J Therm Anal Calorim
DOI 10.1007/s10973-013-3505-5
Pyrolysis model of oil sand using thermogravimetric analysis
Qing Wang • Chunxia Jia • Qianqian Jiang •
Yin Wang • Deyin Wu
Received: 4 June 2013 / Accepted: 29 October 2013
 Akadémiai Kiadó, Budapest, Hungary 2013
Abstract In this paper, the derivative thermogravimetry
(DTG) curve displays an overlapping peak which consists
of two subpeaks for the major oil-producing stage of
Indonesian oil sand. This study was conducted to supple-
ment the insufficiencies of the previous studies, which
neglected or oversimplified the processing of the overlap-
ping peak and did not determine the kinetic mechanism.
First of all, we assume a two-component parallel reaction
model to describe the mass-loss process of the major oil-
producing stage (overall stage) to obtain the separated
stages. Then, we present an asymmetric multi-peak fitting
method, bi-Gauss, to separate the overlapping peak. Based
on the results of the bi-Gauss method, the kinetic mecha-
nism was obtained using the integral master plot method,
followed by the determination of the activation energy by
the integral iso-conversional non-linear (NL-INT) method.
The results show that the bi-Gauss method can produce
satisfactory fitting results. Moreover, the separated stages
follow single mechanism; while the overall stage does not
follow a single mechanism and the mechanisms of the front
and back segments of the overall stage are in accordance
Q. Wang  Q. Jiang  Y. Wang
Engineering Research Centre of Oil Shale Comprehensive
Utilization, Ministry of Education, Northeast Dianli University,
Jilin City 132012, Jilin, China
e-mail: rlx888@126.com
C. Jia (&)
North China University of Electric Power, Beijing 102206,
China
e-mail: jiachunxia_215@126.com
D. Wu
Indra Boedijono, Indadi Group, Taman Jati Baru Barat 1,
Jakarta 10150, Republic of Indonesia
with those of the separated stages, which prove the reli-
ability of the two-component parallel reaction model.
Keywords Oil sand  Pyrolysis 
Thermogravimetric analysis  Overlapping peak
Introduction
Thermal methods have been extensively used for the
recovery and upgrading processes of oil sand bitumen to
obtain the main product: synthetic crude oil. These pro-
cesses, including in situ combustion, surface-mining ther-
mal cracking and thermal conversion (or coking), are
aimed at heating the oil sand, to vaporize the volatile
compounds, pyrolytically decompose the larger non-vola-
tile molecules into lighters, refine hydrocarbons and obtain
residual carbon (char or coke) [1–3]. Therefore, it is nec-
essary to study the pyrolysis kinetics of oil sand for a more
comprehensive understanding of the pyrolysis process and
mechanism so that the results could be used to guide the
recovery and upgrading processes, design the retorting and
combustion reactors, and improve the quality of thermal
byproducts.
In recent years, with the improvement of thermoanalysis
technique, thermal analysis of fuels has been extensively
used as a means of determining the kinetic parameters of
samples pyrolysis [4–7]. Oil sand pyrolysis has typically
been studied using thermogravimetric analysis (TG).
Although there are certain differences between the pyro-
lysis processes of oil sands from different locations, the
process can be divided into 2 [8–10] or 3 [11–15] stages
prior to reaching 600 C. Oil sand includes a wide range of
components; therefore, the number of parallel, competitive,
and consecutive reactions in the pyrolysis process is quite
123
 Q. Wang et al.

numerous. It is impractical to develop a chemical reaction [32] functions. However, DTG curves of the major oil-
model that covers all the components in the pyrolysis producing stage in this paper cannot be fitted using sym-
process comprehensively. Thus, the pseudo-components metric functions, i.e., neither Gaussian nor Lorenzian
that efficiently simplify the real pyrolysis process have function, because of the asymmetric properties observed.
been widely accepted. Barbour et al. [16] proposed the Fortunately, the theory [23, 26, 27] and empirical results
following global reaction to describe the oil sand pyrolysis [33–36] of bi-Gauss method have been suitably applied for
process: Bitumen ! Oil þ Gas þ Coke. This reaction is the asymmetric peak in analytical chemistry; however,
also known as an overall single-component reaction model. little application for TG has been reported. Therefore, we
Other reactions belong to the multi-component reaction consider the simple asymmetry function, bi-Gauss, which
model. For example, Rosenvold et al. [11] and Lin et al. is a modification of the Gaussian function to try to separate
[13] realized that the light and heavy organics that the overlapping peak. Then, we calculate the activation
decompose one after the other represent the reaction of energy for the separated stages and the overall stage by the
maltene and asphaltene. Hayashitani [17] assumed that oil integral iso-conversional non-linear (NL-INT) method and
sand bitumen consists of asphaltene and maltene only and the two-component parallel reaction model, respectively.
used a four pseudo-component reaction model to describe Finally, we use the integral master plot method to select the
the oil sand pyrolysis process. Phillips et al. [18] used a six most probable mechanism function for the separated stages
pseudo-component reaction model to describe the solid and the overall stage. The procedures and methods pre-
phase reaction of oil sand below 693 K. Seader and sented in this paper could be applicable to a much wider
coauthors [19] presented a more complex reaction model range of similar kinetic problems.
by combining the solid phase and gas phase reactions of oil
sand with the results of Lin and Phillips. Starting from its
original overall first-order kinetic [15, 16, 20] based on the Experimental
overall single-component reaction model, many optimized
methods [8–10, 12–14, 20–22] have been developed later Materials
to estimate the kinetic parameters for the entire pyrolysis
process (or certain stage) based on the multi-component Oil sand samples, labeled KA BUNGKA (S1) and LAW-
reaction model. ELE ST3 (S2) for this study, were obtained from Indone-
The derivative thermogravimetry (DTG) curves of oil sia. Prior to use, the samples were crushed and screened to
sand samples in this paper contain two clear subpeaks at the desired particle sizes. The proximate analysis, ultimate
the major oil-producing stage. The two subpeaks are so analysis, heating value, and Fischer assay were conducted
close that they have partly overlapped. After reviewing the
DTG curves of other oil sands, only the Alberta oil sand at
Table 1 Properties of Indonesian oil sands
350–600 C showed a similar behavior [15]; however, the
author made no explanation or treatment to those subpeaks. Properties S1 S2
In general, each peak represents a pyrolysis reaction of the Proximate analysis (mass%, ad)
corresponding pseudo-component. Therefore, it seems Moisture/% 1.30 1.06
unreasonable to describe the two subpeaks using an overall Ash/% 46.68 48.03
single-component reaction model. What’s more, another Volatile/% 52.02 50.91
deficiency is the lack of the determination of kinetic Fixed carbon/% a
0.00 0.00
mechanism according to plenty of literatures. Thus, the Ultimate analysis (mass%, daf)
purpose of this paper is to separate the overlapping peak
Carbon/% 55.59 55.43
based on a more suitable two-component parallel reaction
Hydrogen/% 4.54 5.48
model, and then try to determine the kinetic mechanism of
Oxygen/%a 36.95 36.12
the pyrolysis of Indonesian oil sands.
Nitrogen/% 0.79 0.75
In general, there are some kinds of mathematical sepa-
Sulfur/% 2.73 2.22
ration methods of overlapping signals in analytical chem-
Fischer assay data (mass %, ad)
istry such as the multi-peak fitting (deconvolution),
Oil/% 20.41 18.91
Fourier-transform and wavelet transformation, etc. Various
Water/% 1.40 1.50
methods are based on the selection of elementary functions
Char/% 74.07 76.24
[23–27]. More recently, the multi-peak fitting as the most
Gas/%a 4.12 3.35
popular method has been successfully applied in the field
Heating value/kJ kg-1 (ar) 9,798.50 9,494.42
of biomass pyrolysis to separate the overlapping peak of
a
the DTG curve by the Gaussian [28–31] and Lorenzian By difference

123
Pyrolysis model of oil sand
according to the ASTM standard. The properties of the
samples are listed in Table 1.
Thermogravimetric analysis
In this research, thermogravimetry (TG:DTG) experiments
were conducted with a SDT-Q600 thermogravimetric
analyzer at heating rates of 5, 15, and 25 C min-1 in a
range of ambient temperature to 550 C under a steady
flow of nitrogen (80 L min-1). In all cases, the average
initial sample mass was about 10 mg, and the particle size
was 0–0.2 mm.
Three oil sands samples exhibit similar patterns of
thermal decomposition as pyrolysis temperature was
increased. The analysis of these curves demonstrates that
there are three stages of mass-loss profile best illustrated
in the derivative curves. Although many chemical and
physical processes contribute to the observed mass loss
of oil sand, three basic stages encompass the conversion:
the lower temperature region, from ambient up to
approximately 130 C, produced mass loss which has
been attributed to the loss of moisture, which accounts
for almost 2 % of sample mass. The subsequent stage
took place at 150–520 C, wherein represents a slow
mass loss at 380–500 C and accounts for almost 8 % of
sample mass, can be assumed as the decomposition of
light hydrocarbons and desorption of organic gases;
however, a major portion of mass loss with a maximum
rate at about 450 C is due to the thermal decomposition
of indigenous bitumen. In the third stage, between 580
and 750 C, the mass loss is attributed to the decom-
position of carbonate minerals. At the same time, the
presence of CO2 (which evolved as a product of car-
bonate decomposition) and which at high temperature
reacted with residual char to form CO also caused some
mass loss.
From the DTG curves, it can be seen that heating rate
also affects the mass loss at a certain temperature. For
example, at the same temperature, the lower the heating
rate, the more the volatile material evolved. The effect of
heating rate to overall mass loss is not clear, but it obvi-
ously shortens the time of decomposition, advanced the
rate of mass loss.
Theoretical
Separation of overlapping peak
Basic idea of multi-peak fitting method
The multi-peak fitting method, which increases the signal
resolution by a mathematical algorithm based on the
appropriate function as the peak fitting function, is valid to
separate overlapping peaks in the DTG curve. The basic
idea of this method is as follows: first, choose an appro-
priate function to describe the DTG curve of the subpeak
and select three initial parameters: peak height, peak
position, and full width at half maximum (FWHM) to form
a three-parameter matrix P. Second, apply the Levenberg–
Marquardt algorithm to obtain the matrix P with repeated
iterations until the sum of squares of the differences
between the experimental and fitted data SS (Eq. 1) meets
the minimum value.
Xn
SS ¼ wi ½yi  fi ðxi ; PÞ2 ð1Þ
i¼1
where wi is the weighted factor and n is the number of
iterations.
In the above non-linear least square fitted method, the
fitted result would not converge if inappropriate initial
parameters were selected. Therefore, another evaluation
function v2 (reduced Chi squared) should be used to
ascertain the number of iterations. In this way, the calcu-
lations would be performed with the actual number of
iterations when the tolerance (the relative variation of twice
iterations) is achieved before the original number of iter-
ations, which was arbitrarily defined. Here, v2 have various
forms with their own wi , as for the no weighting form, each
point has the same weighted factor (wi ¼ 1) and the v2 can
be defined as:
Xn
v2 ¼ ðyi  fi Þ2 ð2Þ
i¼1
Bi-Gauss multi-peak fitting method
In theory, the thermal-effect peak of a simple reaction
should be a single peak with a symmetrical shape. The
Gaussian or the Lorentzian function is commonly used to
solve this kind of peak. In practice, the real peak is likely
not strictly symmetrical, which needs a modified function
to correctly fit the peak. We suggest an asymmetric
Gaussian function bi-Gauss, to describe the overlapping
peak in the DTG curve. The bi-Gauss function can be
expressed by
8 h i
< H exp ðxi  xc Þ2 =2r21 ; xi \xc
fi ¼ h i ð3Þ
: H exp ðxi  xc Þ2 =2r2 ; xi [ xc
2
where H is the peak height, r1 is the left-FWHM, r2 is the
right-FWHM, and r1 6¼ r2 . Different values of FWHM r
indicate that each branch of asymmetric peak can be
described separately by the function with the own value of
width parameter [26, 27]. In addition, the parameter values
can be simply determined from the experimental curve
[33].
123
 Q. Wang et al.

Multi-component parallel reaction model The integral form of the kinetic equation in the non-
isothermal pyrolysis is given by
The multi-component parallel reaction model regards the Z T
overall stage as a result of the combination of several GðaÞ  A=b expðE=RT ÞdT ¼ ðA=bÞ  IðE; TÞ ð9Þ
0
independent pyrolysis reactions by neglecting the interac-
tions among pseudo-components; i.e., if we assume that a where GðaÞ is the integral form of the kinetic mechanism
subpeak represents an independent reaction of pseudo- and IðE; TÞ is the temperature integral.
component, the overall stage kinetic parameters can be The kinetic mechanism GðaÞ of the substance is the
obtained by weighting and superimposing the subpeak same at the selected a for different b. In this case, it leads
kinetic parameters. The weighted factor is the ratio of the to the following relationship:
pseudo-component mass loss to the total mass loss. ðA=b1 ÞIðEa ; T1 Þ ¼ ðA=b2 Þ  IðEa ; T2 Þ ¼   
In non-isothermal pyrolysis, the differential form of the ¼ ðA=bn Þ  IðEa ; Tn Þ ð10Þ
kinetic equation of component i is given by
dai =dT ¼ Ai =b expðEi =RT Þfi ðaÞ ð4Þ where n is the number of heating rates. When i 6¼ j,
rearranging Eq. (9) gives
where ai is the conversion, Ai is the apparent pre-expo-   
bj  IðEa ; Ti Þ bi  IðEa ; Tj Þ ¼ 1 ð11Þ
nential factor, b is the heating rate, Ei is the apparent
activation energy, R is the universal gas constant, T is the Superposition of the expansion terms of the Eq. (10), the
absolute temperature, and fi ðai Þ is the differential form of problem is converted into one that determines the most
kinetic mechanism. probable activation energy Ea to meet the following equation:
The weighted factor of component i can be calculated 
X n X n   
using 
XðEa Þ ¼ min b  IðEa ; Ti Þ bi  IðEa ; Tj Þ
 i¼1 j6¼i j
ri ¼ ðMi0  Mif Þ=ðM0  Mf Þ ð5Þ 

X
m
 nðn  1Þ
ri ¼ 1 ð6Þ
i¼1
ð12Þ
where Mi0 and Mif are the initial and final mass of com-
Using the secondary rational approximation of Senum-
ponent i, respectively, M0 and Mf are the initial and final
Yang (Eq. 12) to simply IðEa ; TÞ, an optimization
mass of sample, respectively; m is the number of pseudo-
algorithm can be programed by a FORTRAN software.
component.   
The conversion and activation energy of the overall IðEa ; TÞ ¼ Teu ðu þ 4Þ u2 þ 6u þ 6 ð13Þ
stage can be calculated by
Kinetic mechanism
Xm
a ¼ ðM0  MT Þ=ðM0  Mf Þ ¼ ðri ai Þ ð7Þ
i¼1 The most probable kinetic mechanism can be determined
X
m by the integral master plot method proposed by Gotor [39]
E¼ ðri Ei Þ ð8Þ with the premise of accurate E value. Therefore, the
i¼1 E value obtained by the NL-INT method can be used here.
The integral form of kinetic equation Eq. (8) can also be
where MT is the sample mass at temperature T.
written as
GðaÞ  ðA=bÞ  IðE; TÞ ¼ ðAE=bRÞ  PðuÞ ð14Þ
Calculation of kinetic parameters
Using a reference point at a ¼ 0:5, the following
Activation energy equation can be easily derived from Eq. (13):
GðaÞ=Gð0:5Þ ¼ PðuÞ=Pð0:5Þ ð15Þ
One of the model-free methods, integral iso-conversional
non-linear (NL-INT) method which was developed by where the temperature integral PðuÞ can be expressed by
Vyazovkin [37], is chosen to determine the activation the secondary rational approximation of Senum-Yang:
energy in this paper. This method produces an insignificant   
PðuÞ ¼ eu =u ðu þ 4Þ u2 þ 6u þ 6 ð16Þ
amount of error because it does not use the oversimplified
temperature integral approximation and has no limit to the Substituting the average E value of the overall stage and
validity of u ¼ E=RT, while the linear iso-conversional the corresponding temperature T at the selected a under
method requires that u  13 [38]. different b into the right side of Eq. (15) allows the

123
Pyrolysis model of oil sand

Fig. 1 DTG curves of S1 A 0.05

(a) and S2 (b) oil sands at 100

Mass loss rate/% K–1

various heating rates 0.00

Mass loss/%
–0.05
90

–0.10
5K min–1
80
–0.15
15K min–1
a: 5/K min–1
b: 15/K min–1 25K min–1
–0.20
70 c: 25/K min–1
–0.25
200 300 400 500 600 700 800 900 300 400 500 600 700 800 900
Temperature/K Temperature/K
S1 (A)–TG S1 (A)–DTG

B 100 0.05
0.00

Mass loss rate/% K–1

90 –0.05
Mass loss/%

–0.10
80
–0.15

70 5/K min–1 –0.20

15/K min–1 5K min–1
25/K min–1 –0.25 15K min–1
60 25K min–1
–0.30
50 –0.35
200 300 400 500 600 700 800 900 300 400 500 600 700 800 900
Temperature/K Temperature/K
S2 (B)–TG S2 (B)–DTG

experimental master plot of PðuÞ=Pð0:5Þ versus a to be
drawn; then, arbitrary a values (e.g., 0.05, 0.10…0.95, 1) can
be substituted into appropriate integral kinetic mechanisms
to produce the standard master plot of GðaÞ=Gð0:5Þ versus a.
If the experimental plot coincides with (or approximates to)
the standard plot, the chosen GðaÞ is correct.
Pre-exponential factor
To determine the pre-exponential factor, first substitute the
GðaÞ and E into Eq. (13); then, take the natural logarithm
of both sides of the equation. After transposing and rear-
ranging, the equation is given by
ln PðuÞ þ lnðE=bRÞ ¼ ln½GðaÞ  ln A
By taking the linear regression of ½ln PðuÞ þ lnðE=bRÞ
versus ln½GðaÞ, one can obtain the pre-exponential factor
from the straight line of intercept  ln A.
Results and discussion
Analysis of the pyrolysis process
The pyrolysis process can be described by the DTG curve,
as shown in Fig. 1. As the two samples display similar
pyrolysis characteristics both the mass-loss processes can
be divided into three stages:
• In the temperature range of 80–160 C, one obtains a
pronounced mass-loss peak that corresponds to the
evaporation of moisture. The mass loss in this stage is
approximately 2 % of the sample mass, slightly larger than the
moisture contents according to the Fischer assay (c.f. Table 1).
• In the temperature range of 160–350 C, S2 has a very
small but much wider peak at 200–300 C while the
peak of S1 drops continuously and joins the next stage.
We assume that the oil sand bitumen consists of
asphaltene and maltene only, and the mass loss of this
stage attributes to the decomposition of maltene. As
summarized in reaction formula (a), no coke is formed
[40]. It is a low-degree decomposition stage, and
approximately 8 % sample mass has been decomposed.
Maltene ! Oil þ Gas ðaÞ
ð17Þ
• In the temperature range of 350–520 C, two
pronounced peaks at 400 and 460 C at 5 C min-1
could be observed. The mass loss is approximately
20 % of the sample mass, which is in accordance with
the oil contents of the Fischer assay. Hence, it is
considered a major oil-producing stage. In addition, we
attributed the first peak to the decomposition of
asphaltene (primary reaction b) and the second peak
to the secondary decomposition of the product of the
primary reaction (secondary reaction c).
Asphaltene ! Heavy oil þ Coke þ Gas ðbÞ
Heavy oil ! Light oil þ Coke þ Gas ðcÞ
It is worth noting that the second peak at 25 C min-1 of
S1 (c.f. Fig. 1a) is a very weak peak due to short exposure

123
 Q. Wang et al.

Fig. 2 Results of bi-Gauss A 12 B 18

multi-peak fitting for S1 (a) and experimental experimental

–1
–1
S2 (b) at different heating rates: 10 fitted 16 fitted

Conversion rate *10 /K

Conversion rate *10 /K
peak 1
a 5 K min-1, b 25 K min-1,

3
3
14 peak1
peak 2
and c 25 K min-1 8 12 peak2
10
6
8
6
4
4
2 2
0
600 620 640 660 680 700 720 740 760 600 620 640 660 680 700 720 740 760
Temperature/K Temperature/K
(a) 5 K min–1
12

–1
–1

experiment 14

Conversion rate *10 /K

Conversion rate *10 /K

10 fitted experiment
12

3
3

peak1 fitted
8 peak2 10 peak1
peak2
8
6
6 ⽿2
⽿1
4 4
2
2
0
0 600 620 640 660 680 700 720 740 760 780
620 640 660 680 700 720 740 760 780 800
Temperature/K Temperature/K
(b) 25 K min–1

14

–1
12
–1

experiment

Conversion rate *10 /K

Conversion rate *10 /K

fitted 12 experiment
3
3

10 fitted
peak1 10
peak2 peak1
8 8 peak2
⽿1
6 6
⽿1 ⽿2
⽿2 4
4
2
2
0
0 620 640 660 680 700 720 740 760 780 800
620 640 660 680 700 720 740 760 780 800
Temperature/K Temperature/K
(c) 25 K min–1

time to a certain temperature at the higher heating rate. It is temperature, which should volatilize at a lower
known that fragmentary peaks may lead to inaccurate temperature, so that the DTG curve shifts to a higher
results (e.g., inaccurate multi-peak fitting results, activation temperature region.
energy results by the model-free method). Thus, the
appropriate choice of heating rate for the Indonesian oil Separation of overlapping peak for the major oil-
sand is important. The original purpose of this study is to producing stage
apply the kinetic parameters calculated by TG for the
design of oil sand retorting reactor; therefore, the heating As can be seen from Fig. 1, the existence of two peaks
rates of 5, 15, and 25 C min-1 have been chosen based on overlapped in the major oil-producing stage in the tem-
experience. Because of the unique characteristics of perature range of 350–520 C can be described by the two-
Indonesian oil sand, a comprehensive study on the low- component parallel reaction model. The multi-peak fitting
or medium-level heating rate is necessary to achieve more method is applied to separate the overlapping peak.
accurate kinetic results. With an increase of the heating
rate, the peak on the DTG curve shifts to a higher Bi-Gauss multi-peak fitting results
temperature region. The mass-loss process happens in a
shorter time at a higher heating rate, which makes the part To use the bi-Gauss multi-peak fitting method, the rela-
of a relatively light organic substance volatilize at a higher tionship of da=dT versus T for the major oil-producing

123
Pyrolysis model of oil sand

Table 2 Characteristic parameters of the bi-Gauss multi-peak fitting method

Sample b Peak1 Peak2 R
a b c c
Trange /K Tpeak /K r1 Trange /K Tpeak /K r2

S1 5 600–760 673 0.5447 665–760 730 0.4553 0.9984

15 620–780 711 0.5474 710–780 757 0.4526 0.9992
25 640–790 723 0.6263 720–790 765 0.3737 0.9993
S2 5 600–760 678 0.4177 670–760 730 0.5823 0.9991
15 620–780 708 0.5545 705–780 755 0.4455 0.9985
25 630–790 730 0.5756 720–790 767 0.4244 0.9996
a
Temperature range
b
Peak temperature
c
Weighted factor of component i, i ¼ 1; 2

stage is plotted firstly. Each step of peak fitting procedures

240
can be easily processed in the peak fitting module (PFM)
which is built in an OriginPro 7.5 software as given in the 220

literature [41]. Due to space limitations, we only show the 200 S1-peak2
fitting results at 5 C min-1.
E/kJ mol–1
180
As shown in Fig. 2, the separated stages (peak1 and S2-peak2
160
peak2) as well as the fitted curve are obtained. The fitting
curves of bi-Gauss method almost coincide with the 140 S1-peak1

experimental curves. The fitting correlation coefficient R 120 S2-peak1

reaches to 0.9984 and 0.9991, respectively.
100

Pyrolysis characteristics of the major oil-producing stage
The characteristic parameters of pyrolysis for the separated
stages obtained by the bi-Gauss method are listed in
Table 2. The table displays the pyrolysis characteristics
with the increasing of the heating rate as follows: First, the
subpeaks shifted to higher temperatures and became shar-
per; furthermore, the temperature difference between two
subpeaks decreased (the original temperature difference is
57 and 52 C for S1 and S2 at 5 C min-1); finally, the
proportion of the area of peak2 decreased, which may be
interpreted as the delay in the secondary decomposition
reaction of the product of asphaltene due to incomplete
heating absorption. These results, which are in accordance
with the academic analysis, demonstrate the credibility of
the fitting results by the bi-Gauss method [33–35].
Calculation of kinetic parameters for the major oil-
producing stage
Kinetic parameters of separated stages
The NL-INT methods are introduced to calculate the dis-
tribution of activation energy curve E–a at the main con-
version range of 0.2–0.8. The average value of E can be
calculated to determine the kinetic mechanism using the
integral master plot method.
80
0.2 0.3 0.4 0.5 0.6 0.7 0.8
α
Fig. 3 E-a curves of NL-INT method
From the E–a curves in Fig. 3, it illustrates that the dis-
tribution of E fluctuates slightly within the main range;
therefore, the pyrolysis reaction in the separated stages fol-
lows single kinetic mechanism. In addition, the trends of the
E–a curves for peak1 or peak2 of both samples exhibit almost
the same trends, suggesting that the kinetic mechanisms for
peak1 or peak2 of both samples should be similar. It also can
be observed that, for each sample, the average E value for
peak1 (as listed in Table 4) is close to each other, but that of
the S1 for peak2 is apparently smaller than that of S2. This is
to say that the pyrolysis reaction in the temperature range of
peak2 for S2 occurs faster. Furthermore, the E value of peak2
is higher than that of peak1 in any samples, which confirms
the academic analysis that the occurrence of the secondary
decomposition reaction is more slowly than that of the pri-
mary reaction [20].
Once the average value of E is known, the value can
be used to determine the kinetic mechanism using the
integral master plot method. In this paper, we only
investigate the kinetic mechanism at 5 C min-1. This is
because the pyrolysis process of the oil sand represents
the intrinsic mechanism at the thermal equilibrium state

123
 Q. Wang et al.

Table 3 Commonly used mechanisms for the pyrolysis of solid state material
Mechanism Symbol f ðaÞ GðaÞ

Two-dimensional diffusion (Valensi Eq.) D1 ½ lnð1  aÞ1 a þ ð1  aÞ lnð1  aÞ

h i
1 1
h i
1 2
Two-dimensional diffusion (Jander Eq., n ¼ 2) D2 1
ð1  aÞ2 1  ð1  aÞ2 1  ð1  aÞ2
h i
1 1
h i
1 2
Three-dimensional diffusion (Jander Eq., n ¼ 3) D3 3 2

2 ð1  aÞ 1  ð1  aÞ 1  ð1  aÞ3
3 3

h i1
Three-dimensional diffusion (G-B Eq.a) D4 3 13 1  23 a  ð1  aÞ3
2

2 ð1  aÞ 1
h i1 h i2
Three-dimensional diffusion (Z-L–T Eq.b) D5 13
ð1  aÞ3 1
4 1
3
2 ð1  aÞ ð1  aÞ 1
3

Nucleation and nuclei growth (A-E Eq.c, n ¼ 1) A1 1a  lnð1  aÞ

 aÞ½ lnð1  aÞ2
1 3
Nucleation and nuclei growth (A-E Eq., n ¼ 1:5) A1.5 2
3 ð1
2
½ lnð1  aÞ
aÞ½ lnð1  aÞ1
2
Nucleation and nuclei growth (A-E Eq., n ¼ 2) A2 1
2 ð1  ½ lnð1  aÞ
1 1
Exponential nucleation (Mample Eq., n ¼ 2) P2 2a a2
Order type chemical reaction OC ð1  aÞ2 ð1  aÞ1 1
a
Ginstling–Brounstein equation
b
Zhuralev–Lesokin–Tempelman equation
c
Avrami–Erofeev equation

Fig. 4 Experimental and A 3 3

B 3 3
D3 D2
standard master plots of D1 D3
D2 D5
separated stages of S1-peak1 P2 D1
experimental master plot experimental master plot A2 D4
(a), S1-peak2 (b), S2-peak1 (c), 2 2 P(u)/P(0.5)
2 P2 2

G(α )/G(0.5)
G(α )/G(0.5)

standard master plot standard master plot

P(u)/P(0.5)
and S2-peak2 (d) A1 OC

1 1 1 1

0 0 0 0
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.2 0.3 0.4 0.5 0.6 0.7 0.8
α α

C 3
D2
3
D 3
A1.5
3
OC D2
D3 D1
D3 D1
experimental master plot P2
P2 2 experimental master plot 2
2
G(α )/G(0.5)
P(u)/P(0.5)
G(α )/G(0.5)

P(u)/P(0.5)
standard master plot standard master plot

1 1 1 1

0 0 0 0
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.2 0.3 0.4 0.5 0.6 0.7 0.8
α α

Table 4 Kinetic parameters of separated stages

at low-level heating rates. The process does not show
effects, such as diffusion, that are caused by thermal Sample Peak E/kJ mol-1 Mechanism A/s-1 R
hysteresis. In addition, the effects of various heating rates
S1 Peak1 145 ± 27 OC 4.48E?10 0.99997
on the characteristics of the components differ from each
Peak2 188 ± 12 D3 2.03E?12 0.99980
other due to the extremely complex composition of oil
S2 Peak1 146 ± 27 OC 4.59E?10 0.99976
sand. We realize that the multiple heating rates may lead
Peak2 159 ± 13 D2 3.66E?11 0.99999
to various kinetic mechanisms. This could serve as future
research direction.
The significant master plots, as listed in Table 3 [42], are the determination of E and A are listed in Table 4. The results
given in Fig. 4 with experimental plot. The kinetic param- show that both peak1 of S1 and S2 follow a chemical reaction
eters and the linear correlation coefficient R generated during (OC) mechanism, while peak2 of S1 follows the three-

123
Pyrolysis model of oil sand

Fig. 5 Experimental and A3 3

B 3 3
D3 D1
standard master plots of the A2
D3
A2 D1
major oil-producing stage of S1 experimental master plot A1.5 D2 A
P2 1.5 2

G(α )/G(0.5)
(a) and S2 (b) 2 2 experimental master plot

G(α )/G(0.5)

P(u)/P(0.5)
2

P(u)/P(0.5)
standard master plot P2
standard master plot
OC

1 1 1 1

OC
OC

0 0 0 0
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.2 0.3 0.4 0.5 0.6 0.7 0.8
α α

dimensional diffusion (D3) mechanism, and peak2 of S2
follows the two-dimensional diffusion (D2) mechanism.
Kinetic parameters of the major oil-producing stage
The E values of the separated stages were substituted into
Eq. (7) to obtain the E value of the overall stage at
5 C min-1. The results of S1 and S2 are 165 and
154 kJ mol-1, respectively. Studies on the high-degree
decomposition of different oil sands at low heating rates (5
or 10 C min-1) show varying E values. For example, the
E value of Tumuji oil sand [9] calculated by Coats-Redfern
method is 161 kJ mol-1, that of the Asphalt Ridge oil sand
[12] calculated by the Anthony-Howard method is
251 kJ mol-1, that of the Whiterocks oil sand [13]
obtained by the modified Anthony-Howard method is
121 kJ mol-1, that of the Alberta oil sand [15] by the
Coats-Redfern method is 246 kJ mol-1, and that of the
Karamay oil sand [22] obtained by a combination of the
Freeman and Coats-Redfern method is 56.7 kJ mol-1.
Relative to the oil sands all over the world, the activation
energy of Indonesian oil sand has a moderate value.
Based on the result of the E value, the kinetic mecha-
nism for the major oil-producing stage for S1 and S2
could be determined using the integral master plot
method. As shown in Fig. 5, the mechanism of the overall
stage certainly does not follow a single mechanism, which
is consistent with expectations. If the master plots are
divided using the reference point at a ¼ 0:5, the overall
stage mechanisms of the front and back segment are
identical with those of the separated stages. In addition,
the weighted factors of peak1 and peak2 are located
approximately at ri ¼ 0:5 (c.f. Table 2). Once again, the
front segments of S1 and S2 follow the OC mechanism,
while the back segment of S1 follows the D3 mechanism
and the back segment of S2 follows the D2 mechanism.
The high level of similarity in the kinetic mecha-
nism between separated stages and the overall stage
demonstrates the reliability of the kinetics analysis,
especially for the two-component parallel reaction
model.
Conclusions
In this paper, we focus on the problem of the overlapping
peak in the DTG curve for the pyrolysis of Indonesian oil
sand. We realize that the two-component parallel reaction
model may be more appropriate to describe the major oil-
producing stage, in which the DTG curve displays two
pronounced and asymmetric subpeaks. Based on the sat-
isfying results of the bi-Gauss method, we determined the
kinetic mechanism by the NL-INT method with the integral
master plot method. The results of the kinetic parameters
show that the E values of the overall stage are 165 and
154 kJ mol-1 for S1 and S2, respectively. The separated
stages corresponding to the pseudo-component follow
single kinetic mechanism due to the small range variation
of Evalue, while the mechanism of the overall stage cer-
tainly does not follow a single mechanism as expected. If
the overall stage was divided using the reference point at
a ¼ 0:5, both of the front segments of S1 and S2 follow the
chemical reaction mechanism. The back segment of S1
follows the three-dimensional diffusion mechanism (Jander
Eq.), and the back segment of S2 follows the two-dimen-
sional diffusion mechanism (Jander Eq.), which are in
accordance with the mechanisms of the separated stages.
The unity of the kinetic mechanisms of the overall stage
and the subpeaks demonstrates the reliability of the two-
component parallel reaction model. Furthermore, the bi-
Gauss multi-peak fitting method could be applicable to a
much wider range.

123

Acknowledgements The authors would like to thank Mr. Deyin Wu
from Indonesia for the supply of oil sand samples. Natural Science
Foundation of China (51276034).
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