Fuel 153 (2015) 240–248

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Fuel
journal homepage: www.elsevier.com/locate/fuel

A method for characterization of bitumen

Bahareh Azinfar, Mohsen Zirrahi, Hassan Hassanzadeh, Jalal Abedi ⇑
Department of Chemical and Petroleum Engineering, Schulich School of Engineering, University of Calgary, 2500 University Drive NW, Calgary, AB T2N 1N4, Canada

h i g h l i g h t s

 A characterization method is proposed for bitumen and heavy oils.

 Residue curve method is used to model the simulated distillation data.
 Proposed model accurately regenerates solubility of light solvents in bitumen.

a r t i c l e i n f o a b s t r a c t

Article history: Characterization of bitumen is a necessary step to perform phase equilibrium computations involved in
Received 5 January 2015 bitumen production and processing. This study presents a methodology for bitumen characterization
Received in revised form 28 February 2015 using a residue curve map. A fugacity–activity coefficient approach is applied to model the thermody-
Accepted 2 March 2015
namic equilibrium of the species in the gas and liquid phases. The Peng–Robinson equation of state
Available online 13 March 2015
(PR-EoS) and NRTL activity model are utilized to calculate the fugacity and activity coefficients in the
gas and liquid phases, respectively. The proposed model was evaluated using experimental simulated dis-
Keywords:
tillation (SD) data as well as experimental solubility data of light hydrocarbon (CH4, C2H6) and non-hy-
Heavy oil
Bitumen characterization
drocarbon gases (CO2, N2) in bitumen. The molecular weight, specific gravity, and SD curves were
Simulated distillation represented using defined pseudo-components. The tuned EoS was able to regenerate the solubility data
Solubility with an acceptable accuracy (AARD less than 5.6% and 4.5% for hydrocarbon and non-hydrocarbon sol-
NRTL model vents, respectively). The proposed method can be applied for bitumen characterization and to predict
the solubility of the light gases in bitumen.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction
Increase of worldwide energy demand besides the decline of
conventional oil reserves resulted more attention toward bitumen
and heavy oil recourses. Currently, thermal oil recovery is the lead-
ing processes for bitumen and heavy oil extraction in Alberta.
Disadvantages of thermal recovery methods such as high energy
and water consumption, water pollution and greenhouse gas emis-
sion have raised the interests to find alternative methods such as
solvent injection.
Characterization of bitumen is the initial step for all thermody-
namic and phase behavior calculations. Crude oil assay obtained
from distillation experiments is the common tool to characterize
hydrocarbon mixtures and petroleum fractions. The underlying
idea is that hydrocarbon molecules, which boil at a range of tem-
perature, are lumped into a pseudo-component and assigned an
average boiling temperature [1,2].
⇑ Corresponding author.
E-mail address: jabedi@ucalgary.ca (J. Abedi).
Bitumen and extra heavy oil assays should be obtained under
deep vacuum distillation to avoid possible thermal cracking at
temperatures higher than 523 K. Standard tests such as D5236
ASTM test [3] and based on gas chromatography (GC) have been
developed to characterize high boiling point hydrocarbon mix-
tures. Simulated distillation is fast, repeatable, and inexpensive.
Additionally, a small amount of bitumen/heavy oil sample (less
than 1 ml) is required for the analysis [1].
Saajanlehto and Alopaeus [4] and Saajanlehto et al. [5] have
used distillation curve data to develop a characterization method
for Perturbed-Chain Statistical Associating Fluid Theory (PC-
SAFT). Their model has been verified to represent density, sat-
uration pressures for propane-Athabasca bitumen and CO2–pro-
pane–Athabasca bitumen systems and solubility of hydrogen in
heavy oil. They proposed a single carbon number type character-
ization method for heavy oils and bitumen. In their model, each
cut of crude oil was split into saturate, aromatic and polyaromatic
(SAP) fractions based on its boiling point. Therefore, distribution of
SAP in crude oils is assumed universal.
Doherty and Perkins [6–8] developed the residue curve map to
model the simple distillation assay. This model calculates the loci

http://dx.doi.org/10.1016/j.fuel.2015.03.005
0016-2361/Ó 2015 Elsevier Ltd. All rights reserved.
 B. Azinfar et al. / Fuel 153 (2015) 240–248
of saturation temperatures of the mixture versus the composition
of the liquid phase in the flask during the distillation. To apply this
model there is no need to know the exact condition and procedure
of the distillation process. Only pressure at which the test has been
carried out and the resulting experimental distillation curve are
required. This is the remarkable advantage of the model developed
by Doherty and Perkins [6–8].
Residue curve map has been used by Satyro and Yarranton [2]
to characterize several oil samples using distillation curve data.
They assumed ideal gas and liquid phases in their thermodynamic
equilibrium calculations. While this assumption is quite well
applicable for the gas phase, it may not be valid for the liquid phase
especially for heavy oil and bitumen. Ortiz et al. [9] used the resi-
due curve map upon well-defined mixtures to tune equation of
state parameters and then calculated the phase behavior data.
One of the important parameters in heavy oil and bitumen
applications is the solubility of light components in bitumen or
heavy oil. Prediction of solubility of gaseous solvents in bitumen
is key for reservoir simulation and engineering studies of bitumen
production, upgrading, fractionation and refining. Once the solubil-
ity of solvent in bitumen is defined, density, viscosity and other
physical properties can be calculated using the established meth-
ods. In previous solubility models bitumen has been considered
as single pseudo-component (such as Zirrahi et al. [10]; Fu et al.
[11]) or multicomponents (such as Kariznovi et al. [12]; Eastick
et al. [13]; Huang and Radosz [14]; Mehrotra and Svrcek [15]).
After definition of the pseudo-components, a proper equation of
state should be tuned to find the binary interaction parameters
(kij). The tuned equation of state then can be used to find
thermophysical properties required for engineering calculations.
Tuning of equation of state for conventional oils is typically per-
formed using the data obtained from PVT experiments such as con-
stant composition expansion (CCE), differential liberation and
separator tests. For bitumen, aforementioned laboratory tests are
not common. Therefore, there are no independent calculations to
find and tune the interaction parameters between pseudo-compo-
nents. Some studies estimated the interaction parameters using
correlations while some ignored these interaction parameters
[14,15].
Kariznovi et al. [12] defined the pseudo-components and their
properties such as molecular weight, specific gravity to match
the average molecular weight and specific gravity of bitumen.
They tuned the normal boiling point, acentric factor, and EoS
parameters (XA and XB) of pseudo-components and the binary
interaction parameters between solvent-pseudo-component (ks-
pc) to match the experimental solubility data.
Eastick et al. [13] and Huang and Radosz [14] characterized Cold
Lake bitumen using five pseudo-components to calculate solubility
of CO2 in the bitumen and its pseudo-components. They applied
Peng–Robinson equation of state (PR-EoS) and statistical associat-
ing fluid theory (SAFT), respectively. Mehrotra and Svrcek [15]
divided Cold Lake bitumen into three pseudo-components, includ-
ing asphaltene, distillable and undistillable maltene. They used PR-
EoS to model the gas and liquid phases and ignored the interaction
between pseudo-components.
Previously, we used the Krichevsky–Ilinskaya’s equation [10] to
correlate solubility of solvents in bitumen where bitumen was
assumed as a single component without characterizing the bitu-
men. In this work we propose an approach using the simulated dis-
tillation (SD) data to characterize the bitumen by applying the
residue curve map. We apply the u–c (u is the fugacity coefficient
of a component in the gas phase and c is the activity coefficient of
the component in the liquid phase) approach to model the
thermodynamic equilibrium of gas and liquid phases. We use the
NRTL activity model to capture the non-ideal behavior of bitumen
molecules. The major difficulty to apply NRTL model is the
241
introduction of additional binary interaction energy parameters.
While some methods have been presented in literature to find
these parameters, their application to complex mixture such as
bitumen has not been confirmed. To overcome this problem, we
determine the interaction energy parameters between the
pseudo-components of bitumen using the residue curve map
method.
After characterization of the bitumen, we follow the u–c
approach to calculate the solubility of light hydrocarbon and
non-hydrocarbon gases (solvents) in bitumen. Using this approach,
the energy interaction parameters between molecules of the sol-
vent and the pseudo-components are the only required parameters
to be tuned for solubility calculations.
In summary, we propose a general approach with a solid
thermodynamic background to characterize bitumen. The devel-
oped method can be used to calculate the required interaction
parameters and solubility of light solvents in bitumen.
Application of this methodology can be an alternative for expen-
sive laboratory PVT tests. Therefore, it will decrease the costs of
bitumen characterization and find many applications in phase
behavior studies related to bitumen and extra heavy oil production
and refining.
The rest of this paper is organized as follow: first, we present
our methodology to characterize bitumen. Then, the solubility
model is presented. Next, accuracy of the approach is evaluated
using experimental data and discussed followed by the summary
and conclusion.
2. Bitumen characterization procedure
We use the results obtained from simulated distillation (SD)
assay to characterize the bitumen. The SD test results in mass per-
cent of the distilled (% off) versus the temperature. Residue curve
map, which is the trajectory of bubble point temperature of the
mixture from the initial to the end state of batch distillation, is
applied to represent the simulated distillation results. As described
by Doherty and Perkins [6–8] liquid composition changes during
the simple batch distillation can be represented by:
dxðnÞ
¼ xðnÞ  yðxðnÞ; TÞ ¼ Fðn; xÞ ð1Þ
dn
where x = [x1, x2, xs, . . .., xN] and y = [y1, y2, ys, . . ., yN] are the liquid
and gas mole fraction arrays, respectively, N is the number of
pseudo components, n is the dimensionless time called warped time
varying from 0 to +1 where n = 0 corresponds to the start of the dis-
tillation (t = 0) and n = +1 corresponds to the time when the dis-
tillation flask becomes empty. Liquid hold-up in the flask is
calculated by:
H ¼ H0 expðnÞ ð2Þ
where H is the liquid hold-up and subscript 0 denotes the initial
hold-up [6]. At each warped time, the liquid phase is at saturation
condition (T = Tsat) and the gas phase composition can be obtained
using the saturation temperature equilibrium calculations. The set
of Eqs. (1) and (2) was solved using fourth-order Runge–Kutta
method with the warped time interval Dn as:
1
xnþ1 ¼ xn þ Dnðk1 þ 2k2 þ 2k3 þ k4 Þ ð3Þ
6
where
k1 ¼ f ðnn ; xn Þ ð4Þ
 
1 1
k2 ¼ f nn þ Dn; xn þ Dnk1 ð5Þ
2 2
242 B. Azinfar et al. / Fuel 153 (2015) 240–248

 
1 1 We used the central finite difference to find the right hand of Eq.
k3 ¼ f nn þ Dn; xn þ Dnk2 ð6Þ
2 2 (22) with temperature difference of 1 K (DT = 1). Other properties
of bitumen and heavy oil that should be considered for character-
k4 ¼ f ðnn þ Dn; xn þ Dnk3 Þ ð7Þ ization are the average molecular weight (M) and specific gravity
(SG). We also used the following mixing rules to find the average
T sat ¼ f ðxn ; PÞ ð8Þ molecular weight and specific gravity of bitumen [1].
X
sat xi M i ¼ M a v e ð23Þ
yn ¼ KðT ; xn Þxn ð9Þ
X xi M i M av e
nn ¼ nn1 þ Dn ð10Þ ¼ ð24Þ
SGi SGav e
Hn ¼ H0 expðnn Þ ð11Þ Correlation of Rao and Bardon [21] was applied to relate the
boiling point of each pseudo-component to its molecular weight
H 0 M  Hn M n as given by:
%off ¼ 100 ð12Þ
H0 M  
T bi
where M is the molecular weight, n is the step index and Dn is the ln M i ¼ ð1:27 þ 0:071K w Þ ln ð25Þ
22:31 þ 1:68K w
integration step of the warped time. This parameter (Dn) was set to
0.005 as the optimum integration step for the sake of accuracy and where Tb is the boiling temperature and Kw is the Watson character-
low run time for calculations. Tsat and K are the saturation tempera- ization factor. Then, we used SØreide [22] correlation to relate the
ture at the distillation pressure and equilibrium constant at Tsat and molecular weight and specific gravity of each pseudo-component.
P, respectively. To find the equilibrium constant, ideal gas phase This correlation has been developed using 843 samples obtained
was assumed (u = 1). Therefore, thermodynamic equilibrium can from 68 reservoir fluids. This correlation is given by:
be written as:
SGi ¼ 0:2855 þ C f ðM i  66Þ0:13 ð26Þ
yi P ¼ xi i Psat
c i ð13Þ
where Cf obtained to satisfy the Eq. (26) for representation of
where Psat and ci are the saturation pressure and the activity coeffi- experimental specific gravity of reservoir fluid using its molecular
cient of component i in the liquid phase, respectively. To find the weight. This parameter is typically between 0.27 and 0.31 [22].
saturation pressure, Lee–Kesler [16] equation was used as given by: To perform characterization, first, 28 pseudo-components were
defined with boiling point range from 300 to 1110 K with interval
ln Psat 0
r ¼ h þxh
1
ð14Þ
of 30 K. The lower bound (300 K) is between boiling point of C4H10
and C5H12, which are the lightest possible hydrocarbon in bitumen.
6:09648
h0 ¼ 5:92714   1:28862 ln T r þ 0:169347T 6r ð15Þ The lightest hydrocarbon component in bitumen is usually C7H16
Tr to C10H22. The upper limit that simulated distillation can capture
is C120H242 with a boiling point of 1023 K. Therefore, the range of
15:6875
h1 ¼ 15:2518   13:4721 ln T r þ 0:43577T 6r ð16Þ 300 to 1110 K can safely capture the hydrocarbon components pre-
Tr
sented in bitumen. Since the simulated distillation apparatus is
where Tr and Pr are the reduced temperature (Tr = T/Tc) and pressure calibrated with normal paraffin (n-alkanes) components, we used
(Pr = P/Pc), respectively, and x is the acentric factor. Furthermore, Twu [23] correlations to calculate the molecular weight, critical
NRTL model was applied to calculate the activity coefficient of com- temperature and pressure for each pseudo-component using its
ponents in the mixture as given by [17]: boiling point. Also, acentric factor was obtained using Lee–Kesler
P P
j xj sji Gji
X xj Gjj  xs G
 equation [1], which has been presented specifically for petroleum
lnðci Þ ¼ P þ P sij  Pl l lj lj ð17Þ fractions [24]. Next, mole fraction of each pseudo-component
k xk Gki j k xk Gkj k xk Gkj was optimized by solving Eqs. ((1)-(12)) to find the best match of
the SD assay results.
where Gij is a characteristic of interaction energies between mole-
After finding the mole fraction distribution of the pseudo-com-
cules of i and j given by [17]:
ponents present in bitumen, the average Watson characterization
Gij ¼ expðaij sij Þ ð18Þ factor is obtained to find the average molecular weight of the bitu-
men using Eqs. (23) and (25). Then, SØreide correlation (Eq. (26)) is
g ij  g jj tuned with Cf = 0.308 to match the experimental specific gravity of
sij ¼ ð19Þ
RT bitumen or heavy oil using Eqs. (24) and (26). Characterization
where g is the energy interaction parameter and a specifies the ran- procedure is shown in a diagram shown in Fig. 1.
domness in the mixture. In this work a = 0.3 was assumed for all
pseudo-components of bitumen [18]. Energy interaction parameter 3. Solubility modeling
between molecules i and j (gij) was calculated assuming the geo-
metric mean proposed by Vetere [19] as: The output of characterization scheme is a multicomponent
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi system, which is not suitable for computationally demanding ther-
g ij ¼ g jj  g ii ð20Þ
mal reservoir simulators. Reservoir fluids are usually lumped into
Tassios [20] proposed defining the energy parameter of mole- manageable number of pseudo-components to decrease the run
cule i by the heat of vaporization (DHvap) as follows: time required for compositional and thermal reservoir simulations
[1,24]. Molecular weight, Mi, which separates the groups is
g ij ¼ DU ¼ ðDHv ap  RTÞ ð21Þ obtained as given by [24]:
Applying Clausius–Clapeyron equation we reach to: Mi ¼ M 1 ðMn =M 1 Þi=NH ð27Þ
v ap sat
DH d ln P where NH is the number of groups (pseudocomponents), i = 1, . . .,
¼ ð22Þ
RT dT NH, M1 is the molecular weight of the lightest component and Mn
 B. Azinfar et al. / Fuel 153 (2015) 240–248 243

Fig. 1. Flow chart used to characterize the bitumen.

is the molecular weight of the heaviest component. Components After grouping of the components using the scheme described
with molecular weight falling between Mi1 and Mi are lumped in above, we use the u–c approach to calculate the solubility of gases
group i. Next, mixing rules proposed by Lee and Kesler [16] were in bitumen for the sake the consistency with the characterization
applied to find the critical properties and acentric factor of each procedure described earlier. Therefore, the thermodynamic
group as follows: equilibrium of a component in gas and liquid phases can be written
h PP 3
i as:
1=3
1
8 i j xi xj ðV ci þ V 1=3
cj Þ L
V cg ¼ P 2 ð28Þ yi ui P ¼ xi ci f i ð33Þ
i xi
where u denotes the fugacity coefficient of specie i in the gas phase.
 3
fL is the fugacity in hypothetical liquid state given by Prausnitz et al.
PP 0:5
1
8V cg i j xi xj ðT ci T cj Þ V ci1=3 þ V cj1=3 as [18]:
T cg ¼ P 2 ð29Þ !
i xi L 0 V Li ðP  1:013Þ
f i ¼ f i P c exp ð34Þ
P RT
xx
xg ¼ Pi i i ð30Þ
i xi and f0 is the reduced hypothetical liquid fugacity at atmospheric
pressure. VLi is the partial molar volume of component i in the liquid
Z cg ¼ 0:2905  0:085xg ð31Þ phase.
Prausnitz et al. [18] reported f0 in a graphical format, which was
Z cg RT cg later presented by Riazi and Vera [25] using the correlation given
Pcg ¼ ð32Þ
V cg by:
 
where Tc, Pc, Vc and Zc are critical temperature, pressure, volume and 0 8:19643
f i ¼ exp 7:902   3:08 lnðT r Þ ð35Þ
compressibility factor of the group, respectively. R is the universal Tr
gas constant and x is the acentric factor.
244 B. Azinfar et al. / Fuel 153 (2015) 240–248

where Tr is the reduced pressure (Tr = T/Tc). Fugacity coefficient of Table 1

specie i was calculated using Peng–Robinson equation of state Mole fraction and properties of characterized bitumen.

(PR-EoS) as given by [18,26]: Pseudo Normal boiling Mole Molecular Specific

components point (K) fraction (%) weight gravity
RT aaðTÞ
P¼  ð36Þ PC1 300 0.24 76.8 0.7051
V  b VðV þ bÞ þ bðV  bÞ PC2 330 0.80 96.4 0.7657
PC3 360 1.43 118.8 0.8013
where PC4 390 4.83 143.8 0.8280
PC5 420 3.38 171.7 0.8500
0:45724R2 T 2C PC6 450 2.00 202.5 0.8691
a¼ ð37Þ
PC PC7 480 13.19 236.3 0.8861
PC8 510 3.54 273.2 0.9016
PC9 540 6.86 313.2 0.9159
0:07780RT C
b¼ ð38Þ PC10 570 10.65 356.4 0.9293
PC PC11 600 4.97 403.0 0.9419
PC12 630 8.04 452.8 0.9537
h i2 PC13 660 6.09 506.1 0.9650
aðTÞ ¼ 1 þ kð1  T 0:5
r Þ ð39Þ PC14 690 3.30 562.9 0.9758
PC15 720 8.83 623.2 0.9862
PC16 750 2.66 687.2 0.9962
k ¼ 0:37464 þ 1:54226x  0:26992x2 x < 0:49 PC17 780 0.14 754.7 1.0058
ð40Þ PC18 810 1.52 826.0 1.0151
k ¼ 0:3796 þ 1:485x  0:1644x2 þ 0:01667x3 x P 0:49
PC19 840 3.13 901.1 1.0240
where x is the acentric factor. Activity coefficient of solvent PC20 870 1.19 980.0 1.0328
PC21 900 2.55 1062.8 1.0412
molecules in liquid phase has been obtained using NRTL model as PC22 930 2.99 1149.5 1.0495
presented in Eqs. (17)–(19). Interaction energy parameters of the PC23 960 0.25 1240.2 1.0575
pseudo-components of bitumen were calculated using Eqs. (20)– PC24 990 1.56 1334.9 1.0653
(22). The only parameter that should be tuned is the interaction PC25 1020 2.08 1433.7 1.0730
PC26 1050 2.43 1536.6 1.0804
energy parameter between solvent and pseudo-components.
PC27 1080 1.31 1643.7 1.0877
Interaction energy parameter between solvent and pseudo-compo- PC28 1110 0.04 1755.1 1.0949
nents molecules is a function of temperature and changes for differ-
Property of the Cold Lake bitumen
ent pseudo-components [27]. Therefore, a generalized equation was
Experimental [11] Calculated AARD (%)
assumed to calculate the interaction energy parameter between sol-
vent molecules and pseudo-component i as given by: Molecular weight 533 527.23 1.08
Specific gravity 0.986 0.987 0.10
ssi ¼ A þ B  T þ C  Mi þ D  T ri ð41Þ
Interaction energy parameters between solvent molecule and
1000
pseudo-component i were assumed symmetric (sis = ssi). To tune
the interaction energy parameters, experimental solubility data
at maximum pressure of each isotherm was applied as proposed 900
by Huang and Radosz [14]. The objective function was defined
Temperature (K)

and minimized as given by: 800

n  calc exp 
1X xi  xi 

OF ¼  exp  ð42Þ 700
n i xi
Experimental Data
Proposed Model
where n is the number of experimental data points. Optimization 600
toolbox of MATLAB R2012a was used for regression and optimiza-
tion in this work. 500

4. Results and discussion 400

0 20 40 60

The characterization procedure described in the previous sec-

tion (Fig. 1) was applied to the Cold Lake bitumen sample. The
experimental SD data curve was extracted from the work of Yu
et al. [28]. The original data was reported in a graphical format
and as a result, a deviation approximately 2 K is observed in the
extracted data. The mole fraction, molecular weight, specific grav-
ity, and boiling point of the pseudo-components are given in
Table 1. A comparison of the experimental SD curve and the results
calculated by the presented model is shown in Fig. 2. A good agree-
ment can be found from this figure and the results confirm that the
presented model can accurately regenerate the experimental SD
curve.
Both the calculated and measured values for the specific gravity
and molecular weight of Cold Lake bitumen are given in Table 1.
The Watson characterization factor (Kw) was 15.8 and the Cf of
the Søreide equation was 0.308. The very small deviation between
the calculated and experimental values shows that the obtained
% Mass Distilled
Fig. 2. Comparison of the Yu et al. [28] experimental values and the calculated
simulated distillated curve data.
pseudo-components can accurately represent the Cold Lake
bitumen.
After finding the pseudo-components, grouping calculations
performed to lump them into five new pseudo-components. The
mole fraction, average molecular weight, critical properties and
acentric factor of each group were obtained and are given in
Table 2.
The characterized bitumen was introduced into the presented
solubility model to calculate the solubility of the light hydrocarbon
solvents (CH4 and C2H6) and non-hydrocarbons (CO2 and N2). Eq.
(41) presents the binary interaction energy parameters as a linear
function of temperature, molecular weight, and reduced
 B. Azinfar et al. / Fuel 153 (2015) 240–248 245

Table 2 0.4
Mole fraction and properties of lumped pseudo-components.
299.95 K, Mehrotra and Svrcek [29]
319.15 K, Mehrotra and Svrcek [29]
Pseudo Mole Molecular Critical Critical Acentric
376.55 K, Mehrotra and Svrcek [29]
components fraction weight temperature Pressure factor

Mole fraction of CH 4
373.15 K, Fu et al. [11]
(K) (MPa) 0.3 Proposed Model
PC1 0.1268 153.4 570.85 2.517 0.3965
PC2 0.3922 306.8 700.12 1.572 0.6750
PC3 0.2905 551.2 820.60 0.909 1.0563
PC4 0.1163 1005.9 958.19 0.453 1.5650 0.2
PC5 0.0742 1485.4 1061.0 0.274 1.9135

temperature. The linear function successfully captured the interac- 0.1 (a)
tion between the pseudo-components and the solvent in the mix-
ture. Table 3 lists the parameters required to calculate binary
2 4 6 8 10
interaction parameters for light hydrocarbon solvents (CH4 and
Pressure (MPa)
C2H6) and non-hydrocarbons (CO2 and N2).
The experimental data for solvent solubility in bitumen is very 0.4
scarce in the open literature. Here, we apply the same reference
data sets [11,29] used in our previous study [10] to validate the 343.15 K, Fu et al. [11]
350.55 K, Mehrotra and Svrcek [29]
developed characterization procedure as well as the solubility 423.15 K, Fu et al. [11]

Mole fraction of CH4

model. It is worth noting that in the previous work [10] we used 0.3
Proposed Model

the Krichevsky–Ilinskaya’s equation to correlate solubility of sol-

vents in bitumen where bitumen was assumed as a single compo-
nent without characterizing the bitumen. Fig. 3 compares the
experimental CH4 solubility data with the results of the proposed
model. The experimental data was recorded at temperatures to
423.15 K and pressures up to 11 MPa. The calculated CH4 solubility
results are very close to the experimental data, which was repre-
sented by the proposed model with an Absolute Average Relative
Deviation (AARD) of less than 4.7%. The experimental data reported
by Mehrotra and Svrcek [29] for temperatures up to 376.15 K was
represented with an AARD of 3.4%. Data of Fu et al. [11] produced a
data set covering temperatures up to 423.15 K. The Fu et al. [11]
data at 373.15 K, 10 MPa and 423.15 K, 6 MPa show scatter and
do not follow the trend found in the other experimental data sets.
Therefore, these data points were not considered in the calculation
of the AARD between the experimental and calculated CH4 solubil-
ity data. Lower methane solubility was found in the Fu et al. [11]
data at 343.15 K than the Mehrotra and Svrcek [29] data at
350 K. Since higher solubility is expected at lower temperatures,
it seems plausible to observe more deviation between the results
of our proposed model and the experimental data of Fu et al.
[11]. We found an AARD of 6.2% between the Fu et al. [11] data
and the results of our model.
Fig. 4a and b compare the C2H6 solubility experimental data and
the results of the proposed model. An AARD equal to 6.3% was
found. At high temperature and pressure conditions, our proposed
model slightly underestimates the experimental C2H6 solubility
data. A similar deficiency for methane solubility at 343.15 K was
observed when ethane solubility data from Fu et al. [11] at
343.15 K and Mehrotra and Svrcek [29] at 350 K were compared.
However, compared with other models available in the literature,
our model predicts the experimental data with a better accuracy
(see Table 4).
For non-hydrocarbon solvents, the experimental solubility data
for CO2 and N2 was obtained from the literature [28,29].
0.2
0.1
(b)
2 4 6 8 10
Pressure (MPa)
Fig. 3. Comparisons of the results of the proposed model with the experimental
CH4 solubility data in bitumen. Experimental data was obtained from Fu et al. [11]
and Mehrotra and Svrcek [29]. The same reference solubility data sets [11,29] were
used in our previous study [10] for validation purpose.
Fig. 5a and b illustrate ability of the proposed model to reproduce
the experimental CO2 solubility data for Cold Lake bitumen. An
AARD of less than 2.0% was found when the Mehrotra and Svrcek
[29] experimental data was regenerated at subcritical and super-
critical conditions. In the subcritical and supercritical regions, the
energy interaction parameters were different. Table 3 presents
these parameters for CO2 molecules in different regions. The model
is more accurate in the subcritical region where the experimental
data for the solubility of CO2 in Cold Lake bitumen had an AARD
less than 1.5%. This change in the accuracy of the model may be
related to the change of the energy interaction parameters
between pseudo-components with sub- and supercritical CO2
molecules.
Yu et al. [28] reported an extensive data set including tempera-
tures up to 523.1 K and pressures up to 16 MPa for CO2 solubility in
Cold lake bitumen. As mentioned in Table 4, the model reproduced
this data set with an AARD of less than 5.8%. The model predictions

Table 3
Parameters for implementation of Eq. (35) to determine the binary interaction energy parameter of the solvents and pseudo-components.

Solvent A B C D
CH4 1.593 8.8262  104 2.9303  103 1.0354  103
C2H6 9.1211  102 8.6345  104 9.9354  105 2.0314  103
CO2(supercritical) 0.8329 2.7713  103 1.9092  106 0.2809
CO2(subcritical) 5.9255 2.2605  102 4.0392  103 10.801
N2 4.7267 1.1687  103 3.6593  103 7.129  102
246 B. Azinfar et al. / Fuel 153 (2015) 240–248

0.8 0.7
(a)
0.6

Mole fraction of CO2

Mole fraction of C2H6

0.6 0.5

0.4

0.4
297.35 K, Mehrotra and Svrcek [29] 0.3
325.25 K, Mehrotra and Svrcek [29] 288.15 K, Mehrotra and Svrcek [29]
349.35 K, Mehrotra and Svrcek [29] 299.15 K, Mehrotra and Svrcek [29]
343.15 K, Fu et al. [11] 0.2 350.05 K, Mehrotra and Svrcek [29]
Proposed Model Proposed Model
0.2
0.1
(a)
2 4 6 8 10 2 4 6 8 10 12
Pressure (MPa) Pressure (MPa)

0.8
0.8 325.65 K, Mehrotra and Svrcek [29]
(b) 323.3 K, Yu et al. [28]
371.05 K, Mehrotra and Svrcek [29]
373.3 K, Yu et al. [28]
0.6 473.7 K, Yu et al. [28]

Mole fraction of CO2

Mole fraction of C2H6

0.6 523.1 K, Yu et al. [28]

Proposed Model

0.4
0.4

373.15 K, Fu et al. [11]

374.25 K, Mehrotra and Svrcek [29]
0.2
423.15 K, Fu et al. [11]
0.2 Proposed Model
(b)
2 4 6 8 10 2 4 6 8 10 12
Pressure (MPa) Pressure (MPa)

Fig. 4. Comparisons between the results of the proposed model and experimental Fig. 5. Comparisons of the results of the proposed model and the experimental CO2
C2H6 solubility data in bitumen. Experimental data was obtained from Fu et al. [11] solubility data in bitumen. Experimental data was obtained from Yu et al. [28] and
and Mehrotra and Svrcek [29]. Mehrotra and Svrcek [29].

Table 4
AARDs of the experimental solubility data of light solvents in bitumen and the results of the proposed model and other predictive models.

Exp. data Predictive models AARD (%) Temperature range (K) Pressure range (MPa)
CH4
Mehrotra and Svrcek [29] Proposed model 3.4 299.85–376.95 2.57–10.07
Mehrotra and Svrcek [15] 2.7
Kariznovi et al. [12] 3.74
Fu et al. [11] Proposed model 6.2 343.15–423.15 2.17–11.83
Mehrotra and Svrcek [15] 4.5
Fu et al. [11] 4.82
C2H6
Mehrotra and Svrcek [29] Proposed model 5.7 296.05–375.85 1.02–10.07
Mehrotra and Svrcek [15] 5.7
Kariznovi et al. [12] 7.64
Fu et al. [11] Proposed model 7.2 343.15–423.15 2.62–10.96
Mehrotra and Svrcek [15] 6.5
Fu et al. [11] 4.72
CO2
Mehrotra and Svrcek [29] Proposed model 2.0 287.85–371.35 2.14–10.95
Kariznovi et al. [12] 8.89
Eastick et al. [13] 6.8
Mehrotra and Svrcek [15] 1.9
Yu et al. [28] Proposed model 5.8 323.15–523.1 4–16.04
Huang and Radosz [14] 5.67
Huang and Radosz [30] 5.44
N2
Mehrotra and Svrcek [29] Proposed model 7.6 303.85–371.35 2.46–10.66
Kariznovi et al. [12] 5.62
Mehrotra and Svrcek [15] 8.1
P x 
xexperimental 
AARD (Absolute Average Relative Deviation) = 1n  calculated
xexperimental .
 B. Azinfar et al. / Fuel 153 (2015) 240–248
0.16
0.14
304.15 K, Mehrotra and Svrcek [29]
329.95 K, Mehrotra and Svrcek [29]
0.12 370.95 K, Mehrotra and Svrcek [29]
Mole fraction of N 2
Proposed Model (333.15 K)
0.10
0.08
0.06
0.04
0.02
2 4 6 8 10
Pressure (MPa)
Fig. 6. Comparisons of the results of the proposed model and the experimental N2
solubility data in bitumen. Experimental data was obtained from Mehrotra and
Svrcek [29].
of the solubility of N2 in bitumen were compared with the
Mehrotra and Svrcek [29] experimental N2 solubility data, result-
ing in an AARD of 7.6%. Fig. 6 shows the comparison between
results of the proposed model and experimental data of N2 solubil-
ity in bitumen. This experimental data does not show consistent
trend with temperature while increasing N2 solubility by increas-
ing pressure can be found.
We also compared the predictions of the proposed model with
those of the models reported in the literature (Table 4). Our pro-
posed model proved to be more accurate in some cases. Table 4
highlights the applicability and accuracy of the proposed model
for calculating the solubility of light hydrocarbon and non-hydro-
carbon solvents in bitumen over a wide range of temperatures
and pressures. This method can be used for bitumen character-
ization and solubility calculations involved in bitumen recovery
and processing.
5. Conclusions
The ability to accurately characterize bitumen and predict the
solubility of solvents in bitumen are essential to engineering
calculations for bitumen production, upgrading, fractionation,
and refining. Due to the high molecular weight and boiling point
of the hydrocarbon molecules present in bitumen, conventional
characterization methods are not applicable or are not
straightforward.
In this work, we proposed a fast, accurate, and inexpensive
methodology based on solid theoretical background to characterize
bitumen and tune an equation of state to predict the solubility of
light solvents in bitumen. The residue curve map method was
applied to characterize the bitumen using simulated distillation
(SD) data. The Peng–Robinson equation of state (PR-EoS) and the
NRTL activity model were applied to capture the departure from
the ideal state in the gas and liquid phases. The proposed method
successfully characterized the bitumen and was applied to esti-
mate the interaction parameters of the pseudo-components.
The results of the characterization compared favorably with the
experimental molecular weight, specific gravity, and simulated
distillation (SD) curve of the bitumen. We verified the applicability
of the proposed model for calculation of the solubility of light sol-
vents in bitumen by comparison with the experimental data. The
calculated and the experimental solubility data of CH4, C2H6, CO2
and N2 were in good agreement (AARD less than 5.6 and 4.5% for
hydrocarbon and non-hydrocarbon solvents, respectively). The
247
accuracy of the proposed model was also compared with that of
some of the predictive models reported in the literature and
acceptable accuracy was found.
This model can be applied to characterize bitumen and extra
heavy oils. Application of the proposed model for bitumen
characterization eliminates the need for expensive physical dis-
tillation data and will find many applications in bitumen produc-
tion, upgrading, and refining.
Acknowledgments
The authors would like to thank the reviewers for their con-
structive comments. The authors also wish to express their
appreciation for the financial support of all member companies
of the SHARP Research Consortium: Alberta Innovates Energy and
Environment Solutions, Athabasca Oil Sands, BP Canada Energy
Group ULC, Brion Energy, Chevron Energy Technology Co.,
Computer Modelling Group Ltd., ConocoPhillips Canada, Devon
Canada Co, Foundation CMG, Husky Energy, Japan Canada Oil
Sands Limited, Nexen Energy ULC, Laricina Energy Ltd., Natural
Sciences and Engineering Research Council of Canada (NSERC),
Osum Oil Sands Co., PennWest Energy, Statoil Canada Ltd.,
Suncor Energy and Total E&P Canada. The support of the
Department of Chemical and Petroleum Engineering and the
Schulich School of Engineering at the University of Calgary is also
acknowledged.
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