Fuel 86 (2007) 1069–1078

www.fuelfirst.com

Effects of asphaltene content on the heavy oil viscosity

at different temperatures
Peng Luo, Yongan Gu *

Petroleum Technology Research Centre (PTRC), Petroleum Systems Engineering, Faculty of Engineering, University of Regina,
Regina, Saskatchewan, S4S 0A2 Canada

Received 29 May 2006; received in revised form 18 October 2006; accepted 24 October 2006
Available online 21 November 2006

Abstract

Asphaltene content plays an important role in determining the high viscosity of heavy oil. This paper presents an experimental and
theoretical study of the specific effects of asphaltene content on the heavy oil viscosity at different temperatures. In the experiment, a
deasphalted heavy oil is obtained by using a standard ASTM method to precipitate asphaltenes from a crude heavy oil. Then eleven
reconstituted heavy oil samples are prepared by adding the precipitated asphaltenes into the deasphalted heavy oil at a different asphal-
tene content each time. The viscosities of such reconstituted heavy oil samples with different asphaltene contents are measured at six
different constant temperatures by using a cone-plate viscometer. Theoretically, two viscosity models for a colloidal dispersion system
are applied to find the best fit to the experimental data by using non-linear regression. The following four important parameters are thus
determined to characterize the reconstituted heavy oil samples: the solvation constant, shape factor, intrinsic viscosity, and maximum
packing volume fraction. The detailed non-linear regression results show that the state of asphaltene particles in the heavy oil changes
with the asphaltene content and temperature and that this state change strongly affects the heavy oil viscosity.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Viscosity modeling; Asphaltene content; Heavy oil viscosity

1. Introduction
With the gradual depletion of conventional light and
medium oil resources, more attention is focused on how
to effectively and economically recover tremendous uncon-
ventional heavy oil and bitumen reserves. The western
Canada contains a large amount of heavy oil and bitumen
deposits [1], among which approximately 70%–80% of the
original-oil-in-place (OOIP) remains unrecovered at the
economic limit after the cold production [2]. Heavy oil
and bitumen can be categorized by their high viscosities
(i.e., higher than 100 mPa s for heavy oil and 10,000 mPa s
for bitumen) and low API gravities (i.e., lower than
20.0°API for heavy oil and 10.0°API for bitumen) [3].
*
Corresponding author. Tel.: +1 306 585 4630; fax: +1 306 585 4855.
E-mail address: Peter.Gu@Uregina.Ca (Y. Gu).
URL: http://uregina.ca/~gupeter2/ (Y. Gu).
Due to their extremely high viscosities, the heavy oils can-
not be effectively recovered by using some existing oil
recovery techniques for the conventional light and medium
crude oils.
The high viscosity of heavy oil is a crucial factor that
strongly affects its up-stream recovering, down-stream
surface transporting and refining processes. A better
understanding of the origination of its high viscosity can
greatly help to find more effective and economical methods
for recovering the heavy oil and reducing the related capital
and/or operating costs. In the literature, there are a num-
ber of theoretical models and empirical correlations for
predicting the crude oil viscosity [4–6]. However, some rig-
orously developed viscosity models for a simple liquid can-
not be directly applied to accurately predict the viscosity of
a heavy oil sample due to its rather complex composition.
The chemical and physical properties of a heavy crude oil
can change dramatically from one reservoir to another.

0016-2361/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2006.10.017
1070 P. Luo, Y. Gu / Fuel 86 (2007) 1069–1078

In practice, several empirical correlations are obtained by temperature. The detailed regression results are used to
using non-linear curve-fitting techniques [7,8]. They have study the specific effects of the asphaltene content on heavy
no or little theoretical basis and are only applicable to oil viscosity and analyse the different states of the asphal-
the heavy oils tested under the specified experimental tene particles in the heavy oil samples at different
conditions. temperatures.
In the past, several experimental studies have shown
that heavy oil viscosity is strongly dependent on the volume 2. Experimental
fraction, chemical structures, and physicochemical proper-
ties of its asphaltenes, which are the most polar and/or 2.1. Materials
heaviest components in heavy oil [9,10]. An effective way
to model the viscosity of a heavy oil is to consider it as a The heavy oil sample was collected from the Lloydmin-
colloidal suspension system, in which the asphaltene parti- ster area, Canada. The density and viscosity of the cleaned
cles are dispersed [11]. The heavy oil is found to follow the field oil sample are equal to qoil = 988 kg/m3 and loil =
theories formulated for predicting the effect of dispersed 24,137 mPa s at the atmospheric pressure and 23.9 °C,
solid particles on the viscosity of a colloidal suspension sys- respectively. The asphaltene content of the crude heavy
tem [12–14]. According to the existing suspension viscosity oil is found to be wasp = 14.50 wt.% (n-pentane insoluble).
theories, the volume fraction and aggregation state of The compositional analysis result of this heavy oil obtained
asphaltene particles in a given heavy oil sample can greatly by using the simulated distillation is given in Table 1. It can
affect its viscosity. be seen from this table that there are no light components
The effect of asphaltene content on the heavy oil viscos- under C12 and that there is a large fraction of heavy com-
ity has long been studied. Mack [15] measured the viscosity ponents with C50+ = 47.50 wt.%. Given the asphaltene
data for a Mexican asphalt, which clearly show an increase content of wasp = 14.50 wt.% (n-pentane insoluble), it
of its viscosity with its asphaltene content. The viscosity of becomes obvious that the carbon numbers of most asphalt-
a reconstituted oil with 20 vol.% of asphaltenes was 367 enes in this heavy oil are much larger than C50. The purity
times higher than that of the deasphalted oil (i.e., maltenes) of n-pentane (Fisher Scientific, USA) used in precipitating
at the room temperature. Also it was concluded that the the asphaltenes and measuring the asphaltene content is
significant viscosity increase with the asphaltene content 99.9%.
is probably due to strong aggregation of asphaltene parti-
cles. Dealy [16] added 5 wt.% asphaltenes into an Athaba- 2.2. Oil sample preparation
sca bitumen sample with the original asphaltene content of
16 wt.% (n-pentane insoluble) and found that the bitumen The experimental procedure for preparing the reconsti-
viscosity increases from 300,000 to 1,000,000 mPa s. More- tuted heavy oil samples with different asphaltene contents
over, Storm and Sheu [13] applied four viscosity models for is described below. In the preparation, first, asphaltenes
a colloidal dispersion system to study the relative viscosity were precipitated from the original crude heavy oil by using
of a Ratawi vacuum residue as a function of asphaltene the standard ASTM D2007 method. More specifically, one
weight percentage. It was found that the Ratawi asphaltene volume of heavy oil was mixed with 40 volumes of n-pen-
particles have spherical shapes and are considerably sol-
vated with the solvation constants of 2.4–2.9 at 93 °C.
Table 1
The maximum packing volume fraction of asphaltene par- Compositional analysis result of the original crude heavy oil (wasp =
ticles at which the viscosity of the Ratawi vacuum residue 14.50 wt.%, n-pentane insoluble)
approaches infinity was determined to be 0.35. Argillier Carbon wt.% Carbon wt.% Carbon wt.%
et al. [14] studied the effects of asphaltene and resin con- number number number
tents on heavy oil rheological properties. They found that C1 0.00 C18 2.08 C35 1.47
the intrinsic viscosities of two different heavy oils are equal C2 0.00 C19 2.13 C36 1.40
to 12.8 and 10.1 at 20 °C, and suggested that the resins can C3 0.00 C20 1.87 C37 0.87
form steric layers around the asphaltene particles to pre- C4 0.00 C21 2.28 C38 0.85
C5 0.00 C22 1.50 C39 1.35
vent their aggregation.
C6 0.00 C23 2.24 C40 1.23
In this paper, an experimental study is conducted to C7 0.00 C24 2.08 C41 0.62
measure the viscosities of eleven reconstituted heavy oil C8 0.00 C25 1.66 C42 0.61
samples with different asphaltene contents at six different C9 0.00 C26 1.56 C43 1.10
constant temperatures. The measured relative viscosity C10 0.00 C27 1.80 C44 0.80
C11 0.00 C28 1.85 C45 0.80
dependence of each heavy oil sample on its asphaltene con-
C12 0.86 C29 1.56 C46 0.57
tent is interpreted by using two viscosity models for a col- C13 1.14 C30 1.50 C47 0.72
loidal dispersion system. Non-linear regression of the C14 1.33 C31 1.93 C48 0.72
experimental data is undertaken to determine the solvation C15 1.74 C32 1.78 C49 0.68
constant, shape factor, intrinsic viscosity, and maximum C16 1.75 C33 1.04 C50+ 47.50
C17 2.01 C34 1.02 Total 100.00
packing volume fraction of the asphaltene particles at each
 P. Luo, Y. Gu / Fuel 86 (2007) 1069–1078
tane, which was used as a precipitant. The mixture was agi-
tated by using a magnetic stirrer (SP46925, Barnstead/
Thermolyne Corporation, USA) for 12 h and then filtered
through a 2.5 lm filter paper (Whatman, England). The
filter cake, which was mainly composed of precipitated
asphaltenes, was kept rinsing with n-pentane until n-pen-
tane remains colorless. On the other hand, the filtrate
was distilled to recover the dissolved n-pentane and the
remainder was the deasphalted heavy oil (i.e., maltenes).
The precipitated asphaltenes and the remaining maltenes
were slowly dried on the heated magnetic stirrer until their
weights did not change from the readings of an electric
balance (PM 4600, Mettler Toledo, Canada). Then the
asphaltenes were ground and sifted through a 75 lm sieve
(RX-29, Fisher Scientific, USA). Finally, the reconstituted
heavy oil samples with different asphaltene contents were
prepared by dispersing a different amount of sifted asphalt-
enes into the maltenes each time and agitating the mixture
for 1 h at 80 °C.
The density of maltenes was measured by using a digital
densitometer (DMA 512 P, Anton Paar, USA) and found
to be qmal = 962 kg/m3 at the atmospheric pressure and
23.9 °C. Also the density of the crude heavy oil was mea-
sured to be qoil = 988 kg/m3 under the same conditions.
Thus the density of asphaltenes can be estimated from
the following equation:
wasp
qasp ¼ 1 1wasp
; ð1Þ

qoil qmal
where wasp is the weight percentage of asphaltenes in the ori-
ginal crude heavy oil, which is equal to wasp = 14.50 wt.%
(n-pentane insoluble) in this study. With the measured qmal,
qoil, and wasp, the density of asphaltenes was found to be
qasp = 1175 kg/m3. Moreover, the weight percentage w of
asphaltenes in each reconstituted heavy oil sample can be
converted into the volume fraction / by
qsample
/¼ w; ð2Þ
qasp
where qsample is the density of each reconstituted heavy oil
sample calculated from its weight percentage by using lin-
ear interpolation of the measured densities of the maltenes
and original crude heavy oil at the atmospheric pressure
and 23.9 °C.
2.3. Oil viscosity measurement
After each reconstituted heavy oil sample was prepared,
its viscosity measurement was conducted at the atmo-
spheric pressure and different constant temperatures by
using a cone-plate viscometer (DV-II+, Brookfield Engi-
neering Laboratories, USA). During the measurement, a
heavy oil sample of 0.5 ml was placed and sheared between
a stationary flat sample cup and a slightly coned spindle,
which was rotated at a preset rate. The torque exerted on
the spindle by the heavy oil sample was proportional to
1071
the shear stress. This torque was measured and displayed
on a digital LCD panel equipped with the viscometer,
and finally converted into the viscosity reading from a
pre-calibrated viscosity versus torque chart. The viscosity
datum was recorded when the measured torque was in
50–100% of the full scale. The constant temperature during
the viscosity measurement was maintained by using a
heated circulating water bath (Haake DC10, Thermo Elec-
tron Corporation, USA) with the accuracy of ±0.1 °C. The
viscosity measurement for the original crude heavy oil was
carried out three times and the average value of the three
measured viscosity data was noted. The largest rela-
tive error in the viscosity measurements was found to be
3.39%. It was found that in the tested temperature range
of T = 20.0–60.0 °C and asphaltene volume fraction range
of / = 0–13.50 vol.% (i.e., w = 0–16.01 wt.%), the heavy oil
sample behaves as a Newtonian fluid, and that its measured
viscosity varies in the range of l = 118.7–53,672 mPa s.
3. Viscosity modeling
It has been well known that the presence of dispersed
solid particles or liquid droplets in a colloidal dispersion
significantly affects its viscosity. The relative viscosity of a
colloidal dispersion can be expressed as [17]:
l
lr ¼ ¼ 1 þ m/eff þ k 1 /2eff þ k 2 /3eff þ    ; ð3Þ
l0
where the relative viscosity lr is defined as the ratio of the
viscosity l of the colloidal dispersion to the viscosity l0 of
the dispersing liquid (i.e., the continuous phase); m is called
the shape factor of the dispersed solid particles or liquid
droplets [18]; k1 and k2 are two coefficients; and /eff repre-
sents the effective volume fraction of the dispersed phase in
the colloidal dispersion after it is solvated in the dispersing
liquid. The ratio of the effective volume fraction /eff of the
solvated phase to its original dry volume fraction / is
referred to as the solvation constant K:
/eff
K¼ ; ð4Þ
/
where / represents the dry volume fraction of the dispersed
phase prior to its dispersion. Therefore, in terms of the dry
volume fraction of the dispersed phase in the colloidal dis-
persion, the relative viscosity of the colloidal dispersion can
be generally expressed as
l
lr ¼ ¼ 1 þ ½l/ þ K 1 /2 þ K 2 /3 þ    ; ð5Þ
l0
and
½l ¼ Km: ð6Þ
Here, the intrinsic viscosity [l] is introduced when the dry
volume fraction / of the dispersed phase is used, which
represents the joint effects of solvation and shape of the dis-
persed phase on the relative viscosity; K1 = k1K2 and
K2 = k2K3.
1072 P. Luo, Y. Gu / Fuel 86 (2007) 1069–1078
Einstein [19] pioneered in modeling the viscosity of an
infinitely diluted dispersion and developed the following
Einstein equation:
lr ¼ 1 þ 2:5/: ð7Þ
In the above equation, the intrinsic viscosity [l] is equal to
the shape factor m = 2.5 for rigid spherical particles with no
solvation effect (i.e., K = 1). In many practical cases, how-
ever, several factors make the Einstein equation inapplica-
ble. They include the solvation effect, non-sphericity, and
high concentration of the dispersed phase. In the literature,
different viscosity models for a colloidal dispersion have
been proposed to take account of these factors.
Pal and Rhodes [20] suggested the following viscosity
model to consider the solvation effect of a concentrated
emulsion:
2:5
lr ¼ ð1  K/Þ : ð8aÞ
This equation is applicable for the dry volume fraction of
the emulsion droplets to be higher than 0.1. The shape fac-
tor of m = 2.5 in the Pal–Rhodes equation indicates that the
emulsion droplets are assumed to be spherical. For the
non-spherical dispersed solid particles in a suspension,
the above equation can be generalized by introducing the
shape factor m [21]:
m
lr ¼ ð1  K/Þ ; ð8bÞ
where the solvation constant K and the shape factor m can
be used as adjustable parameters and determined simulta-
neously by using the non-linear regression if the measured
lr versus / data are available.
The computational scheme for the two-parameter (K
and m) search used in this study is briefly described below.
For the heavy oil samples with different dry asphaltene vol-
ume fractions at each constant temperature, the following
objective function is defined to quantify the overall discrep-
ancy between the theoretically calculated relative viscosity
lrci from the generalized Pal–Rhodes equation with some
guessing values of the solvation constant K and the shape
factor m and the experimentally measured relative viscosity
lrmi at the same dry volume fraction /i of the dispersed
asphaltene particles, i = 1, 2, . . ., n:
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u n 
u1 X lrci  lrmi 2
EðK; mÞ ¼ t ; ð9Þ
n i¼1 lrmi
where n represents the number of the reconstituted heavy
oil samples with different asphaltene volume fractions
tested at the same temperature, n = 11 in this study. Math-
ematically, the objective function E(K, m) is equal to the
root-mean-squared relative error between the theoretically
calculated and experimentally measured relative viscosities
for the heavy oil samples with different asphaltene contents
at the same temperature. Hence, the global minimum
objective function E(K, m)min represents the best fit of the
theoretically calculated relative viscosities to the experi-
mentally measured data by applying the non-linear regres-
sion. The corresponding global optimum values of K and m
are the determined solvation constant and shape factor for
the reconstituted heavy oil samples with different asphal-
tene volume fractions tested at the same constant
temperature.
It is worthwhile to point out that according to the
generalized Pal–Rhodes equation, Eq. (8b), the emulsion
viscosity approaches infinity only if the effective volume
fraction (/eff = K/) of the emulsion droplets is equal to
unity. Physically, the viscosity of a colloidal dispersion
approaches infinity if the solid particles or liquid droplets
are so densely dispersed and packed that there is no free
space for them to move around. In this case, the effective
volume fraction of the dispersed solid particles or liquid
droplets is less than unity and is termed the maximum
packing volume fraction /max. Mooney [22] considered this
crowding effect of the dispersed phase and formulated the
following semi-empirical equation:
" #
½l/
lr ¼ exp /
: ð10Þ
1  /max
This equation has two parameters, i.e., the intrinsic viscos-
ity [l] and the maximum packing volume fraction /max,
both of which can be determined by applying the two-
parameter ([l] and /max) search and the non-linear regres-
sion, similar to the case for the generalized Pal–Rhodes
equation. It is also of great interest to compare the intrinsic
viscosity obtained from the above Mooney equation and
[l] = Km, where the solvation constant K and the shape fac-
tor m are obtained from the generalized Pal–Rhodes equa-
tion. On the other hand, it is worthwhile to note that the
maximum packing volume fraction /max obtained from
the Mooney equation should be considered as the maxi-
mum effective packing volume fraction if the dispersed
phase is solvated in the dispersing liquid.
Finally, the liquid viscosity dependence on temperature
can be described by using the Arrhenius equation, which
was derived from the Eyring’s theory of viscosity [23]:
  
Ea 1 1
lðT Þ ¼ lðT 0 Þ exp  ; ð11Þ
R T T0
where l(T) is the liquid viscosity at the absolute tempera-
ture T; l(T0) is the liquid viscosity at a reference tempera-
ture T0; Ea is the activation energy of viscous flow (J/mol);
R is the universal gas constant (J/K mol). The Eyring’s the-
ory states that in order for a liquid molecule to move, the
other surrounding molecules must move into the adjacent
vacant sites to create a free space for the molecule to enter.
The viscous flow of any liquid can be generally regarded as
a thermally activated process. At a higher temperature, the
liquid molecules have higher thermal energy so that they
can more easily overcome an energy barrier and move into
the adjacent vacant sites. In this paper, the above Arrhe-
nius equation is used to study the temperature effect on
the viscosity of the reconstituted heavy oil sample with
the same asphaltene volume fraction. More specifically,
 P. Luo, Y. Gu / Fuel 86 (2007) 1069–1078 1073

T0 = 60 °C is chosen as the reference temperature and Eq. measurements are conducted at six different constant tem-
(11) can be rewritten as peratures in the range of 20–60 °C. Fig. 1 shows the mea-
  sured absolute viscosity of the reconstituted heavy oil
lðT Þ Ea 1 1
ln ¼  : ð12Þ sample versus its asphaltene volume fraction at different
lð60  CÞ R T 333:15
  constant temperatures. It is clearly seen from this figure
lðT Þ 1 1 1 that the asphaltene content in heavy oil plays a dominant
A plot of ln versus  results in a
lð60  CÞ R T 333:15 role in determining its high viscosity, particularly at low
straight line with the slope of Ea, which is the activation en- temperatures. For example, at the reservoir temperature
ergy of viscous flow for the reconstituted heavy oil sample. of 23.9 °C, the viscosity of the original crude heavy oil with
the asphaltene content of wasp = 14.50 wt.% (/asp =
4. Results and discussion 12.19 vol.%) is equal to 24,137 mPa s. The viscosity of the
reconstituted heavy oil sample with zero asphaltene con-
4.1. Measured viscosities at different temperatures tent (i.e., maltenes) is only 1,767 mPa s at the same temper-
ature, which is over one order lower than that of the
In this study, eleven reconstituted heavy oil samples are original crude heavy oil.
prepared, whose dry asphaltene volume fractions range In this paper, the relative viscosity is defined as the ratio
from 0 to 13.50 vol.% (i.e., w = 0–16.01 wt.%). Viscosity of the viscosity of the reconstituted heavy oil sample with a

60000
20.0°C
23.9°C
50000
30.0°C
40.0˚C
Viscosity μ [mPa⋅s]

40000 50.0°C
60.0°C

30000

20000

10000

0
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14
Asphaltene volume fraction φ

Fig. 1. Measured viscosity of the reconstituted heavy oil sample versus the asphaltene volume fraction at different constant temperatures.

22
20.0°C
20 23.9°C
18 30.0°C
40.0°C
16 Concentrated region
Relative viscosity μ r

50.0°C
14 60.0°C

12
10
8
6 Diluted region
4
Tangled region
2
0
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14
Asphaltene volume fraction φ

Fig. 2. Measured relative viscosity of the reconstituted heavy oil sample versus the asphaltene volume fraction at different constant temperatures.
1074 P. Luo, Y. Gu / Fuel 86 (2007) 1069–1078

known asphaltene content to that of maltenes with no volume fraction becomes higher, the asphaltene particles in
asphaltene content at the same temperature. Fig. 2 shows heavy oil become more concentrated and the short-range
the measured relative viscosity of the reconstituted heavy inter-particle interactions become more pronounced. The
oil sample versus the asphaltene volume fraction at differ- relative viscosity versus the asphaltene volume fraction
ent constant temperatures. Roughly speaking, there are starts to deviate from the linear relation and increase more
three different regions in the asphaltene volume fraction quickly. Also the relative viscosity becomes more sensitive
range tested. First, at low asphaltene volume fractions to the temperature in this region. Thirdly, after the asphal-
(/ 6 5 vol.%), the relative viscosity of each reconstituted tene volume fraction in the reconstituted heavy oil sample
heavy oil sample increases slowly and almost linearly with exceeds /asp = 12.19 vol.% in the original crude heavy oil,
the asphaltene volume fraction at all the temperatures. The the relative viscosity increases most quickly with the
relative viscosity is the least sensitive to the temperature in asphaltene volume fraction and is the most sensitive to
this case. In such a diluted region, the asphaltene particles the temperature. The dispersed asphaltene particles are
are sufficiently far away from each other and thus the inter- close to each other and become tangled. There exist strong
actions among them are negligible. Slow increase in viscosity inter-particle interactions among the dispersed asphaltene
with the asphaltene volume fraction is due to the long- particles in the third region.
range hydrodynamic interactions between the asphaltene It should be noted that increase of the relative viscosity is
particles and the maltenes [24]. Secondly, as the asphaltene much larger at higher asphaltene volume fractions and lower

5
13.50 vol.%, Ea = 80.42 kJ/mol
12.19 vol.%, Ea = 78.34 kJ/mol
4 10.35 vol.%, Ea = 74.93 kJ/mol
6.68 vol.%, Ea = 69.07 kJ/mol
3.17 vol.%, Ea = 64.15 kJ/mol
3
μ (60oC)

0 vol.%, Ea = 61.03 kJ/mol

μ (T)
ln

0
0.00 0.01 0.02 0.03 0.04 0.05
1 1 1
( − ) [mol/kJ)]
R T 333.15
Fig. 3. Plots in terms of the Arrhenius equation for six reconstituted heavy oil samples with six different asphaltene contents.

85
Activation energy of viscous flow E a (kJ/mol)

80

75

70

65

60
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14
Asphaltene volume fraction φ

Fig. 4. Activation energy of viscous flow versus the asphaltene volume fraction for eleven reconstituted heavy oil samples.
 P. Luo, Y. Gu / Fuel 86 (2007) 1069–1078 1075

temperatures. For example, at 20.0 °C, as the asphaltene 3.2

volume fraction increases from 5.08 to 13.50 vol.%, the cor-
responding relative viscosity increases from 2.6 to 20.8. At
60 °C, however, the relative viscosity increases only from
1.9 to 7.8 in the same asphaltene volume fraction range. 3.1

Solvation constant K
Fig. 3 shows the plots in terms of the Arrhenius equa-
tion, Eq. (12), for six reconstituted heavy oil samples with
six different asphaltene contents and Fig. 4 shows the deter-
3.0
mined activation energy of viscous flow versus the asphal-
tene volume fraction curve for eleven reconstituted heavy
oil samples. The activation energies of viscous flow deter-
mined in this study are in the same range of 60–85 kJ/ 2.9
mol for petroleum asphaltenes reported in the literature
[25–27]. It is clearly seen from Fig. 4 that the activation
energy Ea increases almost linearly with the asphaltene vol-
ume fraction /. This is because at a higher asphaltene vol- 2.8
ume fraction, there exist stronger attractive inter-particle 5.5 5.6 5.7 5.8 5.9 6.0 6.1 6.2 6.3 6.4 6.5
interactions among the dispersed asphaltene particles. Shape factor v
Therefore, a higher activation energy of viscous flow is
required to overcome these attractive inter-particle interac- 2.7
tions and enable the heavy oil sample to flow [28].

2.6
4.2. The solvation constant K and the shape factor m
Solvation constant K

In this study, the generalized Pal–Rhodes equation, Eq.

(8b), is used to find the best fit to the experimentally mea-
sured relative viscosity data shown in Fig. 2 in the asphal-
tene volume fraction range of / = 0–13.50 vol.%. In Eq.
(8b), the solvation constant K and the shape factor m are
chosen in the ranges of 1–5 and 2.5–10, respectively.
Fig. 5a and b show the contours of the objective function
E(K, m) defined in Eq. (9) at two different temperatures of
20 and 60 °C, respectively, where lrc is calculated from
the generalized Pal–Rhodes equation. It can be seen from
these two figures that E(K, m) is strongly dependent on both
K and m in the chosen ranges. When temperature increases
from 20 to 60 °C, the contours move downwards to the
left-hand side and become wider.
Table 2 summarizes the obtained non-linear regression
results, including the correlation coefficients R2, at six dif-
ferent constant temperatures. The corresponding intrinsic
viscosity [l] is calculated from Eq. (6) as a product of the
solvation constant K and the shape factor m. This table
shows that, in general, both the solvation constant and
the shape factor decrease as temperature increases, except
for the solvation constant at T = 60 °C and the shape
factors at T = 40 and 50 °C. Thus the intrinsic viscosity
2.5
2.4
2.3
4.5 4.6 4.7 4.8 4.9 5.0 5.1 5.2 5.3 5.4 5.5
Shape factor v
Fig. 5. Contours of the objective function E(K, m) defined in Eq. (9) at
(a) 20 °C; and (b) 60 °C, where lrc is calculated from the generalized
Pal–Rhodes equation.
decreases quickly with temperature. Meanwhile, the mini-
mum objective function E(K, m)min decreases as tempera-
ture increases. This means that the generalized Pal–
Rhodes equation is more applicable for the heavy oil at a
higher temperature when the inter-particle interactions
among the dispersed asphaltene particles become weaker.
It is worthwhile to note that the generalized Pal–Rhodes

Table 2
Non-linear regression results obtained by using the generalized Pal–Rhodes equation
Temperature (°C) 20.0 23.9 30.0 40.0 50.0 60.0
Solvation constant, K 2.982 2.940 2.912 2.524 2.488 2.494
Shape factor, m 5.934 5.820 5.494 6.032 5.504 5.050
Minimum objective function, E(K, m)min (%) 3.924 3.859 3.469 2.951 2.514 2.400
Intrinsic viscosity [l] = Km 17.695 17.111 15.999 15.225 13.694 12.595
Correlation coefficient, R2 0.994 0.993 0.995 0.996 0.996 0.997
1076 P. Luo, Y. Gu / Fuel 86 (2007) 1069–1078

equation has been proposed for a simple dispersion system

20
with no interactions among the dispersed phase.
For analysis purpose, here, the asphaltene particles are
assumed to be spherical. At a lower temperature, there is
19
a stronger solvation effect and thus the effective volume

Intrinsic viscosity [ μ]
of the solvated asphaltene particles becomes larger
[29,30]. In terms of the definition of the solvation constant,
18
the average radius of the solvated asphaltene particles is
larger
pffiffiffiffi than that of the dry asphaltene particles by a factor
of 3 K . At a higher temperature, the adsorbed resins at the
17
outmost layers have higher kinetic energy and thus can be
more readily desorbed from the asphaltene particles. As a
consequence, the solvation constant is reduced. For
16
instance, at 20 °C, the average radius of the solvated
pffiffiffiffiffiffiffiffiffiffiffi
asphaltene particles is about 3 2:982 ¼ 1:439 times of that
of the dry asphaltene particles. When temperature increases
pffiffiffiffiffiffiffiffiffiffiffi 15
to 60 °C, this ratio is reduced to 3 2:494 ¼ 1:356. In partic- 0.50 0.55 0.60 0.65 0.70
ular, the solvation constant decreases quickly when tem- Maximum packing volume fraction φ max
perature increases from 30 to 40 °C. This indicates that
the resins at the outmost layers can be easily desorbed from 15
the asphaltene particles in this temperature range. The
hydrogen bonds and charge-transfer p–p bonds between
the asphaltene particles and the resins at the outmost layers 14
are broken in this case [31].
Intrinsic viscosity [ μ]

In the literature, the shapes of the dispersed asphaltene

particles in a heavy oil sample were found to be spherical
(m = 2.5) [13,32], ellipsoidal (m > 2.5) [33], and disk-like
(m > 2.5) [34]. In this study, the large differences of the
determined shape factors of m = 5.050–6.032 from m = 2.5
indicate that the asphaltene particles tested in this study
are non-spherical. It is also found that the shape factor
decreases as temperature increases. It is speculated that at
a higher temperature, more resins at the outmost layers
are desorbed from the asphaltene particles so that their
shapes are more rounded, closer to the spherical shape.
4.3. The intrinsic viscosity [l] and the maximum packing
volume fraction /max
With the Mooney equation, Eq. (10), similar two-
parameter search and non-linear regression are applied to
determine the intrinsic viscosity [l] and the maximum
packing volume fraction /max in the ranges of [l] = 5–20
and /max = 0.2–1.0, respectively. Fig. 6a and b show the
contours of the objective function E([l], /max) at 20 and
60 °C, respectively. It is seen from these two figures that
the objective function E([l], /max) is much more sensitive
to the intrinsic viscosity [l] than to the maximum packing
volume fraction /max. As temperature is increased, the
contours move downwards, which indicates a consider-
ably decreased intrinsic viscosity [l] at an increased
temperature.
Table 3 lists the detailed non-linear regression results,
including the correlation coefficients R2, for six different
constant temperatures obtained by using the Mooney
equation. It is found that the intrinsic viscosities [l] deter-
mined from the Mooney equation are in an excellent agree-
13
12
11
10
0.60 0.65 0.70 0.75 0.80
Maximum packing volume fraction φmax
Fig. 6. Contours of the objective function E([l], /max) at (a) 20 °C; and
(b) 60 °C, in which lrc is calculated from the Mooney equation.
ment with [l] = Km given in Table 2, where the solvation
constant K and the shape factor m are obtained by applying
the generalized Pal–Rhodes equation. On the other hand, it
is found that the maximum packing volume fraction /max
increases with temperature. This is because at a higher tem-
perature, more resins at the outmost layers are desorbed
and thus the effective volumes of the solvated asphaltene
particles become smaller. In this case, more asphaltene
particles can be dispersed in the heavy oil sample. Further-
more, Table 3 shows that the minimum objective function
E([l],/max)min decreases as temperatures increases. It
should be noted that the Mooney equation is derived for
a simple dispersion system, in which the inter-particle inter-
actions are neglected. At a higher temperature, the interac-
tions among the dispersed asphaltene particles in the heavy
 P. Luo, Y. Gu / Fuel 86 (2007) 1069–1078
Table 3
Non-linear regression results obtained by using the Mooney equation
Temperature (°C) 20.0
Intrinsic viscosity [l] 17.520
Maximum packing volume fraction, /max 0.598
Minimum objective function, E([l], /max)min (%) 3.902
Correlation coefficient, R2 0.996
oil samples tested are weaker so that the Mooney equation
becomes more applicable.
It is interesting to note that, here, the intrinsic viscosity
[l] of the asphaltene particles dispersed in their natural
medium (i.e., maltenes) is found to be considerably larger
than those of the asphaltene particles dispersed in organic
solvents [14,30,35,36]. If the shape factors m of the asphal-
tene particles are assumed to be almost the same due to
their stiffness, a larger intrinsic viscosity means a larger sol-
vation constant K, as [l] = Km. Thus there exist stronger
interactions (i.e., the solvation effect) between the asphalt-
enes and the resins in the maltenes for the reconstituted
heavy oil samples tested in this study. Altgelt and Harle
[12] found that the asphaltene particles dispersed in their
natural medium (i.e., maltenes) have stronger solvation
effect than those dispersed in some organic solvents, such
as toluene and xylene [35]. This is because the asphalt-
enes and resins have rather similar chemical structures
and strong interactions through the hydrogen bonds and
charge-transfer p–p bonds.
It is known that for a mono-dispersion consisting of the
rigid spherical particles with only mechanical packing, the
maximum packing volume fraction /max is equal to 0.74
for a face-centered cubic packing and 0.68 for a body-
centered cubic packing [37], respectively. The differ-
ences between the maximum packing volume fractions
(/max = 0.598–0.734) determined in this study and the
above-mentioned two typical values may be caused by
the following three reasons. First, in this study, the asphal-
tene particles are found to be non-spherical (m > 2.5) and
probably have different sizes, i.e., polydispersity. Secondly,
there exist strong interactions among the asphaltene parti-
cles, especially at high asphaltene contents. Thirdly, solva-
tion of the asphaltene particles in the maltenes makes their
effective volume fraction much higher than their dry vol-
ume fraction. Hence, at a lower temperature, the deter-
mined /max is lower due to stronger solvation effect. On
the other hand, it is noted that from 30 to 40 °C, /max
obtained from the Mooney equation has a sharp increase.
This corresponds to the sharp decrease of the solvation
constant K obtained from the generalized Pal–Rhodes
equation in the same temperature range, as given in Table
2. Physically, when the solvation effect of the asphaltene
particles becomes weaker at a higher temperature, their
effective volumes are smaller so that the maximum packing
volume fraction /max becomes higher. Obviously, the max-
imum packing volume fraction (/max = 0.598–0.734) deter-
mined in this study represents the maximum effective
packing volume fraction of the asphaltene particles with
1077
23.9 30.0 40.0 50.0 60.0
16.950 15.840 15.130 13.610 12.510
0.609 0.613 0.723 0.734 0.729
3.844 3.411 2.934 2.496 2.375
0.995 0.996 0.997 0.997 0.997
appreciable solvation effect in the maltenes. The maximum
dry packing volume fraction of the asphaltene particles is
lower than the determined maximum effective packing vol-
ume fraction by a factor of the solvation constant, i.e.,
/ = /eff/K [38]. Therefore, the maximum dry packing vol-
ume fraction of the asphaltene particles is estimated to be
in the range of / = 0.201–0.295.
Finally, it is worthwhile to point out that the theoreti-
cally determined maximum packing volume fraction /max
is solely based on geometrical consideration. In practice,
when a sufficient amount of asphaltene particles is dis-
persed in a heavy oil sample, there may not be enough res-
ins in the maltenes to surround and adsorb onto all the
asphaltene particles. In this case, the dispersed asphaltene
particles may aggregate and even precipitate if they become
large enough. Accordingly, the heavy oil viscosity may
increase significantly. It is to be ascertained whether the
asphaltene volume fraction at which the aggregation and
even precipitation of asphaltene particles occur is lower
or higher than the theoretically determined maximum
packing volume fraction /max, at which the asphaltene par-
ticles are so densely dispersed that there is no free volume
for them to move around.
5. Conclusions
This study presents a simple and practical method for
analysing the complex heavy oil with the dispersed asphal-
tene particles by measuring its viscosity versus its asphal-
tene content at different constant temperatures. It is
found that the asphaltene content in a heavy oil sample
plays a dominant role in determining its high viscosity.
The strong attractive interactions among the asphaltene
particles at a high asphaltene content cause the heavy oil
viscosity to increase dramatically. It is also found that at
an increased temperature, the heavy oil viscosity can be
reduced significantly, especially at a high asphaltene
content. Two commonly used viscosity equations for a
colloidal dispersion system, the generalized Pal–Rhodes
equation and the Mooney equation, are applied to model
the viscosity behavior of eleven reconstituted heavy oil
samples with different asphaltene contents at six different
constant temperatures. The solvation constant K and the
shape factor m obtained by using the generalized Pal–
Rhodes equation show that the asphaltene particles are
considerably solvated in the maltenes and that they are
non-spherical. At an increased temperature, the adsorbed
resins at the outmost layers can obtain enough thermal
energy to escape from the asphaltene particles so that both
1078 P. Luo, Y. Gu / Fuel 86 (2007) 1069–1078
the solvation constant K and the shape factor m are reduced.
In addition, the intrinsic viscosity [l] and the maximum
packing volume fraction /max are determined by using the
Mooney equation. The determined intrinsic viscosities [l]
are in an excellent agreement with [l] = Km, where K and
m are obtained by using the generalized Pal–Rhodes equa-
tion. When temperature increases, the maximum packing
volume fraction /max increases as the effective volumes of
the asphaltene particles are reduced due to resin desorption.
In general, it has been found that these two equations give a
better fit between the theoretically predicted and experimen-
tally measured relative viscosities at a higher temperature.
This fact indicates that these two viscosity models are more
suitable for a colloidal dispersion system at higher temper-
atures, at which the inter-particle interactions among the
dispersed phase become weaker.
Acknowledgments
The authors acknowledge the discovery grant from the
natural sciences and engineering research council (NSERC)
of Canada and the innovation fund from the petroleum
technology research centre (PTRC) at the University of
Regina to Y. Gu.
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