SPE 157930

Prediction of Bitumen and Solvent Mixture Viscosity Using Cubic-Plus-

Association Equation of State
Mohsen Zirrahi, Hassan Hassanzadeh, Jalal abedi, University of Calgary, Calgary, Canada, AB

Copyright 2012, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Heavy Oil Conference Canada held in Calgary, Alberta, Canada, 12–14 June 2012.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
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Abstract
Viscosity is an important transport property for engineering design and simulation of bitumen production and transportation.
During the production of bitumen with solvent injection, steam-assisted gravity drainage (SAGD) or expanding solvent
steam-assisted gravity drainage (ES-SAGD), the produced fluid is faced with various temperature, pressure and composition
conditions. Therefore, a model is necessary to predict the viscosity of the mixture of bitumen and solvent in wide ranges of
temperatures, pressures and compositions (T-P-x).
In this work, we propose a semi-theoretical viscosity model based on the Arrhenius mixing rule and considering the effect of
association between the molecules of the solvent and the bitumen. To achieve this purpose, thermodynamic perturbation
theory (TPT) is used. The association part of the cubic-plus-association (CPA) equation of state (EoS) is applied to calculate
the fraction of bonding solvent molecules. We calculate the viscosity of the solvent in wide temperature and pressure ranges
using the modified Enskog theory (MET).
Results show an acceptable agreement between the results of this model and experimental viscosity data of saturated bitumen
with different solvents (CH4, N2, CO2, and C2H6) at various T-P-x ranges. These experimental data cover the typical T-P-x
ranges of oil recovery methods.
Keywords: viscosity, bitumen, solvent, Enskog’s equation, cubic-plus-association

1. Introduction

The viscosity of diluted heavy oil and bitumen is one of the most important transport properties for the design and
engineering calculations of heavy oil and bitumen production and transportation. In addition, the reliability of reservoir
simulation results is highly dependent on estimation of the transport properties of reservoir fluids. Therefore, a predictive and
accurate viscosity model is necessary for most engineering studies in this field.
There are many viscosity models in the literature that predict the viscosity of pure hydrocarbons, heavy oil and bitumen
with acceptable accuracy. Comprehensive reviews were done by Monnery et al. (1995) and Mehrotra et al. (1996). However,
for diluted bitumen and mixtures of heavy oil and solvent, an accurate model is lacking. Various mixing rules have been used
to calculate mixtures of bitumen and solvent. Arrhenius (1887) used a logarithmic mixing rule to predict the viscosities of
mixtures. This mixing rule is proportional to the mole fraction, volume fraction or mass fraction.
The summation of the volumetric fraction of each component multiplied by the fluidity (the inverse of viscosity) of each
component was proposed by Bingham (1914). The power law mixing rule proposed by Kendall and Monroe (1917) is
another type of mixing rule that can be found in the literature. The recommended mixing rule for hydrocarbon blends is
reliable for viscosity ratios of 1 to 100, which is far from the viscosity ratio of heavy oil systems (Shu, 1984).
Observed deviations between the obtained results of the above-mentioned mixing rules and experimental data of
petroleum blends have led to the development of more complex mixing rules. A modified form of the Arrhenius mixing rule
was applied by Lederer (1931) with the introduction of an adjusting parameter. Compared to the previous mixing rules, this
mixing rule has precedence for predicting the viscosity of binary mixtures.
Shu (1984) and Barrufet and Setiadarma (2003) used this mixing rule and suggested formulas for the adjusting
parameter. The proposed formula of Shu (1984) is a function of the density and viscosity of components. Barrufet and
Setiadarma’s mixing rule (2003) is a function of the solvent mole fraction. Barrufet and Setiadarma (2003) reported absolute
2 SPE 157930

average relative deviations (AARDs) of 24-27% in the prediction of the viscosity of diluted heavy oil and bitumen with n-
decane for their model and the model of Shu (1984). Another method for the prediction of the viscosity of saturated bitumen
is the use of mixing rules with the temperature dependent constants as reported by Mehrotra (1992).
The expanded theory (ET) has recently been applied in the calculation of the viscosity of hydrocarbon mixtures.
Motahhari et al. (2011a) represented the viscosities of symmetric hydrocarbons with an AARD of less than 10% for 90 binary
mixtures. This model is applicable for symmetric hydrocarbons. Motahhari et al. (2001b) also tested their model for diluted
bitumen. AARDs of 20-28% for live bitumen and 16-30% for diluted bitumen have been obtained, depending on the mixture
density used in the viscosity calculations. The lower bound of the AARDs was obtained when the measured density was
used.
In this work, we present a viscosity model based on the Arrhenius mixing rule, using modified Enskog theory (MET) and
the cubic-plus-association equation of state (CPA-EoS) to estimate diluted bitumen viscosity. The proposed model is then
compared with experimental data of Cold Lake bitumen (Mehrotra and Scverk, 1988).

2. Viscosity Model

2.1 Pure Solvent

We used modified Enskog theory to calculate the viscosities of pure solvents at given temperatures and pressures. On the
basis of this model, the viscosity of gas rigid spheres is obtained by Hirschfelder et al. (1964):
1  (1)
  0b0    0.8  0.761 
 

where η and η0 denote the viscosities of hard spheres and dilute hard spheres, respectively; parameter b0 is the co-volume; ρ
is the pure solvent density, and χ is given by:
  b0  g ( ) (2)

where g(σ) is the radial distribution function.

To simplify this model, we followed the method of Parsafar and Kalantar (2007). Details of this technique are described
in the mentioned reference (Parsafar and Kalantar, 2007). The final form can be given as:

 (3)
 a  2  b  c
T

where a, b and c are constants that depend on the substance only.

We tuned these parameters by fitting experimental viscosity data of pure solvents, such as methane (CH4), ethane (C2H6),
nitrogen gas (N2) and carbon dioxide (CO2) (Jams and Boyd, 1939; Eakin et al., 1962; Fenghour et al., 1998; Evers et al.,
2002; Wilhelm et al., 2006).
Table 1 summarizes the tuned parameters. The density of these components was obtained by the Peng-Robinson
equation of state (PR-EoS) coupled with the Gaussian volume shift factor proposed by Mennory et al. (1998). The remaining
parameter for the calculation of viscosity from equation (3) is χ. We used the thermal pressure to obtain χ, as suggested by
Enskog (Chapman and Gowling, 1970):
1   P   (4)
 T    1
 RT   T v 

where R is the universal gas constant. Sheng et al. (1989) used the PR-EoS to calculate  given by equation (4).

Using the PR-EoS gives:

P R 1  a(T )  (5)
   
T v  b v(v  b)  b(v  b)  T 

where
a(T )  m  m2 (1  Tr0.5 )  (6)
 a(Tc )  
T  TTc0.5 

where m, a(T) and a(Tc) are calculated by:

m  0.37464  1.54226  0.26992 2 (7)
SPE 157930 3

R 2Tc2 (8)
a(Tc )  0.45724
Pc
RTc (9)
b  0.0778
Pc
2 (10)
a(T )  a(Tc ) 1  m(1  Tr0.5 ) 

where Tc and Pc denote the critical temperature and pressure, respectively; Tr is the reduced temperature, and ω indicates the
acentric factor. The critical properties and acentric factor of pure components were obtained from Danesh (1998).

2.2 Viscosity of Bitumen

In this work, we used a viscosity model reported by Mehrotra and Svrcek (1987) to calculate the viscosity of bitumen as
given by:
ln ln( )   a  a ln T   a P
1 2 3
(11)

Parameters a1-a3 reported by Mehrotra and Svrcek (1987) are shown in Table 2.

2.3 Viscosity of Diluted Bitumen

The following mixing rule is used to calculate the viscosity of bitumen mixtures with CH4, C2H6, N2, and, CO2, as given
by (Arrhenius, 1887):
v  x ln v  x ln v
mix s s b b
(12)

where subscripts s and b denote solvent and bitumen, respectively; and, v is the kinematic viscosity.
It is known that mixing a solvent and bitumen leads to some volume expansion. Such a density reduction results in an
increase in the fluidity and, consequently, a decrease in mixture viscosity. When bonding is formed between a fraction of
solvent and bitumen molecules, this fraction loses its volume expansion contribution, and the mixing rule given by equation
(12) leads to an overestimation of viscosity. Therefore, an effective fraction of solvent can be defined as:
xeff  x X
s s s
(13)

where Xs is the non-bonded fraction of the solvent.

We used the association part of CPA-EoS to calculate the fraction of bonded solvent molecules. By using this method,
the fraction of molecules that are not bonded, Xs, is calculated by (Kontogeorgis et al., 2006):
1 (14)
Xs 
1    x j  X Bj  i j
AB

j Bj

where A and B are the bonding sites on a bitumen or solvent molecule, and ρ is the mixture density. The associating strength,
ΔAiBj , is obtained by (Kontogeorgis et al., 2006):

   Ai B j   (15)
  g (V ) ref exp    1 bij 
Ai B j Ai B j

  RT  

where βAiBj and εAiBj indicate the volume of interaction and association energy between site A of molecule i and site B of
molecule j, respectively; and, g(V)ref denotes the reference fluid radial distribution function, which can be calculated by
according to Kontogeorgis et al. (1999) as:

1 (16)
g (V ) ref 
 1 
1  1.9  b
 4V 

In this work, we consider one site type of association for the molecules of bitumen and solvent. Li and Firoozabadi
(2010) also assumed one type association for the molecules of aromatics and asphaltene. The parameters needed to
implement this model (βAiBj and εAiBj) for Cold Lake bitumen and pure solvents (CH4, C2H6, N2 and CO2) were obtained
based on tuning of experimental data and given in Table 3.
4 SPE 157930

3. Results and Discussion

We used the described model for prediction of the viscosities of pure solvents in the desired temperature and pressure
ranges. Parameters a, b and c, which were obtained from the minimization of error, are given in Table 1. The results showed
good accuracy for this model. The AARD between the results of the proposed model and the pure solvent viscosity from the
experimental data are summarized in Table 4.
The viscosity model proposed by Mehrotra and Scverk (1987) was used to calculate the viscosity of gas-free bitumen.
The calculated error for this model in the prediction of the viscosity of compressed Cold Lake bitumen was 2.1%.
Figure 1 shows the comparison between the experimental viscosity data (Mehrotra and Scverk, 1988) of saturated Cold
Lake bitumen with pure CH4 and the results of the proposed model. This figure indicates good accuracy. The AARD with
this experimental data was less than 7.4%. As shown in Table 5, the best fit was observed at 300 K. Results showed that the
deviation from the experimental data increased with increasing temperature. The AARD from experimental data at 376 K
was 10.5%.
For saturated bitumen with N2, the comparison between the experimental viscosity data and the results of this model are
shown in Figure 2. The calculation showed an AARD of less than 11.7% for our model. Better accuracy could be seen at 330
K with an AARD equal to 6.1%.
The experimental viscosity data of CO2-saturated bitumen was regenerated with an AARD of less than 11%. This
agreement is shown in Figure 3. The results showed that the developed model adequately represented the experimental data
for regions far from the critical temperature. As presented in Figure 3, deviations from the experimental data increased at 299
K, which was close to the critical region. At regions where CO2 was in the gas or supercritical phase, this model was able to
accurately reproduce the experimental viscosity data. For cases when CO2 was in a liquid state, deviations from the
experimental data were more pronounced.
Above the critical region, the results of the proposed model were in good agreement with the experimental data. AARDs
equal to 2.3, 7.1 and 10.8% were obtained for temperatures of 325, 350 and 370 K, respectively, which indicates accuracy of
the proposed model in predicting the viscosity of saturated bitumen with supercritical CO2.
For C2H6-saturated bitumen, the calculated AARD was higher than the other solvents (12.1%). As shown in Figure 4, the
viscosity data of Mehrotra and Scverk (1988) for saturated C2H6-bitumen at 325 K did not follow the same trend as with the
temperatures of 349 and 374 K. Data points above 4 MPa at 325 K were not considered in the comparison. The calculated
AARDs for each temperature are given in Table 5.

4. Conclusion
We applied modified Enskog theory coupled with thermodynamic perturbation theory to predict the saturated bitumen
with CH4, CO2, N2 and C2H6. The proposed model is applicable to temperatures and pressures up to 370 K and 10 MPa,
respectively. Comparisons with experimental viscosity data of pure solvents and Cold Lake saturated bitumen showed
acceptable accuracy.
Experimental viscosity data of pure hydrocarbon solvents, such as CH4 and C2H6, were regenerated with AARDs equal
to 1.97 and 6.47%, respectively. For non-hydrocarbon solvents, such as N2 and CO2, experimental data were represented with
AARDs equal to 1.77 and 2.18%, respectively.
We then tested the proposed model to predict the viscosity of saturated bitumen. The results of the proposed model
showed acceptable accuracy. Experimental viscosity data of saturated bitumen with hydrocarbons (CH4 and C2H6) were
represented with AARDs of about 7.4 and 12.1%, respectively. AARDs equal to 11 and 11.7% were observed for saturated
bitumen with CO2 and N2, respectively.

Nomenclature

List of symbols
a(T) Interaction parameter of equation of state
b Co-volume parameter
g(V)ref Reference fluid radial distribution function
m Equation of state parameter
P Pressure
R Gas universal constant
T Temperature
V Molar volume
x Mole fraction
X Fraction of not bonded
AARD Absolute average relative deviation
Greek symbols
ω Acentric Factor
SPE 157930 5

ν Kinematic viscosity
Δ Associating strength
β volume of interaction
ε association energy
η Viscosity
ρ Density
χ Radial distribution function
Subscripts
0 Reference state
c Critical condition
b Bitumen
r Reduced condition
s Solvent
Superscripts
eff Effective

References
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Barrufet, M.A., Setiadarma, A. 2003. Reliable Heavy Oil–Solvent Viscosity Mixing Rules for Viscosities up to 450 K, Oil–Solvent
Viscosity Ratios up to 4 × 105, and Any Solvent Proportion. Fluid Phase Equilibria 213, 65–79.
Bingham, E. C. 1914. The Viscosity of Binary Mixture. J Phys Chem, 18, 157-165.
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Danesh A. 1998. PVT and Phase Behavior of Petroleum Reservoir Fluids, 1st ed., Elsevier, Amesterdam.
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and Engineering Data, 7 (1), 33-36.
Evers, C., Lösch, H. W., Wagner, W. 2002. An Absolute Viscometer-Densimeter and Measurements of the Viscosity of Nitrogen,
Methane, Helium, Neon, Argon, and Krypton over a Wide Range of Density and Temperature, International Journal of Thermophysics, 23
(6),1411-1439.
Fenghour, A., Wakeham, W. A., Vesovic, V. 1998. The Viscosity of Carbon Dioxide. J phys. Chem Ref Data, 27 (1), 31-44.
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1802.
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Association) Equation of State. Part 1. Pure Compounds and Self-Associating Systems, Ind. Eng. Chem. Res. 45, 4855-4868.
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for Water - Methanol - Alkane Mixtures. Fluid Phase Equilib. 158 - 160, 201.
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2963.
Mehrotra, A. K. 1992. Mixing Rules for Predicting the Viscosity of Bitumens Saturated with Pure Gases, Canadian Journal of Chemical
Engineering, 70, 165-172.
Mehrotra A. K., Svrcek, W. Y. 1987. Viscosity of Compressed Cold Lake Bitumen, The Canadian Journal of Chemical Engineering, 65,
672 675.
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of Chemical Engineering, 66, 656-665.
Mehrotra, A. K., Monnery, W. D., Svrcek, W. Y. 1996. A review of Practical Calculation Methods for the Viscosity of Liquid
Hydrocarbons and Their Mixtures. Fluid Phase Equilbria, 117, 344-355.
Monnery, W. D., Svrcek, W. Y., Mehrotra, A. K. 1995. Viscosity: A Critical Review of Practical
Predictive and Correlative Methods, Canadian Journal of Chemical Engineering, 73, 3-40.
Motahhari, H., Satyro, M. A., Yarranton, H. W. 2011. Predicting the Viscosity of Asymmetric Hydrocarbon Mixtures with the Expanded
Fluid Viscosity Correlation. Ind. Eng. Chem. Res. 50, 12831–12843.
Motahhari, H., Satyro, M. A., Yarranton, H. W. 2011b. rediction of iscosity of Solvent iluted ive Bitumen at Temperature up to
C, CSUG/SPE 149405.
Parsafar, G. A., Kalantar, Z. 2007. Calculation of the Transport Properties of the Dense Fluids Using Modified Enskog Theory and an
Appropriate Equation of State. Fluid Phase Equilibria, 253, 108-117.
Sheng, W., Chen, G. J., Lu, H. C. 1989. Prediction of Transport Properties of Dense Gases and Liquids by the Peng-Robinson (PR)
Equation of State. Int. J. Thermophys., 10 (1), 133–144.
Shu, W.R. 1984. A Viscosity Correlation for Mixtures of Heavy Oil, Bitumen, and Petroleum Fractions, SPEJ, 277–282.
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6 SPE 157930

100
This Model
300 K
319 K
350 K
10 376 K
Viscosity (Pa.s)

0.1

0.01
2 4 6 8 10 12

Pressure (MPa)
Figure 1. Comparsin between results of this model and experimental viscosity data of CH4-saturated bitumen

100 This Model

304 K
330 K
370 K

10
Viscosity (Pa.s)

0.1

0.01
2 4 6 8 10 12

Pressure (MPa)
Figure 2. Viscosity of N2-saturated data predicted by proposed model vs experimental data
SPE 157930 7

This Model
288 K
10 299 K
325 K
350 K
370 K
Viscosity (Pa.s)

0.1

0.01
2 4 6 8 10 12

Pressure (MPa)
Figure 3. Comparsin between results of this model and experimental viscosity data of CO2-saturated bitumen

This model
325 K
349 K
374 K
viscosity (Pa.s)

0.1

0.01

0 2 4 6 8 10 12

Pressure (MPa)

Figure 4. Comparsin between results of this model and experimental viscosity data of C2H6-saturated bitumen
8 SPE 157930

Table 1: The value of a, b and c for implementation of Eq. (3).

Solvent a b c
CH4 1.6193796481790272E-10 1.2001279494158453E-10 2.742600505553163E-10
CO2 1.9236012021524925E-8 6.7462639825141706E-9 2.6677737157132812E-8
N2 3.1735533088767955E-8 9.78328124945472E-9 3.8449737089950474E-8
C2H6 -1.201255075143922E-9 1.7260331902865905E-8 7.343845354604997E-12

Table 2. Parameters for using Eq. (11).

a1 22.13520
a2 -3.473811
a3 0.004288

Table 3. volume of interaction (βAiBj) and association energy (εAiBj) of solvents and Cold Lake bitumen.
AiBj AiBj
β ε
CH4-bitumen 1.4265326061198254 -100061.33889388572
N2-bitumen 31.158688751950038 -138.61550498856008
CO2-bitumen 0.3523758394553751 2913.155564461725
C2H6-bitumen 0.4126847088545283 -103197.45098233456

Table 4. Absolute Average Relative Deviation (AARD) for representation of experimental viscosity data of
pure solvent.
Solvent AARD%
CH4 1.97
CO2 2.18
N2 1.77
C2H6 6.47

Table 5. AARD of predicted results for saturated bitumen by proposed model.

Comp. T (K) P (MPa) Number of data points AARD%
300 2.57-9.93 4 5.4
319 2.58-9.74 4 7.1
CH4
350 2.85-10.04 4 6.2
376 2.61-10.08 4 10.5
304 2.46-10.48 4 13.4
N2 330 2.54-10.66 4 6.1
370 2.53-10.14 4 15.6
288 2.32-10.72 5 8.6
299 2.06-10.6 6 21.2
CO2 325 2.14-10.58 4 2.3
350 2.49-10.94 4 7.1
370 2.27-10.5 4 10.8
325 1.02-6.82 3 21.1
C2H6 349 2.58-10.07 4 12.5
374 2.46-9.98 4 19.8