2592 Ind. Eng. Chem. Res.

2000, 39, 2592-2600

Predictive Heat Model for Australian Oil Shale Drying and

Retorting

Adam J. Berkovich,† John H. Levy,‡ Brent R. Young,*,§ and S. James Schmidt|

Department of Chemistry, Materials and Forensic Science, University of Technology, Sydney, Sydney,
Australia, Division of Energy Technology, Commonwealth Scientific and Industrial Research Organisation,
Lucas Heights Science and Technology Centre, Menai, Australia, Department of Chemical and Petroleum
Engineering, University of Calgary, Calgary, Alberta, Canada, and Southern Pacific Petroleum (Development)
Pty Ltd., Brisbane, Queensland, Australia

The exploitation of Australia’s oil shale reserves has been the subject of much research over
several decades. The extraction of oil from shale is usually a thermal process and therefore oil
shale processing is dominated by heat-transfer and thermal reactions. To fully develop any oil
shale processing technology, knowledge of an oil shale’s thermodynamic properties is desirable.
This paper presents a novel approach for the determination of an oil shale’s thermodynamic
properties and subsequent development of a predictive heat model. This approach involves
experimental determination of the thermodynamic properties of an oil shale’s individual
components, in particular, the unique kerogen and clay minerals in Australian oil shale. The
experimental data was then used to develop a predictive heat model for Australian oil shale
based upon its kerogen and mineral, composition, and concentrations. The predictive heat model
allows investigation of heat capacity, enthalpy, and total enthalpy for Australian oil shale during
the process temperatures of drying and retorting.

Introduction nantly hydrocarbon vapor that is collected and trans-

Australia has a vast reserve of oil shale deposited
throughout its northeastern regions as well as smaller
deposits located in its southeast. The current estimate
of Australia’s in situ shale oil reserve is approximately
23 × 109 barrels, equivalent to 20 times Australia’s
current crude oil reserves.1 In recent years there has
been renewed interest in an Australian oil shale indus-
try.
In Australia, the proposed processing technique is the
AOSTRA-Taciuk continuous flow retort system, which
is based on rotary kiln technology.2 The processor
consists of four compartments: drying/preheating of
feed oil shale, retorting of dried oil shale, combustion
of retorted oil shale, and heat recovery from combusted
oil shale.
Oil shale is fed into the drying/preheating stage of
the processor where it is heated to ≈250 °C. At the
preheat temperature, residual surface moisture as well
as any water associated with the crystal structure of
relevant minerals in the oil shale are liberated. The
preheated oil shale (at 250 °C) then passes into the
retort stage where it is mixed with recycled combusted
oil shale (at 750 °C). The mixing of the preheated and
combusted oil shale results in a retort temperature of
≈500 °C. In the retort, kerogen is pyrolyzed to predomi-
* To whom correspondence should be addressed. Depart-
ment of Chemical and Petroleum Engineering, University of
Calgary, 2500 University Drive N.W., Calgary, Alberta, Canada
T2N 1N4. Phone: (403) 220-8751. Fax: (403) 282-3945.
E-mail: byoung@ucalgary.ca.
† University of Technology, Sydney.
‡ Commonwealth Scientific and Industrial Research Orga-
nization.
§ University of Calgary.
| Southern Pacific Petroleum (Development) Pty Ltd.
10.1021/ie990942g CCC: $19.00 © 2000 American Chemical Society
Published on Web 06/13/2000
ferred to the oil recovery section of the process. The
organic pyrolysis reactions are accompanied by a num-
ber of other thermal reactions due to the mineral
components in the oil shale. These reactions include the
partial decomposition of pyrite, the dehydroxylation of
the clay minerals, and the decomposition of some
carbonate minerals.3
The retorted oil shale is then transferred to the
combustion stage where the residual carbon from the
oil shale is burnt at approximately 750 °C. The com-
busted oil shale is split into two streams. One stream
is recycled through the retort to provide the necessary
heat for retorting. The other stream is fed to a cooling
zone where it transfers heat to the oil shale being fed
into the preheat/drying stage.
The continued development of the AOSTRA-Taciuk
processor for oil shale processing requires appropriate
process models. In a process dominated by heat-transfer
and thermal reactions, knowledge of oil shale thermo-
dynamic properties is important.
The published examination of oil shale thermal
characteristics related to processing dates back some
80 years.4,5 This work examined the reaction heats and
heating requirements of whole Colorado oil shale and
found that reaction heats and heating requirements
were dependent on the oil shale composition. Colorado
oil shale has also been the subject of much work on its
thermal characteristics using differential scanning cal-
orimetry and thermogravimetry.6-10 Comparisons be-
tween pyrolysis heats of Colorado and Devonian oil
shale have also been made.7 The pyrolysis heats for
Colorado oil shale were found to be lower because of the
differences in mineralogy between Colorado and Devo-
nian oil shales, in particular, the influence of pyrite
found in the Colorado shales. Other work has shown a
correlation between total measured enthalpy and oil

shale grade; that is, the higher the oil yield for the shale,
the higher the total measured enthalpy.8-10
The application of thermal analysis to coal and oil
shale has been reviewed.11 Thermogravimetry and dif-
ferential scanning calorimetry have been shown to be
useful tools in determining the oil yield potential,
reaction heats, and effect of minerals in different oil
shales.12-15 Drop calorimetry has also been used to
measure the heat of retorting for Green River oil shale
up to 773 K.16,17 Thermal analysis has also been coupled
with spectroscopy to investigate the retorting behavior
of carbonaceous oil shales from the Nagoorin and
Condor deposits in Australia.21
The thermal properties of Eastern and Green River
oil shales from the United States have also been
determined using a combination of thermodynamic data
from the literature and the average concentrations of
oil shale components, to sum the heat effects for an
average shale.18,19 The heat capacities of kerogen and
kerogen char were estimated using heat capacity data
of model compounds, such as anthracene, polymeric
organic materials, and graphite, and adjusting the heat
capacities according to the hydrogen and carbon con-
tent.18,19
Australian oil shales have a more complex mineralogy
than U.S. oil shales. For example, Australian oil shales
from Stuart/Rundle are a mixture of kerogen, clays,
carbonate minerals, silica minerals, and pyrite. The
thermal decomposition, pyrolysis, and dehydroxylation
of these oil shale components overlap in the temperature
range from 673 to 823 K (400-550 °C).27,3 As a result,
the overall mass loss, enthalpy, and heat capacity
change for oil shale is a combination of all components.
Previous experimental work in oil shale thermal
characterization discussed above has treated oil shale
as a single material. Consequently, thermal character-
ization measurements were made on whole oil shale and
the data then mathematically treated (usually simul-
taneous linear regression) to determine the contribu-
tions of the individual components. This method is
usually satisfactory for oil shales that have a simple
mineralogy, such as the Green River oil shales, which
have a carbonate mineral base and only one dominant
clay mineral. However, this method cannot be applied
satisfactorily to Australian oil shales, in this case Stuart
oil shales, as the diverse mineralogy of Stuart oil shale
makes measurement of thermodynamic properties dif-
ficult. Each component in the oil shale has a different
concentration, different heat capacity, and different
reaction heats, and the temperature range of thermal
reactions overlap each other.28
This paper reports on a new experimental approach
to oil shale thermal characterization, which involves
treating oil shale as a mixture of different components
that have individual thermal characteristics. In par-
ticular, the unique components of Australian oil shale,
kerogen, smectite, kaolinite, and illite, are of the most
interest. By chemical and physical separation of these
unique components from whole oil shale, the thermo-
dynamics of these individual components can be deter-
mined experimentally. The other more common mineral
components found in Stuart oil shale, such as calcite,
quartz, siderite, and feldspar, have well-known ther-
modynamic properties. For these components, thermo-
dynamic data were obtained from databases in the
literature.29-50
This study also employed the use of modulated
Ind. Eng. Chem. Res., Vol. 39, No. 7, 2000 2593
differential scanning calorimetry (DSC)51 for thermo-
dynamic measurements. Modulated DSC is a relatively
new calorimetric technique that is capable of quantita-
tively measuring heat capacity and enthalpy changes
in a single experiment. This particular feature is unique
to this technique and has important consequences for
oil shale analysis.
Siroquant52,53 is a software package for quantitative
analysis of minerals by X-ray diffraction (XRD). It
contains a specialized package for the analysis of clays.54
Siroquant has previously been applied successfully to
Australian oil shales55 and was further developed in this
study to determine mineral concentrations in oil shales,
kerogens, and isolated clay mixtures. The thermal,
spectroscopic, and literature data of the individual
components were collated to develop a predictive heat
model of Stuart oil shale. The model allows prediction
of the thermodynamic properties of an oil shale based
on its mineral and organic composition. The model can
be directly applied or incorporated into oil shale process
models and can be used to investigate the sensitivity of
thermodynamic properties related to an oil shale’s
composition. The predictive heat model was designed
to be interactive, allowing the user to select any tem-
perature range in the drying and retorting process
temperature range.
The model can be used in the process design, optimi-
zation, and control of industrial oil shale drying, retort-
ing, and combustion plant. In process design, reliable
estimates of the heat capacities and reaction enthalpies
of raw, dried, and pyrolyzed oil shales are required for
the determination of heat balances and the subsequent
mechanical design of process equipment. The model can
be directly incorporated into process models for process
optimization by using the model to investigate the
sensitivity of a process related to an oil shale’s composi-
tion. In a similar manner the model is useful in process
control as it may be used to fine-tune the process
operating conditions based on periodic laboratory oil
shale composition measurements.
Experimental Section
Modulated differential scanning calorimetric (MDSC)
analyses were performed on a TA Instruments MDSC
2920 instrument, with a working temperature range of
148 to 998 K. Samples were analyzed in aluminum pans
with aluminum lids in an atmosphere of dry nitrogen
flowing at 120 mL min-1. Nominal sample mass was 5
mg, which was measured to 1 µg with a microbalance.
Samples were equilibrated at 273 K for 5 min and then
heated at 5 K min-1 to 873 K. The modulation ampli-
tude was (1 K with a period of 60 s. Temperature and
enthalpy were calibrated using In, Sn, and Zn stan-
dards. Heat capacity was calibrated with a 99.97%
sapphire standard.
A TA Instruments SDT 2960 instrument was used for
thermogravimetry. The samples were analyzed in open
platinum pans at a heating rate of 5 K min-1 from
ambient to 873 K in an atmosphere of dry nitrogen
flowing at 120 mL min-1.
Two types of oil shale samples were selected for this
study, one set for kerogen isolation and the other set
for clay mixture isolations. Samples with a high kerogen
concentration were selected for kerogen isolation. Both
brown and carbonaceous kerogens were isolated. The
high kerogen concentration required minimum chemical
treatment, as those minerals not affected by the chemi-
2594 Ind. Eng. Chem. Res., Vol. 39, No. 7, 2000

Table 1. Combined Results for Siroquant and Chemical Table 2. Siroquant Analysis Results for Pyrolyzed
Analyses for Isolated Stuart Kerogens Kerogens (Including Organic Matter)

component concentration brown carbonaceous sample PK1 PK5

(% of kerogen) K1 K2 K3 K4 K5 pyrite (% of pyrolyzed kerogen) 10.0 11.4
pyrite 4.7 5.9 3.4 7.9 6.6 pyrrhotite (% of pyrolyzed kerogen) 9.6 7.3
anatase 0.7 0.4 0.7 0.3 0.4 anatase (% of pyrolyzed kerogen) 3.0 1.3
miscellaneous minerals 0.8 0.7 1.6 0.7 0.6 miscellaneous minerals (% of pyrolyzed kerogen) 6.7 3.3
organic matter 93.8 93.0 94.3 91.1 92.4 organic matter (% of pyrolyzed kerogen) 70.7 76.7

Table 3. Siroquant Results for Clay Minerals Isolated

cal treatment would be concentrated to the least extent. from Stuart Oil Shale
The clay minerals in Stuart oil shale usually exist as smectite kaolinite illite quartz albite cristobalite
mixtures of kaolinite, smectite, and illite in different sample (%) (%) (%) (%) (%) (%)
ratios. The three clay types, kaolinite, smectite, and
C1 31.0 19.9 28.1 12.0 2.9 6.0
illite, in Stuart oil shale cannot be separated from each C2 7.5 18.9 25.8 41.4 5.7 0.6
other. Therefore, a range of oil shales was selected for C3 11.6 38.2 20.1 17.8 4.0 8.3
clay isolation to ensure a greater diversity in the C4 0.4 11.7 20.7 58.6 8.6 0.0
composition for adequate characterization of the indi- C5 43.2 14.3 9.0 25.7 7.4 0.4
vidual clays. C6 41.3 17.4 8.8 20.7 9.4 2.5
Kerogen was isolated from oil shale using a HF/BF3 C7 48.9 10.1 28.7 8.9 2.4 1.0
C8 38.7 21.7 11.6 14.9 5.8 7.3
maceration technique56 where carbonate-type minerals C9 30.8 22.0 13.7 25.0 5.8 2.8
are destroyed with hydrofluoric acid and boron trifluo- C10 10.9 28.9 21.7 22.6 4.4 11.5
ride, generated from the reaction of hydrofluoric and C11 73.7 10.6 12.5 2.0 1.2 0
boric acids. Pyrolyzed samples of kerogen and oil shale C12 32.4 15.1 24.6 20.1 5.2 2.5
were also prepared by heating samples to 520 °C in an C13 23.6 20.2 15.5 31.0 6.4 3.3
atmosphere of flowing nitrogen and then quenching the C14 37.7 21.3 9.0 25.8 5.8 0.5
C15 42.6 21.9 8.8 21.1 5.2 0.5
sample at room temperature while the nitrogen atmo- C16 34.6 17.7 9.8 31.6 6.3 0.0
sphere was maintained.
The clay minerals were isolated from oil shale using Table 4. Thermogravimetric Mass Loss at 773 K for
buffered acetic acid and hydrogen peroxide.57 Acetic acid Isolated Kerogens
destroyed carbonate minerals and hydrogen peroxide kerogen initial mass final mass mass loss
destroyed the kerogen. The result was a mixture of clay sample (mg) (mg) (%)
minerals and silica-type minerals such as quartz and K1 10.21 2.22 78.2
feldspar. These heavier silica minerals were separated K2 10.42 2.30 78.0
from the lighter clay mixture by centrifugation. The clay K3 10.49 2.10 80.0
mixtures were comprised of kaolinite, smectite, and K4 19.74 5.23 73.5
illite, in varying ratios. K5 19.13 5.99 68.7
XRD patterns were collected using a Siemens Kri- Table 5. Dehydroxylation Mass Losses for Clays Isolated
stalloflex X-ray generator equipped with two powder from Stuart Oil Shale
cameras with Bragg-Brentano geometry. A Philips
dehydroxylation dehydroxylation
PW2276/20 X-ray tube was used at a power of 30 mA sample mass loss (%) sample mass loss (%)
and 45 kV to produce cobalt X-rays. Samples were
mounted in aluminum sample holders of dimensions 44- C1 10.9 C7 17.1
C2 14.2 C8 15.9
mm long (in the plane of the X-rays), 12.5-mm wide, C3 3.0 C9 17.6
and 1.7-mm deep. XRD patterns were collected from C4 8.6 C10 15.6
3.00° to 90.00°, at intervals of 0.04° 2θ using a count C5 5.4 C11 13.4
time of 10 s/interval. C6 5.5 C12 19.4

Results and Discussion correct measured thermodynamic data on isolated Stu-

Initially, 66 oil shale samples from the Stuart deposit
were acquired and their XRD patterns measured. The
patterns were analyzed using Siroquant to determine
mineral concentrations in the oil shales. Samples to be
included in the study were selected using these data.
Five samples were selected for kerogen isolation and 16
samples were selected for clay mineral isolation.
The purity of kerogen and clay minerals isolated from
Stuart oil shale was assessed using XRD and chemical
analyses. Siroquant analysis of the XRD patterns
determined the concentrations of any mineral inclusions
in the isolated materials. XRD patterns of isolated
brown and carbonaceous kerogen showed peaks arising
from anatase and pyrite: minerals which are inert to
the chemical treatments used to isolate the kerogen. The
combined results of the Siroquant and chemical analy-
ses are shown in Table 1, while Table 2 presents
Siroquant analysis results for pyrolyzed Stuart kero-
gens. These concentrations were subsequently used to
art kerogen and pyrolyzed kerogen.
The X-ray patterns of the isolated clays also showed
low concentration of included minerals: quartz, cristo-
balite, and albite. These silica-based minerals were
unaffected by the chemical treatments and could not be
completely separated from the clays by centrifugation.
However, the concentrations of these minerals are
relatively low and corrections for their effects could be
made in subsequent analyses. Siroquant results for the
isolated clays also show a diverse range of clay concen-
trations in each sample (Table 3).
Results of thermogravimetric analyses performed on
the isolated kerogen and clay samples are summarized
in Tables 4 and 5.
The raw heat capacity of pyrolyzed brown and car-
bonaceous isolated kerogen was measured using modu-
lated DSC over the temperature range 273-773 K (0-
500 °C). The heat capacity of pure pyrolyzed kerogen
(PK) was calculated by subtracting the heat capacities
of the mineral matter components from the raw heat

Table 6. Heat Capacity Equation Coefficients (J g-1 K-1)
for Pyrolyzed Kerogens
sample
coefficients PK1 PK5
a 2.503 -7.490 × 10-2
b -1.781 × 10-2 7.535 × 10-3
c 6.690 × 10-5 -1.889 × 10-5
d -9.100 × 10-8 3.035 × 10-8
e 4.355 × 10-11 -1.906 × 10-11
R2 1.0000 0.99877
std. dev. 2.792 × 10-10 0.008
capacity data. Heat capacity data for R-alumina were
used for the miscellaneous minerals, which in any case
represent only a small proportion of the material. These
corrected data were fitted to a fourth-order polynomial
equation of the type Cp ) a + bT + cT2 + dT3 + eT4.
The coefficients are given in Table 6.
The heat capacity of kerogen isolated from Stuart oil
shale was measured using modulated DSC. However,
at temperatures above 623 K, pyrolysis of the kerogen
with the accompanying loss of mass began to influence
the heat capacity data and a different approach had to
be used. The heat capacity of isolated kerogens was
measured up to 673 K (the beginning of pyrolysis).
These data were corrected for moisture present in the
samples, measured by TG/DTA, so that the heat capac-
ity determinations were reported on a dry basis. The
measured heat capacities were also corrected for min-
eral inclusions (Table 1). The adjusted data were fitted
to the fourth-order polynomial Cp ) a + bT + cT2 +
dT3 + eT4 to give the coefficients in Table 7. The
temperature range used for fitting was 273-623 K
because the onset of pyrolysis began to influence the
results in the temperature region above 623 K (350 °C).
The initial attempts to measure heat capacities of
kerogens with the modulated DSC resulted in very low
values of heat capacity data after pyrolysis. These
values were often negative and quite different from the
values for the heat capacity of the pyrolyzed kerogen
as measured above, after allowance was made for the
change in mass. Further investigation showed that the
modulated DSC heat flow curve base line after pyrolysis
was wrongly positioned because the instrument could
not cope with the large mass losses of 69%-80% that
occur during kerogen pyrolysis.28 A possible solution was
to dilute the kerogens with R-alumina and measure the
heat capacities of the mixtures, such that the alumina
would help retain sufficient material in the sample pan
during and after pyrolysis to give good coupling of the
sample with the pan and hence the thermocouple
sensor. This was attempted, but because of the loss of
pyrolysis products, it was not possible to encapsulate
the samples properly, resulting in heat capacity data
that were still inconsistent with pyrolyzed kerogen data.
The following method was employed to obtain con-
sistent data. As stated previously, accurate heat capac-
Table 7. Heat Capacity Equation Coefficients (J g-1 K-1) from 273 to 623 K for Isolated Kerogens
coefficients K1 K2
a -5.185 -2.674
b 5.781 × 10-2 2.356 × 10-2
c -1.809 × 10-4 -3.816 × 10-5
d 2.632 × 10-7 2.950 × 10-8
e -1.423 × 10-10 -1.008 × 10-11
R2 0.99418 0.99875
std. dev. 0.027 0.014
Ind. Eng. Chem. Res., Vol. 39, No. 7, 2000 2595
Figure 1. Heat capacity curves for Stuart kerogen K1 (solid) and
K5 (dash) between 273 and 773 K.
ity data had been measured for the kerogen up to the
temperature prior to pyrolysis beginning at about 623
K. Heat capacity data for pyrolyzed kerogen have also
been accurately measured across the full temperature
range, to 773 K. It was reasonable to assume that the
change in heat capacity between kerogen and pyrolyzed
kerogen would be proportional to the change in mass of
the kerogen. This change was therefore modeled using
the thermogravimetric data obtained under the same
heating conditions for the same sample (Table 4). Thus,
the heat capacity value of kerogen at 623 K was taken
as the initial value. The heat capacity value for the same
kerogen pyrolyzed at 773 K (in J gpyrolyzed kerogen-1) was
converted to J gkerogen-1 on the basis of mass loss
observed by thermogravimetry (Table 4), corrected for
the included minerals and taken as the final value. The
difference between the initial and final values was then
multiplied by the fraction of mass loss occurring at 1 K
intervals between 623 and 773 K, and each value was
subtracted from the initial value to construct the model
curve. These data were poorly fitted with a fourth-order
polynomial equation so an eighth-order polynomial
equation was used over this temperature range to give
the coefficients as shown in Table 8. The full heat
capacity curves for a kerogen sample K1 (brown) and
K5 (carbonaceous) are shown in Figure 1.
Initial attempts to measure the enthalpy of pyrolysis
for isolated Stuart kerogens using modulated DSC also
gave unexpectedly low values, as found for the heat
capacity measurements. These low results were at-
tributed to the very large mass loss in the sample during
pyrolysis and to the very endothermic nature of the
pyrolysis reaction.
To solve this problem, the kerogens were diluted with
alumina before the enthalpies of pyrolysis were mea-
sured. Alumina is inert over this temperature range and
kerogen sample
K3 K4 K5
-7.623 -4.087 -5.260
7.334 × 10-2 4.069 × 10-2 5.109 × 10-2
-2.346 × 10-4 -1.245 × 10-4 -1.408 × 10-4
3.361 × 10-7 1.753 × 10-7 1.887 × 10-7
-1.777 × 10-11 -9.161 × 10-11 -9.840 × 10-11
0.99858 0.99875 0.99779
0.012 0.011 0.017
2596 Ind. Eng. Chem. Res., Vol. 39, No. 7, 2000

Table 8. Heat Capacity Equation Coefficients (J g-1 K-1) During pyrolysis, part of the pyrite is converted to
from 623 to 773 K for Isolated Kerogens pyrrhotite, assumed to be by reduction with hydrogen
sample generated in the organic cracking process.18,60,61 The ∆H
coefficients K1 K5 for this reaction was calculated as 290.4 J g-1, at the
peak temperature of 748 K (475 °C), using Cp and ∆H
a -6.765 × 105 -4.948 × 105
b 5.360 × 103 4.002 × 103
data for pyrite and pyrrhotite. The analysis of the
c -1.671 × 101 -1.289 × 101 pyrolyzed kerogen (Siroquant data) shows that the
d 2.427 × 10-2 2.008 × 10-2 reaction does not proceed to completion, being only
e -1.149 × 10-5 -1.270 × 10-5 55.4% complete at 793 K (520 °C). When this same
f -1.134 × 10-8 -3.690 × 10-9 factor is used for kerogen from sample 65219K, ∆Hpyrite
g 1.680 × 10-11 9.444 × 10-12
h -6.762 × 10-15 -4.007 × 10-15
for 65219K was calculated as 160.9 J gpyrite analyzed-1.
i 5.326 × 10-19 2.599 × 10-19 Then, when the concentration of pyrite in the kerogen
R2 0.9995 0.9999 is taken into account (5.9%), ∆Hpyrite for 65219K2 was
std. dev. 0.021 0.009 7.56 J gkerogen-1. In addition, the dilution effect of the
pyrite, and for the anatase and miscellaneous minerals
Table 9. Enthalpies of Pyrolysis of Stuart K1 Kerogen
Diluted in r-Alumina
that were assumed inert during pyrolysis, also has to
be accounted for. The result is a ∆H of 364 J g-1 for the
concentration concentration enthalpy of pyrolysis of Stuart brown kerogen.
of kerogen (%) ∆H (J g-1) of kerogen (%) ∆H (J g-1)
Although heat capacities were measured on the clay
30 27.20 70 188.1 mixtures isolated from Stuart oil shale, the heat capaci-
50 121.8 80 267.0
60 179.0 ties of the individual clays were not calculated from the
experimental data. The errors associated with indi-
Table 10. Regression Line Parameters for Stuart 65219K vidual heat capacities (deconvoluted from heat capaci-
Kerogen in r-Alumina ties measured on the mixtures) were large compared to
parameter standard error the differences among the heat capacities of the indi-
slope 4.56 0.41 vidual clays. This occurred because the constitutions of
intercept -108.0 16.6 the various clays are all so similar: the chemical
R2 0.974 formulas of smectite, kaolinite, and illite all consist of
number of observations 5 aluminum, silica, and oxygen (that is, an alumino-
degrees of freedom 3 silicate-base structure) with minor contributions by
other substituents, such as potassium, calcium, or iron.
provided bulk to the sample, thereby reducing the mass
Therefore, the value of the heat capacity of the clay is
change occurring in the sample during the experiment
while sample contact with the sensor was maintained. influenced more by the alumino-silicate-base structure
Diluted kerogen samples were prepared in concentra- (which is similar for all clays) rather than by the
tions of 30%, 50%, 60%, 70%, 80% w/w kerogen. Heat substituents. This was evident from the literature heat
flow curves for the diluted samples were measured by capacity data for smectite, kaolinite, and illite,36,45,49
modulated DSC. The pyrolysis peak from the heat flow where capacity values for these clays are similar.
curve was integrated to calculate enthalpy of each Consequently, heat capacity data from the literature
diluted kerogen sample and these data are presented were used for the individual clays.
in Table 9. Heats of dehydroxylation were measured using modu-
A linear regression between measured enthalpy and lated DSC for mixtures of smectite, kaolinite, and illite
kerogen concentration was performed and the regres- isolated from Stuart oil shale. These results are sum-
sion parameters are shown in Table 10. From these marized in Table 11 which also shows the dehydroxy-
coefficients, a raw enthalpy value for a kerogen concen- lation enthalpies corrected for the mineral inclusion
tration of 100% was calculated as 348.2 J g-1. This value concentrations (Table 3) and the enthalpy change as-
must then be corrected for mineral inclusions in the sociated with the R to β transition of quartz. The
kerogen (Table 1). normalized concentrations of smectite, kaolinite and
Table 11. Dehydroxylation Enthalpies for Clays Isolated from Stuart Oil Shale
dehydroxylation x1, x2, x3, y,
peak normalized normalized normalized ∆Hdehyrox’n ∆Hdehyrox’n
temperature concentration concentration concentration (measured) (corrected)
sample (K) smectite kaolinite illite (J g-1) (J g-1)
C1 726.77 0.392 0.252 0.356 201.5 253.2
C2 738.03 0.144 0.362 0.494 139.3 258.4
C3 728.70 0.166 0.546 0.288 231.2 328.1
C4 766.98 0.012 0.357 0.631 120.5 348.8
C5 759.62 0.650 0.215 0.135 218.8 325.0
C6 761.20 0.612 0.258 0.130 247.4 363.7
C7 732.86 0.558 0.115 0.327 220.4 250.3
C8 734.89 0.538 0.301 0.161 178.4 245.6
C9 729.19 0.463 0.331 0.206 187.5 278.3
C10 718.89 0.177 0.470 0.353 233.7 376.2
C11 743.77 0.761 0.110 0.129 225.6 233.0
C12 729.32 0.449 0.209 0.341 219.8 300.7
C13 726.61 0.398 0.341 0.261 249.9 416.0
C14 788.18 0.554 0.313 0.132 240.0 349.3
C15 773.70 0.581 0.299 0.120 247.9 335.5
C16 732.19 0.557 0.285 0.158 249.1 395.8

Table 12. Simultaneous Linear Regression Results for
Isolated Clays
constant 0
std error of y 56.4
R2 0.2230
number of observations 19
degrees of freedom 16
x coefficients 265.3 535.2
error of coefficients 42.8 105.2
Table 13. Dehydroxylation Enthalpies for Smectite,
Kaolinite, and Illite
clay ∆Hdehydroxylation (J g-1) error (J g-1) % error (J g-1)
smectite 265 (43
kaolinite 535 (105
illite 146 (92
illite used for the regression analysis described below
are also shown in Table 11.
The dehydroxylation enthalpies for the individual
clays, smectite, kaolinite, and illite, were calculated
using a simultaneous linear regression analysis of the
measured experimental data. The normalized concen-
trations of smectite, illite, and kaolinite were assigned
to regression ranges x1, x2, and x3, respectively. The
corrected enthalpies for each sample from each experi-
ment were assigned the regression range, y. A simul-
taneous linear regression was performed to fit values
of x1, x2, and x3 to y to calculate coefficients of x (the
regression line was forced through the origin). The
coefficients of x were equal to the dehydroxylation
enthalpy for each individual clay. The results of the
simultaneous linear regression analysis and subsequent
dehydroxylation enthalpy values are shown in Tables
12 and 13.
Inspection of the regression data shows relatively high
errors for the fitted coefficients and subsequent dehy-
droxylation enthalpies. This is mirrored in the value of
R2. There are a number of possible reasons for this.
First, errors have been introduced by the difficulty in
measuring the base line on the high-temperature side
of the peak, resulting in low values for the illite, as it
was possible that part of this peak was beyond the upper
temperature limit of the calorimeter. Indeed, the en-
thalpy for illite has the highest relative error. Second,
the error calculated for simultaneous linear regression
analyses is dependent on the number of degrees of
freedom in the data set. It is possible that if more
samples were measured, there would be a reduction in
the calculated error. Finally, it is quite probable that
the individual clays within the clay mixtures are not
identical, and this leads to significant variation in the
enthalpies, which are reported in the errors. For ex-
ample, it is difficult to believe that all the smectite clays
have identical formulas given that the degree of sub-
stitution may vary within the deposit given that mate-
rial was laid down at different geological times. Even
kaolinite, which has a relatively uniform chemical
formula, has been shown to exhibit different enthalpies
of dehydroxylation dependent upon the crystallinity of
the sample.62-66 Given these considerations, however,
this is the first time that the dehydroxylation enthalpies
have been measured for the clays in oil shales and
represent a major step forward in our ability to be able
to calculate the thermochemical properties of oil shales.
The enthalpy associated with dehydration of oil shale
was also determined using modulated DSC. An average
value of 2196 J g-1 at a peak temperature of 110 °C for
the loss of water was found for 12 oil shale samples.
Ind. Eng. Chem. Res., Vol. 39, No. 7, 2000 2597
Table 14. Sources of Error in the Predictive Heat Model
error source total error (%)
literature heat capacity data 8
literature enthalpy data 5
XRD/Siroquant 3
MDSC heat capacity measurements 1-3
MDSC enthalpy measurements <1
146.0
MDSC temperature measurements <0.5
92.4
polynomial fitting <1
This value is approximately equal to the latent heat of
vaporization for water, 2258 J g-1 at 110 °C.67
The data measured for kerogen and clay minerals
16
20
isolated from Stuart oil shale were combined with
63 literature data for the other mineral components in
Stuart oil shale and used to develop a predictive heat
model. The literature usually revealed several sources
of data for a particular mineral component. In such
cases, an average data set was calculated for each
component and these data were refitted to the same
fourth-order polynomial as the experimental data.
Primarily, the model allows prediction of an oil shale’s
thermochemical properties based upon its mineral
composition. The model was written in a spreadsheet
environment and has been designed for use by process
engineers and others involved in oil shale processing;
therefore, the model is interactive and has different
levels of complexity depending upon the user needs.
The model takes experimental- and literature-sourced
thermodynamic data for each oil shale component,
namely, heat capacity and reaction enthalpy, and
combines them with the concentration of each compo-
nent determined from Siroquant to calculate a total
thermodynamic value for a given oil shale. To use the
model, the user simply inputs concentration values for
each oil shale component and a temperature range. The
user is able to input a temperature range between 0 and
500 °C (this covers the process temperature range of
drying and retorting). The model then calculates values
for heat capacity, sensible heat (integrated heat capac-
ity), and reaction enthalpy for the specified concentra-
tion of each oil shale component. The model then sums
these thermodynamic data and calculates a total en-
thalpy (the sum of sensible heat and reaction enthalpies)
for the whole oil shale. The interactive nature of the
model allows the user not only to predict heat data for
known oil shale feedstocks but also to investigate heat
data for different feedstock scenarios.
Errors arise from the heat capacity and enthalpy data
from literature sources, error in the concentration of
each oil shale component from Siroquant analyses, and
the error from polynomial fitting of experimental and
averaged literature data. Table 14 lists error sources
and the approximate error associated with those sources.
The largest source of error in the database model is
the heat capacity data from the literature. Although
most heat capacity data for the minerals in oil shale
had a quoted accuracy of <1%, others had a quoted
accuracy of between 1% and 2%, and the total error for
all components whose literature dataare used in the
database model is 8%. The enthalpy data from the
literature showed a greater accuracy and the total error
for all oil shale mineral components was 5%. The errors
quoted for the modulated DSC measurements in this
study were determined from analysis of high-purity
(99.9%) mineral standards for enthalpy and heat capac-
ity and high-purity (99.98%) metal standards melting
temperatures for temperature measurements.
2598 Ind. Eng. Chem. Res., Vol. 39, No. 7, 2000
Table 15. Comparison of Integrated Heats Determined
from Predictive Heat Model and Modulated DSC,
298-623 K (25-350 °C)
integrated integrated
heat-predictive heat-modulated
heat model DSC
sample (J g-1) (J g-1)
O1 536 515
O2 509 492
O3 348 356
O4 480 450
O5 456 420
The predictive heat model was validated by compar-
ing the total enthalpy calculated by the model with an
experimentally determined total enthalpy using modu-
lated DSC. Five oil shales from the sample suite, O1,
O2, O3, O4 and O5, were selected for comparison
because these samples showed suitable differences in
their mineralogy, which ensured that the selection was
representative of oil shale from the Stuart deposit.
The comparison was performed in the following way.
The concentration of the mineral components in each
oil shale was entered into the database model and the
total enthalpy calculated for the temperature range
298-623 K (25-350 °C). This temperature range was
selected so that the mass loss interferences described
above would not affect the integrated heat determina-
tion. The integrated heat was determined by measuring
the heat capacity of the oil shales for the same temper-
ature range above using modulated DSC. The modu-
lated DSC data was then plotted versus temperature
and fitted to a fourth-order polynomial, Cp ) a + bT +
cT2 + dT3 + eT4. This expression was then integrated
and the integrated heat calculated. Table 15 shows the
comparison between integrated heats calculated from
the predictive heat model and the integrated heats
determined from modulated DSC experiments.
The above results show good agreement between the
database model and experimental results, with the
predicted values being within 5% of the experimental
values, which is well within the experimental error.
The database model can also be used to calculate total
enthalpy of retorted oil shale. Oil shale sample O2 was
used as an example. Estimates were made of the
concentrations of components in a retorted oil shale on
the basis of mass loss (TG) data. The heat capacities of
pyrolyzed kerogen and dehydroxylated clay minerals
measured by modulated DSC were incorporated into the
database model so that the total enthalpy of retorted
oil shale could be calculated. The concentrations of
decomposition products of minerals in the original oil
shale were calculated from the mole ratios of the
decomposition reactions of each component.
A sample of retorted oil shale was prepared from a
sample of O2 oil shale in a manner similar to the
preparation of pyrolyzed kerogen. The retorted shale
was then analyzed by modulated DSC to determine the
heat capacity for the temperature range 298-773 K
(25-500 °C). Further validation of the model was
performed by comparing the total enthalpy calculated
by the database model and that determined by modu-
lated DSC for retorted oil shale.
Table 16. Heat Capacity Coefficients from Modulated DSC of Retorted O2 Oil Shale for the Temperature Range 298-773
K (25-500 °C)
sample a b
O2 0.2350 0.002 123
Figure 2. Oil shale grade versus total enthalpy.
The heat capacity from modulated DSC was fitted to
a fourth-order polynomial and the total enthalpy cal-
culated. Table 16, shows the heat capacity coefficients
for retorted O2 shale. The total enthalpy for O2 was
determined to be 551 J g-1, compared to the database
model calculation of 516 J g-1 for retorted O2 oil shale.
Again, excellent agreement is obtained between experi-
mental and model results.
As is apparent from the above, the predictive heat
model cannot be validated against experimental data
over the full range of process temperatures (298-773
K) for whole oil shale. This is where the predictive heat
model supersedes experimental techniques. The data-
base model was developed using critically reviewed
literature data as well as thermodynamic data mea-
sured on the unique components isolated from Stuart
oil shale. The complex nature of Australian oil shale
mineralogy was the reason that thermodynamic data
could not be determined on whole oil shale directly and
therefore required this approach. That is, a suitable
predictive heat model was developed so that the thermal
characteristics of whole oil shale can be explored over
the full range of processing temperatures.
It has been shown8,18 that a linear relationship exists
between U.S. oil shale grade (in liters of oil per ton of
shale at 0% moisture (LTOM)) and total enthalpy. The
predictive heat model was used to calculate the total
enthalpy for the oil shale samples in the sample suite.
The total enthalpy was then plotted versus LTOM and
displayed in Figure 2.
Inspection of Figure 2 shows at best an approximate
linear relationship with some substantial deviations. In
a similar attempt27 at correlating total enthalpy versus
oil shale grade for a series of Australian oil shales from
different deposits, no clear correlation was found. The
reason for the differences in correlating oil shale grade
with total enthalpy can be attributed to differences in
mineralogy of the oil shales being compared.
The linear correlation found previously8,10,18 was for
Green River and Eastern oil shales from the United
States. Both of these oil shales have relatively simple
mineralogies compared to those of Australian oil shales.
The Green River oil shales have a simple predominantly
c d e
1.0255 × 10-6 -4.708 × 10-9 2.958 × 10-12

carbonate mineral base, of calcite and dolomite, which
do not decompose at retorting temperatures. Smectite
has also been found in Green River oil shales, though
only in very small amounts (<10%). In essence, these
minerals simply act as a diluent for kerogen that leads
to a linear relationship between enthalpy and grade.
Indeed, the results presented in this study for pyrolysis
enthalpies of kerogen diluted in alumina showed an
almost perfect linear relationship. However, the oil
shales studied here have a diverse range of carbonate
minerals and clays that have a tremendous effect on
the heat requirements during processing (total en-
thalpy), depending upon their respective concentrations.
These effects have also been observed for Rundle oil
shale,16 where it was found that a significant amount
of extra heat was required for the retorting of Rundle
shale compared to that of Green River oil shale. The
Rundle shale examined in that study is akin to Stuart
oil shale because it is from a shale deposit that is
contiguous with Stuart.
The nature of Australian oil shales requires a more
complex approach to predicting their thermal charac-
teristics rather than simple correlations that have been
used for U.S. oil shales. This only increases the calibre
of the predictive heat model developed here as a tool
for investigating the thermal characteristics of Austra-
lian oil shales.
Conclusions
The continued development of oil shale processing
technologies and the re-emerging Australian oil shale
industry have provided the impetus for accurate deter-
mination of oil shale thermodynamic properties. The
complexity of Australian oil shale mineralogy warranted
a new approach for the determination of these proper-
ties. The new approach involved the chemical and
physical separation of the unique components of Aus-
tralian oil shale and then thermal analysis of these
materials to measure heat capacity, reaction enthalpy,
and sensible heats. The isolated components and their
original oil shales were also analyzed by X-ray diffrac-
tion and Siroquant to determine mineral concentrations.
The experimental thermodynamic data, literature-
sourced data, and Siroquant data were then combined
to develop a predictive heat model that allows heat
capacity, enthalpy, and total enthalpy to be predicted
during the processes of drying and retorting, on the
basis of an oil shale’s composition.
Acknowledgment
The authors gratefully acknowledge the support of
Southern Pacific Petroleum (Development) Pty Ltd. and
the Australian Research Council for support during this
research project.
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Received for review December 30, 1999
Revised manuscript received April 24, 2000
Accepted April 24, 2000
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