OTC 15278

Thermal Flow Properties of Heavy Oils

I. Henaut, J-F. Argillier, C. Pierre (Institut Franais du Ptrole), M. Moan (Universit de Brest)
Copyright 2003, Offshore Technology Conference

This paper was prepared for presentation at the 2003 Offshore Technology Conference held in
Houston, Texas, U.S.A., 58 May 2003.

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Abstract
A major flow assurance challenge in the near future is the
production and transport of heavy oils: although these
petroleum products represent very important reserves, their
exploitation is limited by their high viscosity. The paper
discusses the origin of this high viscosity in order to ultimately
develop operating guidelines. It focuses on the relationship
between the composition of heavy oils, in particular their
asphaltenes and resins contents, and their flow properties. The
structural analysis and rheological measurements that were
performed revealed how strongly the transportability of heavy
oils depends on thermal conditions, especially in deepwater
ones. From this study, we conclude that the high viscosity of a
heavy oil comes essentially from the overlapping of its
asphaltenes. We observed that as temperature decreases, not
only the viscosity increases but also the rheological behavior
of heavy oils becomes non Newtonian. Dynamic tests carried
out on several crudes show that at low temperatures, they
develop a shear thinning behavior with no yield stress
appearance. It was checked that this phenomenon comes from
the particular structure of asphaltenes and that it is not due to
the presence of waxy crystals. It is therefore recommended to
take into account this non Newtonian behavior if heavy oils
are to be transported in deepwater conditions.

Introduction. A major flow assurance challenge in the near
future is the production and transport of heavy oils. Despite
very large reserves, their exploitation is limited by their high
viscosity. Actually, the very low mobility of these petroleum
products is making an as such pipeline transportation
impossible. Advanced methods are necessary. They include
upgrading, dilution, formation of oil-in-water emulsions and
heating. These technologies imply high operational and
investment costs so that optimized transport conditions have to
be found. With this aim in view, a detailed study of the
rheology of heavy oils was carried out. It deals with the link
between the constitution and the flow properties of the crude,
and lays emphasis on the role played by temperature. The
understanding of the origin of the high viscosity of heavy oils
will help to improve their methods of transportation,
especially at low temperatures like in expected deepwater
discoveries.

The overlapping of asphaltenes inside a heavy oil
and its consequence on viscosity. One main chemical
characteristics of a heavy oil is its large content in asphaltenes.
These molecules constitute a class of substances defined on
the basis of their solubility in organic solvents: they are
soluble in toluene but insoluble in alkanes such as n-pentane.
Asphaltenes are the heaviest and most aromatic and polar
fraction of a crude oil. These particular components are
described as molecules composed of polycondensed aromatic
rings carrying aliphatic chains that contain acid-base and polar
groups at their edge. It is well recognized that thanks to these
chemical characteristics, asphaltenes can self assemble
through physical interactions and increase the viscosity of a
medium in which they are added. Most of these studies were
realized with simple organic solvents [Reerink and Lijzenga
(1973), Sheu et al. (1991), Yudin et al. (1998), Acevedo et al.
(1999).]. As these solvents are not as complex as heavy oils,
we previously investigated the influence of asphaltenes in
their natural environment by recombining deasphalted oil
(maltenes) and various amounts of asphaltenes [Henaut et al.
(2000)]. The main results of this experimental research are
summarized below.
The rheological measurements realized on the mixtures of
maltenes and asphaltenes revealed that above a critical
concentration of asphaltenes C* these components not only
dramatically increase the viscosity but also intensify the
elastic character.
SAXS performed on the same samples showed that this
phenomenon is due to a structural change:
- when C<C* (dilute domain), the particles of asphaltenes
behave as colloidal particles dispersed in oil. The structural
parameter measured by SAXS can be considered as their
radius of gyration Rg.
- when C>C* (semi-dilute domain), the particles of
asphaltenes overlap. In such a regime, the structural parameter
is the correlation length which is indicative of the mesh size
of the network formed by the asphaltenes.
The experimental data of both techniques are presented in
figure 1 which shows that the observed structural change is
well correlated to an increase of viscosity.
2 OTC 15278

Fig.1 Rheological and structural experiments made on
asphaltenes added to maltenes, T=20C, [Henaut et al.,2000].

A schematic representation of the ordered structure organized
by particles of asphaltenes is given as a function of
concentration (fig.2).


Fig.2 Schematic representation of asphaltenes association.


It can be outlined that the original heavy crude oil contains
17% of asphaltenes and belongs to the semi-dilute domain. Its
asphaltenes are overlapped and its viscosity is high.

Influence of temperature on the association of
asphaltenes and on flow properties of heavy oils.
As the interactions involved in the overlapping of asphaltenes
(- interactions, hydrogen bonding) are thermal
dependent, we assumed that this peculiar morphology could be
modified by temperature. Therefore, the rheological
experiments made at 20C were repeated at several
temperatures varying from 3 to 80C. The viscosity
measurements were carried out in the two domains of
concentrations of asphaltenes (C<C* and C>C*). The results
are successively described.
Influence of temperature in dilute domain.
We have seen that below C* asphaltenes behave as colloidal
particles well dispersed in maltenes. In order to assess the
contribution of these particles on the viscosity of the samples,
we applied the Huggins approach [Huggins (1942), Bouhadda
et al. (2000)] which was initially developed to describe the
viscosity of dilute solutions of long-chain molecules. We used
the following equation:
[ ] [ ] C ' k
C
1
C
1 0 r
+ =

=


with :
: viscosity of the solution,

0
: viscosity of the pure solvent,

r
: relative viscosity,
C : concentration in particles,
[]: intrinsic viscosity,
k' : constant.
The hydrodynamic properties [] and k' can be determined by
plotting
C
1 r
as a function of C (fig.3).
0
5
10
15
20
25
30
35
40
45
0 2 4 6 8 10
C (weight %)

r
-
1
/
C
[]
k'[]
Fig.3 Plots based on Huggins equation for the determination
of [] and k', T=20C.

We precise that the intrinsic viscosity is indicative of the ratio
between the apparent volume occupied by the particles and
their mass and that k' is indicative of the strength of
interactions between the particles through the considered
solvent. The evolution of these two parameters with
temperature is plotted in fig 4.
0
2
4
6
8
10
12
14
16
0 20 40 60 80
T (C)

[

]

(
g
/
g
)

k
'

[]
k'
Fig.4 Evolution with temperature of the hydrodynamic
properties of asphaltenes introduced in maltenes.
OTC 15278 3
It can be noticed that the intrinsic viscosity diminishes when
temperature is raised. We checked that this decrease is due to
the resulting disassociation of the particles of asphaltenes.
Actually the break down of this kind of aggregates with
heating had already been demonstrated by previous SANS
investigations [Thiyagarajan et al, 1995; Roux et al, 2001]
which all observed substantial drops in radii of gyration and
molecular weight.
Concerning the interaction parameter k', it does not seem to be
affected by temperature as its value remains the same for all
the experiments. We attribute this phenomenon to the presence
of resins, the second polar components of a heavy oil that are
known to peptize asphaltenes [Pfeiffer and Saal, 1940] These
molecules are quite abundant inside maltenes (29%).
Whatever the temperature is, resins are enough numerous to
surround the particles of diluted asphaltenes and impede their
interactions through maltenes.

A sum up of these observations is that, when heated or cooled,
diluted particles of asphaltenes in maltenes change of
aggregation degree but stay submitted to the same pair
interactions. This means that the change of viscosity with
temperature of these samples is mostly governed by the
intrinsic viscosity of asphaltenes. It can also be outlined that
while the size of particles will grow because of a decrease of
temperature, C* will diminish : in conditions like in deepwater
ones, the particles of asphaltenes will overlap sooner. In our
case, the critical concentration is estimated at 10% for 3C and
reaches 14% at 80C.

Influence of temperature in semi-dilute domain.
We have seen that above the critical concentration C*,
asphaltenes overlap and give rise to a particularly strong
increase of viscosity. In order to evaluate how this
phenomenon is thermally influenced, the relative viscosity of
the samples was plotted for temperatures comprised between 3
and 80C (cf. fig.5).

0
50
100
150
200
250
0 5 10 15 20 25
weight % asphaltenes

r
dilute domain semi-dilute domain
3C
20C
40C
60C
80C
Fig.5 Evolution with temperature of the relative viscosity of
asphaltenes introduced in maltenes.

The graph shows that the samples of the semi-dilute domain
are much more thermal dependent than the ones belonging to
the dilute domain. We attribute this fact to the more numerous
physical interactions involved in the semi-dilute domain. The
extent of these interactions increase upon a decrease in
temperature [Wallen et al. (1996)]. As a result of the presence
of more abundant interactions that get stronger at lower
temperature, the overlapped asphaltenes entail a higher
viscosity and worsen the transportability of heavy oils at low
temperature.

Influence of resins on thermal properties of heavy
oils.
Like asphaltenes, resins are described on term of their
solubility in organic solvents [Mouraille et al. 1998] and are
considered as important petroleum macromolecules. They are
known to interfere at the periphery of asphaltenes
[Moschopedis and Speight, 1976] and therefore resins are
much involved in the internal organization and flow properties
of heavy oils. Using viscosity measurements, we tried to
characterize this complex structure and to identify how it is
modified by temperature. Resins are very difficult to extract in
large quantity from a crude oil. In order to study their
influence, we chose to prepare samples with maltenes and
asphaltenes that contain different amounts of co-precipitated
resins that is to say asphaltenes extracted with different
alkanes. Three kinds of asphaltenes were obtained thanks to
three different alkanes : n-nonane, n-heptane and n-pentane.
They are respectively named: I9, I7 and I5. I9 can be
considered as the purest asphaltenes of the three precipitated
asphaltenes and will be chosen as the ones that sets the limits
between asphaltenes and resins. With this definition, we can
precise that, in our case, I7 contain 86% of asphaltenes and
14% of resins, and I5 contain 56% of pure asphaltenes and
44% of resins. All of them were introduced in the same
maltenes (the ones coming from the deasphalting made with
pentane) and can be regarded as identified solutes. Their
contribution to increase the viscosity of the maltenes was
compared in a large array of concentrations.

The hydrodynamic properties of the three asphaltenes I9, I7
and I5 were determined in comparison with the same
maltenes. The results are presented in fig.6.
0
2
4
6
8
10
12
14
16
0 20 40 60 8
T (C)
[

]

(
g
/
g
)
a
n
d

k
'

0
[] 5 k' I5
[] 7 k' I7
[] 9 k' I9
Fig.6 Hydrodynamic properties of different asphaltenes
introduced in the same maltenes.

The curves show that despite their deficiency in resins, the
asphaltenes I9 and I7 have the same intrinsic viscosity and the
same interaction parameter as I5. We think that this
phenomenon is due to the resins that are already present in the
maltenes : they counteract the lack of resins of I9 and I7 and
make them similar to I5. Therefore, the three asphaltenes
4 OTC 15278
become equivalent and have the same hydrodynamic
properties.

Meanwhile more and more asphaltenes are added, there will
not be enough resins inside the maltenes to compensate the
lack of resins of I9 and I7. At this point, the asphaltenes poor
in resins become more attractive and begin to get overlapped.
This explains why the critical concentration of I9 and I7 is
smaller than the one of I5 (cf. fig.7). Being more attractive
when C>C*, it can also be noticed that the asphaltenes I9 and
I7 give rise to a stronger increase of viscosity than I5.
0
50
100
150
200
250
300
350
0 5 10 15 20 25
weight % of powder

r
I5
I7
I9
Fig.7 Evolution with temperature of the relative viscosity of the
different asphaltenes introduced in maltenes, T=20C.

By comparing the experiments made at different temperatures,
we observed that the shift behavior between I9, I7 and I5 in
maltenes is not thermal dependent. Actually, the viscosity of
the samples prepared with the three different asphaltenes
changes with temperature with the same extent. This can be
shown with the estimation of the energy of activation of each
sample obtained using an Arhenius plot:
k
RT
E
ln
a
+ =
: absolute viscosity of the sample at T,
Ea : energy of activation,
k : constant.

The samples of asphaltenes I9, I7 and I5 introduced in
maltenes have the same energy of activation (cf. fig.8).
50
75
100
125
150
0 5 10 15 20 25
weight % of powder
E
a

(
k
J
/
m
o
l
)
I5
I7
I9
Fig.8 Energy of activation calculated between 3 and 40C for
samples of different asphaltenes introduced in maltenes.

On the contrary, when the asphaltenes I9, I7 and I5 are
introduced into organic solvents free of resins, the energy of
activation are quite different (cf. fig.9).
0
25
50
75
100
125
150
0 10 20 30 40
weight % of powder
E
a

(
k
J
/
m
o
l
)
I5
I9
Fig.9 Energy of activation calculated between 3 and 30C for
samples of different asphaltenes introduced in xylene.

All these observations mean that the resins present inside the
heavy oils not only delay and disturb the overlapping of
asphaltenes but also reduce its thermal dependence. This
performance can be used to inspire and help the development
of appropriate chemical additives.

Influence of very low temperature on flow properties
of heavy oils.
We have shown that temperature is a crucial parameter
because it controls the extent of the interactions occurring
inside the heavy oils. In order to precise its role on the flow
properties, we have carried out some rheological experiments
at even lower temperatures (from 10 to -20C). Frequency
sweeps between 1 and 40 Hz have been performed. This kind
of oscillatory procedures are very useful to test and
characterize high viscous samples. The very small strain
applied (0.0125%) allows to stay in the linear domain and to
reach high frequencies. The results obtained with the heavy
crude oil are presented in fig.10.
100
1000
10000
100000
1 10
Frequency Hz
|
n
*
|

(
P
a
.
s
)
100
-20C
-5C
0C
10C
20C

Fig.10 Dynamic tests performed on the heavy crude oil at very
low temperatures.

They demonstrate that below 10C, the heavy oil develops a
shear-thinning behavior that gets stronger when temperature
decreases. This level of temperature can be attained in
deepwater conditions, which promotes the study in more detail
OTC 15278 5
of this non Newtonian behavior. At first, we have checked that
no wax crystallization could be at the origin of the shear-
thinning appearance : no entities could be detected by optical
microscopy and no peak of crystallization was observed by
Differential Scanning Calorimetry. Consequently, we have
suggested that the shear-thinning behavior might be attributed
to asphaltenes and more precisely to overlapped asphaltenes.
Therefore, the experiments have been repeated on maltenes
and on a sample containing diluted asphaltenes (cf. fig.11). No
shear-thinning has been observed with these two products. The
heavy oil containing overlapped asphaltenes is the only
sample to lead to a decrease of viscosity under an increasing
shear rate.

100
1000
10000
100000
1 10
Frequency Hz
|
n
*
|

(
P
a
.
s
100
Heavy oil
5% i5s5
Maltenes s5
Temperature 0C

Fig.11 Dynamic tests performed on the heavy crude oil, on
maltenes and on a diluted sample.

The non Newtonian behavior observed upon cooling seems to
result from the overlapping of the particles of asphaltenes.
When a shear rate is applied, the aggregates of asphaltenes
dissociate and consequently the viscosity diminishes. As the
temperature is very low, the asphaltenes are not mobile and
have no time to rearrange. On the contrary, at moderate
temperature, the asphaltenes are more mobile and have the
time to rearrange. While aggregates disoverlap under shear
rate, new ones are formed and the heavy oil remains
Newtonian. We outline that all this experimental research has
been carried out on several crude oils and had lead to the same
conclusions.

Dilution of heavy oils at very low temperature

Dilution is a current method used to reduce the viscosity of
heavy crudes to allow their pipeline transportation [Guevarra
et al. 1998]. This process consists in adding to the crude other
crudes of greater API gravity or light refined products such as
naphtha or kerosene. At temperatures of usual production, the
behavior of heavy oils is Newtonian and so is the one of
diluted samples. A previous study dealing with the dilution
with naphtha of our crude [Argillier et al., 2000] revealed that
the viscosity of diluted mixtures drops dramatically with an
increase of temperature and diminishes less with an increase
concentration of solvent (cf. fig.12). When these two effects
are combined (T=80C and 20% of diluent) it can be outlined
that the viscosity of the oil is reduced by more than 99%
0
0,25
0,5
0,75
1
0 5 10 15 20 25
% dilution (volume)
v
i
s
c
o
s
i
t
y

o
f

d
i
l
u
t
e
d

o
i
l

/


v
i
s
c
o
s
i
t
y

o
f

c
r
u
d
e

o
i
l
3C
20C
40C
60C
80C
Fig.12 - Thermal dependence of the dilution efficiency.

At lower temperatures, like in deepwater ones, we have shown
that a heavy crude oil tends to become shear-thinning. It is
therefore essential to study the behavior of the corresponding
dilute crudes. To do so, dilutions with different concentrations
of naphtha have been prepared and examined at low
temperatures. The rheological experiments have been
performed with a cone and plate geometry at 0C. The flow
curves obtained are presented in fig.13.

400
450
500
550
600
650
1 10 100
Shear rate (s-1)

a

(
P
a
.
s
)
a Shear-thinning behavior of the 5% dilute sample, T=0C.

50
60
70
80
90
100
1 10 100
Shear rate (s-1)

a

(
P
a
.
s
)
b Shear-thinning behavior of the 10% dilute sample, T=0C.
6 OTC 15278
0
1
2
3
4
5
1 10 100
Shear rate (s-1)

a

(
P
a
.
s
)
c Newtonian behavior of the 20% dilute sample, T=0C.

Fig.13 - Rheological behavior of diluted samples, T=0C.

They reveal that dilute samples at small concentrations
(<10%) still lead to a slight shear-thinning behavior. On the
contrary, the sample diluted with 20% of naphtha is perfectly
Newtonian. Despite the dilution, this last sample still has an
asphaltene concentration that is higher than the critical
concentration calculated in maltenes. That this sample is
Newtonian at low temperature means that its asphaltenes are
less overlapped than in maltenes and that their structure might
have been changed by the diluent. Therefore, the chemistry of
the diluent has also to be taken into account [Argillier et al.,
2001].

Conclusion
The flow properties of heavy crude oils have been studied in
terms of their composition and temperature. The experimental
work showed that the high viscosity of heavy oils can be
attributed to the overlapping of their asphaltenes. It has been
demonstrated that without resins, the viscosity would be even
higher. We observed that as temperature decreases, not only
the viscosity increases but also the rheological behavior of
heavy oils becomes non Newtonian with the appearance of a
shear thinning behavior. In such conditions, dilutions still
seems to be an appropriate treatment as it strongly diminishes
the viscosity and the non Newtonian behavior.

Acknowledgements
The authors thank TotalFinaElf for providing the heavy crude
oil and fruitful discussions.

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