. Evolution of Hexanes as a Function of
Pyrolysis Temperature for Sunnyside Tar Sand.
Quartz Reactor at a 4°C/min Heating Rate.
5000
4000
3000-
2000-
1000-
TEMPERATURE, °C
Figure 2. Evolution of Methane aa a Function of
Pyrolysis Temperature for Sunnyside Tar Sand.
Quartz Reactor at a 4°C/min Heating Rate.
<
cc
o
I
z
io
o
o.oo
TEMPERATURE, °C
Figure 3. Evolution of Hydrogen as a Function of
Pyrolysis Temperature for Sunnyside Tar Sand.,
Quartz Reactor at a 4°C/min Heating Rate.
0.12
0.10-
0.08"
0.06-
0.04-
0.02-
0.00 I
50
'
'
250
•*
— '«
450
'
'
650
TEMPERATURE, °C
'
<—
850
Figure 4. Evolution of Carbon Monoxide as a F u n c t i o n of
Pyrolysls Temperature for Sunnyslde Tar S a n d .
Quartz Reactor at a 4°C/min Heating R a t e .
0.3"
TEMPERATURE, °C
Figure 5. Evolution of Carbon Dioxide as a Function of
Pyrolysis Temperature for Sunnyside Tar Sand.
Quartz Reactor at a 4°C/min Heating Rate.
<
DC
O
s
o
o
TEMPERATURE, °C
Figure 6.
Evolution of Water as a Function of P y r o l y s i s
Temperature f o r Sunnyside Tar Sand. Quartz
Reactor at a 4°C/min Heating Rate.
TEMPERATURE, °C