SPE/Petroleum Society of CIM/CHOA 79496
Heavy Oil Rheology as a Function of Asphaltene and Resin Content and Temperature
J-F. Argillier, C. Coustet, I. Hénaut, Institut Français du Pétrole
Copyright 2002, SPE/PS-CIM/CHOA International Thermal Operations and Heavy Oil
Symposium and International Horizontal Well Technology Conference
This paper was prepared for presentation at the 2002 SPE International Thermal Operations
and Heavy Oil Symposium and International Horizontal Well Technology Conference held in
Calgary, Alberta, Canada, 4–7 November 2002.
This paper was selected for presentation by the ITOHOS/ICHWT Program Committee
following review of information contained in an abstract submitted by the author(s). Contents of
the paper, as presented, have not been reviewed by the Society of Petroleum Engineers, the
Petroleum Society of CIM, or CHOA and are subject to correction by the author(s). The
material, as presented, does not necessarily reflect any position of the Society of Petroleum
Engineers, the Petroleum Society of CIM, or CHOA, its officers, or members. Electronic
reproduction, distribution, or storage of any part of this paper for commercial purposes without
the written consent of the Society of Petroleum Engineers, Petroleum Society of CIM, or CHOA
is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300
words; illustrations may not be copied. The abstract must contain conspicuous
acknowledgment of where and by whom the paper was presented. Write Librarian, SPE,
P.O. Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.
Abstract
Because of very important reserves that are of the same
order of magnitude than conventional oils, heavy oils
represent a strategic source of hydrocarbons. The major
difficulty for producing and transporting these crudes comes
from their very high viscosities. The success of exploitation of
these petroleum products requires new treatments to improve
their transport. Such a target implies to better understand the
relationship between the composition of heavy oils, in
particular in terms of asphaltenes and resins content and their
flow properties. Influence of asphaltenes content in the crude
has been particularly studied in our lab : the experimental
work revealed the existence of a critical concentration C*
above which the asphaltenes particles overlapp. This structural
change dramatically increases the viscosity and intensifies the
elastic character of heavy crude oils. A further series of
experiments has focused on the influence of resins: they show
that in dilute regime (C<C*), resins increase the viscosity of
the crude and in concentrated regime (C>C*), which
corresponds to the case of a heavy oil, they lower the
asphaltenes effect on viscosity. Experiments were first carried
out with asphaltenes and nonylphenol as a model of resins and
followed by experimental work on real crude that confirmed
the trends. To understand the rheological behavior of a heavy
crude oil in relation with its internal structure, asphaltenes and
resins have to be simultaneously considered. From this study
we conclude that the origin of the high viscosities of heavy
oils comes from to the entanglement of solvated asphaltene
particles stabilized by resin molecules. A strong influence of
temperature on the rheology is also revealed by high activation
energy measurements. This thermal dependent rheological
behavior shows that the internal organization of the heavy
crude oil is partly based on thermal dependent physical bonds.
Using the reversibility of these physical links, we should be
able to modify the structure of heavy crude oils to facilitate
their transport.
Introduction
The increasing oil demand is leading to the development of
the very large world resources of heavy oils that are of the
same order of magnitude than conventional oils. However,
production and transport of these oils are challenging because
of their very high viscosities. Reduction of the viscosity of
heavy and extra heavy oils is thus necessary to facilitate their
production and their transport. Usual methods of heavy oils
transportation include the crude upgrading, the addition of
diluents, the formation of oil-in-water emulsions and thermal
techniques [1-3]. These technologies imply high operational
and investment costs so that less expensive solutions have to
be found. It is with this objective that the study presented here
was undertaken. It deals with the relationship between the
composition of heavy oils and their flow properties, and
specially the role played by the asphaltenes and the resins, the
most polar and highest molecular weight components. To
determine how these petroleum macromolecules co-exist and
are involved in the viscosity of heavy oils, a rheological
investigation has been realized on different sets of samples.
The understanding of the structure formed by the association
of asphaltenes and resins inside a crude will help to appraise
the origin of high viscosities and to explore new methods
of transportation.
Influence of asphaltenes on the rheological behavior
of heavy oils
Schematically, heavy crude oils can be divided into a non
colloidal liquid, the maltenes and a dark brown powder, the
asphaltenes. Many papers have shown that these particular
solid components can self associate and increase the viscosity
of the middle with each they are mixed. Most of these studies
were realized with simple organic solvents which are not as
complex as maltenes [4-8]. Therefore, in a previous paper we
investigated the influence of asphaltenes in their natural
environment by recombining maltenes and various amounts of
asphaltenes (see Hénaut et al [9]). The main results of this
2 SPE/PS-CIM/CHOA 79496

experimental research are summarized in the first part of this Influence of resins on the rheological behavior of
paper. Most of the trends described in the followings have heavy oils
been observed on several crudes from different origins.
Results shown here have been obtained with an 8°API heavy Using a solvent fraction method, a petroleum can be
crude, for which properties are summarized in table 1. divided into four fractions : Saturates, Aromatics, Resins and
Asphaltenes. According to ASTM 863-69 norm, asphaltenes
SARA SARA (% weight) on C20+ must be precipitated and extracted with pentane. If a longer
alkane is employed, much fewer asphaltenes are obtained [10].
(% weight) pentane heptane heptane SARA fractions
This means that the asphaltenes gotten with a long alkane are
C20+ C H N O S purer than the ones obtained with a short alkane : the short
Asphaltenes 17 14.1 83.8 7.5 1.3 1.7 4.8 alkane precipitates the former asphaltenes and co-precipitates
part of resins (cf. fig.2).
Resins 33 37.3 82.8 8.9 1.5 2.0 4.3
Aromatics 37 37.2 84.3 10 <0.3 1.1 4.0 maltenes obtained with a short alkane asphaltenes precipitated with
a short alkane
Saturates 12 11.4 86.6 13 <0.3 <0.2 <0.1
Saturates Aromatics Resins Asphaltenes
Table 1: Properties of the heavy crude
asphaltenes precipitated with
maltenes obtained with a long alkane a long alkane
The rheological measurements realized on the mixtures of
maltenes and asphaltenes revealed that above a critical
concentration of asphaltenes C* (10% in weight) these Fig.2 - Separation of asphaltenes from heavy oil: influence of the
precipitating alkane.
components not only dramatically increase the viscosity but
also intensify the elastic character. SAXS performed on the
One way to investigate the role of resins in the viscosity of
same samples showed that this phenomenon is due to a
heavy crude oil is to compare the behavior of asphaltenes
structural change:
precipitated with a short alkane (rich in resins) and a long
alkane (poor in resins). Two series of asphaltenes from the
- when C<C* (dilute domain), the particles of asphaltenes
same Venezuelan crude oil have been studied: ones obtained
stay independent from one another and have the same size,
with nonane named I9 (for Insoluble in C9) and ones with
- when C>C* (semi-dilute domain), the particles of
pentane named I5 (for Insoluble in C5). I9 and I5 represent
asphaltenes overlap.
respectively 9.5% and 17% in weight of the crude.
The experimental data of both techniques are presented in
Experimental: pentane and nonane asphaltenes in xylene
figure 1 which shows that they lead to converging results.
These two kinds of petroleum macromolecules have been
added to xylene in various amounts. The viscosity of the
mixtures has been determined with the controlled stress
rheometer AR2000 using a double concentric cylinders. From
the measurements, the relative viscosity ηr of asphaltenes
defined as the ratio between the viscosity of the mixtures and
the viscosity of xylene has been calculated for each sample.
Their values for I9 and I5 are presented in figure 3.

Using a colloidal description the intrinsic viscosity [η] and

the Huggins constant k' calculated in the dilute domain with
the equation : ηr − 1 = [η ] + k' [η ]²C have been determined for
C
both I5 and I9 (cf. Tab.2). k' traduces the tendency of particles
to aggregate.
Fig.1 – Converging results of the rheological and structural
experiments made on asphaltenes added to maltenes, T=20°C, Asphaltenes [η] g/g k'
[Henaut et al.,2000]. I5 3.6 3.8
I9 3.9 7.8
It can be noticed that the original heavy crude oil contains Tab.2 : Rheological characterization of asphaltenes in xylene, T =
17% of asphaltenes and belongs to the semi-dilute domain. Its 20°C.
asphaltenes are overlapped and its viscosity is high.
SPE/PS-CIM/CHOA 79496 3

Interpretation - role of resins

12
I9
10 The most striking result of the presented work is that the
I5 asphaltenes I9 overlap at lower concentration than the
Relative viscosity

8
asphaltenes I5 in xylene. The only difference between these
6 two products is that I5 contains co-precipitated resins. This
shows clearly that the presence of resins prevents the
4
overlapping of asphaltenes. The fact that the Huggins constant
2
k' of I9 is higher than the one of I5 in xylene confirms that the
asphaltenes I9 are submitted to stronger interactions between
0 themselves and explains that they overlap more easily than I5.
0 5 10 15 20 25
This suggests that resins can form a steric layer around
% weight asphaltenes
asphaltenes which impedes their entanglement. These results
are in agreement with the classic representation of asphaltenes
Fig.3 - Relative viscosity of I5 and I9 in xylene, T=20°C.
peptized by resins described by Pfeiffer and Saal [11].
According to the study of Moschopedis and Speight [12] using
Experimental: pentane and nonane asphaltenes in
Infrared spectroscopy, the association between asphaltenes
maltenes
and resins is partly due to hydrogen-bonding interactions.
Gonzalez and Middea [13] insist also on the importance of the
The previous experiments using I5 and I9 have been
aromatic π−π interactions. Another interesting result is that the
repeated with maltenes instead of xylene. The maltenes are the
asphaltenes I9 and I5 have close intrinsic viscosity. A
ones corresponding to a deasphalting of the oil made with
schematic representation, taking into account all the
pentane. Because of the higher viscosity of the samples, the
experimental data, is given in figure 5.
rheological measurements were performed in a cone plate
geometry and not in the double concentric cylinders. The
obtained relative viscosities are plotted in figure 4 and the asphaltene resin
intrinsic viscosities with the Huggins constants are presented
in Tab.3

150

125
I9
I5 I5 I9
100
Relative viscosity

Fig. 5 - Schematic representation of I5 and I9 asphaltenes

in xylene
75

Asphaltenes particles obtained with nonane have larger

50
hydrodynamic volumes and higher masses than those obtained
with pentane. This is confirmed by size exclusion
25
chromatography SEC experiments carried out in THF (figure
0
6).
0 5 10 15 20 25
0.0035
% weight asphaltenes Mw = 6500 g/mol
0.003

0.0025
i5 i9
Fig.4 - Relative viscosity of I5 and I9 in maltenes, T=20°C.
0.002
dXi/dlogM

Mw = 4500 g/mol
0.0015

0.001
Asphaltenes [η] g/g k'
I5 12.8 1.6 0.0005

I9 10.1 2.3 0
5.5 5 4.5 4 3.5 3 2.5 2 1.5
Tab.3 : Rheological characterization of asphaltenes in maltenes, T logMi
= 20°C.
Fig. 6 - Size exlusion chromatography of I5 and I9 in THF
4 SPE/PS-CIM/CHOA 79496

The experiments which have been performed with I5 and

I9 in maltenes lead to the same conclusion: the presence of
resins in I5 prevents the overlapping of asphaltenes. Anyhow
this phenomenon is less pronounced. Probably that part of
resins present in maltenes (cf. fig.2) can adsorb on I9 and
make them similar to I5. The numerous resins in maltenes
screen the interactions between asphaltenes, which explains
that the Huggins constants are weak for I5 and I9 in that case.

To confirm the action of resins, samples containing 16% in

weight of I9 in xylene have been mixed in various proportions
with nonylphenol as a model of resin. Their viscosity is
presented in figure 7.

20

15 Fig.8 - Influence of resins on viscosity (T=40°C)(from Argillier et

Viscosity (mPa.s)

Al [14])

10
5
0 asphaltene system can also give information on the structural
0 20 40 60
% weight of nonylphenol
Fig.7 - Influence of nonylphenol on viscosity of a sample
containing 16% I9 in xylene, T=50°C.
The decrease of viscosity at the beginning of the curve
traduces the ability of nonylphenol to dissociate the
asphaltenes aggregates. Above 30% the nonyphenol starts to
contribute strongly to viscosity with its own viscosity. This
last experiment emphasizes the property of resins to lower the
asphaltenes effect on viscosity.
The same experiment has been carried out with true resins
Influence of temperature
It is well known that temperature has a strong influence
of heavy oil viscosity. Investigation of the thermal behavior of
80 100 organization of the system. Thermal behavior of the heavy
crude has been studied at low temperatures. Oscillatory
dynamic rheological (frequency sweep from 1 to 20 Hz,
smooth aluminum plate-plate 40 mm geometry) results are
presented in figure 9. Above 0°C the crude behaves as a
Newtonian fluid, but below 0°C a shear thinning (or
pseudoplastic) behavior is observed. There is no appearance of
yield stress. It has been checked that no wax crystalization
occurred that could induced such a non Newtonian behavior.
This behavior can be attributed to asphaltene organization as
no shear thinning is observed with maltenes alone in this
temperature range.
100000
-20°C

(Argillier et al [13]). Different samples have been prepared -10 °C

-5 °C
(1 hour at 80°C under gentle stirring) from the two
0°C
followings fractions: 10000
10°C
|n*| (Pa.s)

- a mixture of saturated, aromatics and asphaltenes in the 20°C

proportion corresponding to the original crude, i.e. 12%,
37%, 17% respectively.
- the resins fraction (obtained using a batch process based on 1000
a SARA fractionation)
The evolution of the viscosity as a function of the fraction of
added resins shows (figure 8) the same trend, i.e. a strong
negative deviation, as compared to a model linear mixing law. 100
1 10 100
This decrease of viscosity traduces the ability of resins to Frequence (Hz)
dissociate asphaltenes aggregates. We can notice that a plateau
Fig.9 - Frequency sweep at low temperatures
is obtained at 20% of resins that corresponds to the
concentration of resins in the original crude. Above 60%, Figure 10 also shows that above 0°C the behavior is
resins start to contribute strongly to the viscosity by their mostly viscous-type whereas below 0°C an elastic-type
own viscosity.
SPE/PS-CIM/CHOA 79496 5

behavior is observed. Note that this behavior has been To better understand the influence of temperature the thermal
observed on different crudes. study was also undertaken with I5 and I9 in xylene and
6 maltenes. Results with xylene (figure 12) shows that in the
dilute regime the activation energy is almost the one of xylene
5
Tan delta
alone and does not depend on the solvent of precipitation of
Frequency of 10 Hz
the asphaltene (we are not in overlapped condition). Above
4 C*, the activation energy increases significantly with the
weight percent of asphaltenes and here again we see 2
Tan

3 activation energies depending on the temperature range (below

or above 40°C). The same trend is observed for I5 or I9, with
2 an effect much more important with I9 than with I5.
1 160

Energy of activation Ea (kJ/mol)

i5 i9
140
0
-30 -20 -10 0 10 20 30 120 From 3 to 30 °C
Temperature °C
100 From 30°C to 60°C
Fig.10 - Influence of temperature on the ratio G''/G'=Tanδ 80

These results can be interpreted from the description of the 60

heavy oil as overlapped swollen asphaltene particles: At high 40
temperature relaxation times of the interactions between
swollen particles are fast and the crude behaves as a 20
Newtonian fluid whereas at low temperature all movements 0
are slowed down and shear thinning behavior appears. 0 10 20 30 40
% weight asphaltenes
Flow curves were obtained [9] for different temperatures in
the temperature range (from 0°C to 80°C) where the behavior Fig.12 - Energy of activation as a function of weight percent of
asphaltene (I5 and I9) in xylene
is Newtonian by applying a shear stress sweep (0.03-596 Pa).
When using an Arrhenius plot (figure 11), two domains of These results could be interpreted by a desorption of resins
linearity can be identified corresponding to two activation from asphaltenes when increasing temperature [12, 16]. This
energies: Ea = 116kJ/mol for 3°C <T< 40°C and Ea = 83 effect is shown on the relative viscosity in the semi-dilute
kJ/mol for 40°C <T< 80°C. One possible explanation of this regime where the behavior of I5 and I9 gets closer when
non-linearity is the existence of hydrogen bonds between increasing temperature (figure 13).
asphaltenes and maltenes that are temperature
10000
dependent [15,16].
16 % wt asphaltenes

10 i5 xylene
1000
i9 xylene
Relative viscosity

8
Ea = 116 kJ/mol 100
6
ln ( )

4 10
Ea = 83 kJ/mol
2
1
0 0 20 40 60 80
Température °C
-2 Fig.13 - Influence of temperature on compared effect of I5 and I9
0,0025 0,003 0,0035 0,004 on relative viscosity in the concentrated regime

1/T (K-1 )
In maltenes (figure 14) differences between I5 and I9 are
almost no more noticeable. This is probably due to the
Fig.11 – Arrhenius plot of the heavy crude oil, existence of two presence of large quantities of resins within the maltenes.
activation energies.
There is again a change in the slop at a critical concentration
when going from the dilute to the semi-dilute regime.
6 SPE/PS-CIM/CHOA 79496
150
i5 maltenes
Energy of activation Ea ( kJ/mol)
i9 maltenes
100
50
0 5
% weight asphaltenes
Fig.14 – Energy of activation as a function of weight percent of
asphaltene (I5 and I9) in C5-maltenes
From these observations, we can deduce that the internal
organization of heavy crude oils is based on thermal
dependent links that are reversible. It should be possible to use
this reversibility to adjust the structure of heavy crude oils in
order to facilitate their transport.
Conclusion
Rheological measurements have been successful to
understand how asphaltenes and resins co-exist inside a heavy
crude oil. They have shown that resins can develop a steric
layer around asphaltenes that prevents them from overlapping.
This phenomenon lowers the asphaltenes effect on viscosity. It
has also been indicated that resins can contribute with their
own viscosity to the one of the middle if they are added in
large quantity. In final conclusion, asphaltenes and resins have
to be simultaneously considered to understand the internal
organization and the flow properties of heavy crude oils.
Temperature has also been shown to be a crucial parameter as
part of the interactions occurring in the heavy crude oils are
particularly temperature dependent. Dynamic test carried out
show that at low temperatures, heavy crudes develop a shear
thinning behavior with no yield stress appearance.
Acknowledgements
The authors thank M. Moan (U. of Brest) for fruitful
discussions and advice, I. Merdrignac and E. Robert (IFP) for
chromatographic analysis, L. Barré (IFP) for X-Ray
characterization and TotalFinaElf for their interest in this work
and helpful discussions.
References
From 3°C to 40°C
1. Guevara, E ; Gonzalez, J ; Nuñez, G: "Highly Viscous Oil
Transportation Methods in the Venezuela Industry", Proc. 15th
World Pet. Congress, 495-502, 1998.
2. Gerez, JM ; Pick, AR:"Heavy Oil Transportation by Pipeline", Int.
Pipeline Conf., 2, 699-710, 1996.
3. Urquhart, RD, "Heavy Oil Transportation: Present and Future", J.
Can. Pet. Technol., 25 (2), 68-71, 1986.
4. Sheu, E.Y., De Tar, M.M. and Storm, D.A.: "Rheological
From 40°C to 80°C properties of vacuum residue fractions in organic solvents",
Fuel, vol 70, 1151-1156, 1991.
5. Yudin, I.K., Nikolaenko, G.L., Gorodetskii, E.E., Kosov, V.I.,
Melikyan, V.R, Markhashov, E.L., Frot, D. and Briolant, Y. :
10 15 20 25 "Mechanisms of asphaltene aggregation in toluene-heptane
mixtures", Journal of Petroleum Science and Engineering, 20, 3-
4, 297-301, 1998.
6. Fenistein D., Barré L., Broseta D., Espinat D. et al.:
"Viscosimetric and neutron scattering study of asphaltene
aggregaters in mixed toluene/heptane solvents ,Langmuir, 14, 5,
1013-1020, 1998.
7. Sheu, E.Y., Storm, D.A. and De Tar, M.M. : " Asphaltenes in
polar solvents", Journal of non-crystalline solids, 131-133, 341-
347, 1991.
8. Acevedo, S., Ranaudo, M.A., Pereira, J.C., Castillo, J., Fernandez,
A, Perez, P. and Caetano, M. "Thermo-optical studies of
asphaltene solutions: evidence for solvent-solute aggregate
formation", Fuel, 78 ,9, 997-1003, 1999.
9. Hénaut I., L. Barré, J-F. Argillier, F. Brucy, R. Bouchard:
"Rheological and structural properties of heavy crude oils in
relation with their asphaltenes content", SPE Oilfield Chemistry,
Houston, USA , 13-16 Feb. 2001. SPE N° 65020.
10. Speight.J, Long.R and Trowbridge.D: Fuel, vol 63, may, 1984.
11. Pfeiffer, J.P. and Saal, R.N.J., J. Phys. Chem., 44, 139-149, 1940.
12. Moschopedis S.E., Speight J.G."Investigation of hydrogen
bonding by oxygen functions in Athabasca bitumen", Fuel, 55,
187-192, 1976.
13. Gonzalez G., Middea A.: Colloids and Surfaces , 52,
207-217, 1991.
14. Argillier J-F., L. Barré, F. Brucy, J-L. Dournaux, I. Hénaut, R.
Bouchard, "Influence of asphaltenes content and dilution on
heavy oil rheology", SPE International Thermal Operations and
Heavy Oil Symposium, Porlamar, Margarita Island,
VENEZUELA, 12-14 March. 2001. SPE N° 69711.
15. Acevedo, S., Mendez, B., Rojas, A., Layrisse, I. and Rivas, H. :
"Asphaltenes and resins from the Oricono basin", Fuel, 64,
1741-1747, 1985.
16. Lesueur D., Gerard J-F.: "A structure-related model to describe
asphlat linear viscoelasticity", J. of Rheology, 40 (5), 813, 1996.