SPE 69711
Influence of Asphaltenes Content and Dilution on Heavy Oil Rheology
J-F. Argillier*, L. Barré*, F. Brucy*, J-L. Dournaux*, I. Hénaut*, R. Bouchard**
* Institut Français du Pétrole, Rueil-Malmaison, France, ** TotalFinaElf, Paris La Défense, France
Copyright 2001, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the 2001 SPE International Thermal Operations
and Heavy Oil Symposium held in Porlamar, Margarita Island, Venezuela, 12-14 March 2001.
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, as
presented, have not been reviewed by the Society of Petroleum Engineers and are subject to
correction by the author(s). The material, as presented, does not necessarily reflect any
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Abstract
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. Our aim in this study was first to
understand the role of asphaltenes in these high viscosities and
secondly to evaluate the viscosity reduction efficiency when
blending with different diluents.
Many previous works studied asphaltene associations in
simple organic solvents like toluene or toluene/heptane
mixtures, but these conditions are not representative of heavy
crude oils. Our approach has been to characterize the
rheological behavior of asphaltenes in their natural
environment. Samples coming from the same crude oil have
been prepared with different asphaltenes contents, from 0 to
20%, after deasphaltating and recombination. From viscosity
measurements two concentration regimes were identified: a
diluted regime where the apparent viscosity increases linearly
with the weight fraction of asphaltenes and a concentrated
regime where the viscosity increases dramatically because of
asphaltene particles entanglement. The diluted regime can be
described as a solution of solvated asphaltene particles that are
independent from one another. Natural heavy crude oils
correspond to the concentrated regime and the high viscosities
observed are due to this entanglement of solvated asphaltene
particles. A strong influence of temperature on the rheology is
revealed by measured high activation energies.
Dilution of heavy oils has been studied using various solvents,
in terms of aromaticity, chemical nature and viscosity.
Dilution with low viscosity hydrocarbons, like light crude oil
or naphtha, has shown that the viscosity reduction efficiency is
controlled by the sole viscosity of the diluent and not by its
aromaticity. The aromaticity has no effect up to very high
dilution rate, more than 60% in our tests, where flocculation
may begin. Results have also shown that blending diluents of
different chemical natures and polarities can enhance viscosity
reduction. From these observations, the colloidal description
of heavy oils can be extended to diluted heavy oils, considered
as solutions of asphaltene particles solvated in diluted
maltenes.
Introduction
Heavy oils represent a strategic source of hydrocarbons as
their reserves are of the same order of magnitude as the ones
of conventional oils. The production of these crudes remains
low, in particular because of their very high viscosities. It is
worth noticing that new targets are now the production of oil
below 20° API and more in the range of 8 to 15°API. With
such crude oils are associated production problems that have
never been met. On the subsurface point of view, such high
density comes along with high viscosity, ranging from a few
thousand to million of centiPoises at reservoir temperature. It
means that oil is not flowing and needs a thermal or chemical
activation. If thermal techniques for recovery have been
screened over the past decade, other issues concerning surface
facilities and transportation in long pipelines are remaining.
Typical solutions are to heat the fluid, or to dilute it with a
lighter oil or solvent [1-8]. But such solutions can be
expensive and may be detrimental to projects economics.
There is then a urge to improve the existing solutions or to
find new ones, in order to reduce or by-pass the viscosity of
the heavy oil to be transported. The study presented here has
the objective to better appraise the origin of high viscosities of
the natural heavy crude oils, in order to explore solutions for
transportation. In these regards, chemical and physical
properties of heavy oils were examined, on various samples.
2 J-F. ARGILLIER, L. BARRE, F. BRUCY, J-L. DOURNAUX, I. HENAUT, R. BOUCHARD,
The following questions are those we wish to answer in the
paper. Where do the high viscosities of heavy crude oils come
from? How can the heavy crude oil viscous system be
described ? What does dilution actually achieve and how can
be enhanced the viscosity reduction?
Among the many components of heavy crude oils, the
asphaltenes, well known by operators for the deposit and
plugging it may cause for some light crudes, have been
identified as the key in the crude oil viscosity. Actually, many
studies have shown that these high molecular weight polar
components self-associate more or less severely depending on
different parameters like temperature and concentration. These
experimental work were usually realized using simple organic
solvents like toluene and toluene/heptane mixtures [9-14]
which are not representative of the complex heavy crude oils.
Only few studies have concerned heavy oils or diluted
bitumens[15-23]. The approach we used to answer these
questions was first to investigate the rheological and structural
behavior of asphaltenes in their natural environment. Results
on this point have been detailed in a former paper SPE 65020
[23] and will be summarized in the first part of this paper.
Then the efficiency of different diluents have been studied.
Samples and methods
Heavy oil samples
Samples are prepared from a Venezuelan heavy crude oil. The
asphaltenes are precipitated with pentane using the norm
ASTM 863-69 and then grinded. Remixing of asphaltenes in
maltenes is carried out at 80°C for an hour. SARA
decompositions and analysis of this crude are shown on
Table 1. The diluents that are used are different low viscosity
hydrocarbons, in particular naphtha, kerosene, HCO and LCO
cuts. In order to further investigate the dilution process in
heavy oils, different alcohols are also used in a second part of
the study. The properties of these diluents are gathered in
Tables 2 and 3.
Methods
Viscosity measurements are performed using a controlled
stress rheometer Carri-Med CSL²100. Our approach is based
on a decomposition of the crude in asphaltenes and maltenes
and then recombination. The first point we checked was that
this approach was valid: low angle X-ray scattering and
viscosity measurements have shown that the original heavy
crude and the remixed sample with the same asphaltene
content have exactly the same properties [23]. These results
allowed us to prepare samples with different asphaltenes
weight fraction. Viscosity measurement have been performed
on samples of maltenes recombined with various amounts of
asphaltenes (from 0 to 20% in weight) at different
temperatures. Concerning tests with diluents, 4 dilution rates
(5, 10, 15 and 20% in weight) and 5 temperatures (3, 20, 40,
60 and 80°C) have been tested for each diluent.
SPE 69711
Description of an heavy crude
We are interested in this part in the relationship between the
microscopic interactions between the constituents of a heavy
crude and its macroscopic rheological behavior.
Influence of asphaltenes content
Rheological measurements (Figure 1) show that the viscosity
increases strongly with asphaltenes concentration. Note that
all samples are Newtonian. This results are further interpreted
by analogy to colloidal suspension using the relative viscosity
of the asphaltenes suspended in the maltenes. The relative
viscosity is defined as ηr = η/η0 where η is the viscosity of the
system and η0 the viscosity of the maltenes. The curve (Figure
2) is similar to a typical colloidal viscosity curve. Two
different regimes can be distinguished: a diluted regime where
the relative viscosity increases almost linearly with the weight
fraction of asphaltenes (each particle behaves as if no other
particle was present) and a concentrated regime, above a
critical concentration C* close to 10%, where the relative
viscosity increases strongly with the weight fraction of
asphaltenes. Small angle X-ray scattering (SAXS)
measurements confirm that C* corresponds to a critical
overlap or entanglement concentration: below C*, the particles
remain independent from one another and the radius of
gyration of the asphaltene particle remains constant. Above
C*,a correlation length can be measured that decreases with
the weight fraction of asphaltenes due to particles
entanglement. An important result to be emphasized is that the
original crude corresponds to the concentrated regime. Let us
note also that theses results have been confirmed on samples
of several heavy oils from different origins.
Influence of temperature
Investigation of the thermal behavior of asphaltene system can
give information on the structural organization of the system.
The flow curves presented in Figure 3 show a very strong
influence of temperature. When using an Arrhenius plot, two
domains of linearity can be identified corresponding to two
activation energies: Ea = 116kJ/mol for 3°C <T< 40°C and Ea
= 83 kJ/mol for 40°C <T< 80°C. Different interpretations can
be proposed to explain this non-linearity: existence of
hydrogen bonds between asphaltenes and maltenes that are
temperature dependent [24], thickening of the solvatation shell
of asphaltenes when decreasing the temperature [25-26],
coupling of a fluctuation mode and a diffusion mode as
described in ref. [27]. More work needs still to be done. In
particular structural analysis would be very useful to clarify
this temperature dependent behavior.
Influence of resins
Resins are known [28-30] to have a strong influence on
asphaltenes stabilization within a crude. Their action, usually
described as peptizing, can be represented as their absorbing at
the periphery of asphaltenes micelles and acting as dispersants
stabilizing the interface between the asphaltenes and the rest
SPE 69711 INFLUENCE OF ASPHALTENES CONTENT AND DILUTION ON HEAVY OIL RHEOLOGY
of the crude. An exhaustive study of the role of resins is not in
the scope of this paper. And we will focus on the description
of the influence of resins in the viscosity of the asphaltene
dispersion for the studied Venezuelan crude.
Resins have been obtained using a batch process based on a
SARA fractionation. Different samples have been prepared
(1 hour at 80°C under gentle stirring) from the two followings
fractions:
- a mixture of saturated, aromatics and asphaltenes in
the proportion corresponding to the original crude, i.e.
12%, 37%, 17% respectively.
- the resins fraction
Let us first note that all samples show a Newtonian behavior.
The evolution of the viscosity as a function of the fraction of
added resins shows (figure 4) a strong negative deviation, as
compared to a model linear mixing law. This decrease of
viscosity traduces the ability of resins to dissociate asphaltenes
aggregates. We can notice that a plateau is obtained at 20% of
resins that corresponds to the concentration of resins in the
original crude. Above 60%, resins start to contribute strongly
to the viscosity by their own viscosity. Similar trends with a
decrease of viscosity more or less important have been
observed on several other heavy crudes. Structural analysis of
resins in the dilute regime has been carried out as well and
shows that the presence of resins modifies the conformation of
the asphaltene aggregates, but this point still needs
clarification.
Description of the heavy crude viscous system
From the above results the description that one can draw for a
heavy crude is that of a colloidal system composed of solvated
asphaltene particles entangled in solvent constituted of the
maltenes. Temperature changes the quality of solvent and
modifies, as well as the resins concentration, the initial state of
aggregation of asphaltenes and therefore the rheological
properties of the system. This behavior can be compared to the
one of semi-dilute amphiphilic polymer colloidal solutions
[31].
The high viscosities of heavy crudes are mainly due to the
entanglement of the solvated asphaltenes particles.. The
obvious way to reduce the viscosity by diluting the crude is
indeed compatible with this description as diluting will reduce
the mentioned entanglement, through the. decrease of the
weight fraction of asphaltenes. However, further questions
arise:which phenomenon is actually happening when diluting?
Does the initial aggregation state of asphaltene and/or their
organization in the maltenes change? Questions will be dealt
with in the next paragraph.
Dilution
Let us first calculate the volume of diluent that should be used
to dilute the Venezuelan crude under study so that the
concentration of asphaltenes is reduced close to the critical
3
concentration C*, i.e.: the one that is the limit to enter the
dilute regime. Assuming that the structure of asphaltene
particles does not change during dilution (this point will be
addressed later on in the paper), the calculation shows that to
reach 10 % of asphaltenes (C*,), from the original 17 %, the
volume of dilution has to be 41 %.
Dilution by low viscosity hydrocarbons
Let us note that for all the dilution tests no asphaltene
flocculation has been noticed and that all systems present a
Newtonian behavior in the range of shear rates that has been
explored (from 0.01 s-1 up to 1000s-1).
* Influence of diluent concentration
Figure 5 shows the viscosity reduction obtained by dilution of
the crude with 4 different diluents at 4 different concentration.
Different conclusions can be drawn from this curves:
- the viscosity decreases exponentially with the diluent
fraction, as it is usually observed in the literature,
- the viscosity reduction is enhanced when the diluent is
of low viscosity. Figure 6 shows that with these
diluents the viscosity reduction efficiency is almost
proportional to the diluent viscosity,
- there is no direct relationship between the diluent
aromaticity and the dilution efficiency.
* Influence of diluent aromaticity
To further investigate this effect of aromaticy on the efficiency
of viscosity reduction by dilution we have performed dilution
with mixtures of naphtha with different percentages of
toluene. Results shown in Figure 7 confirm that increasing the
aromaticity of the diluent does not improve the dilution
efficiency. An advantage of using an aromatic diluent could be
the displacement of the onset of flocculation of asphaltenes.
However for most of the heavy crudes we have been dealing
with asphaltenes stand in the crude as if in very good solvent
and start only to flocculate after addition of a large amount of
some “bad” solvent. For example with the Venezuelan crude
used in this study, addition of more than 60% of heptane is
necessary to observe a beginning of asphaltene flocculation.
* Influence of temperature
The evolution of the viscosity of the studied Venezuelan
heavy crude diluted with naphtha with temperature (Figure 8)
shows that the effect is more important at low temperature.
Influence of temperature can be analyzed using a viscosity
reduction parameter as suggested by [5]. This parameter
allows to compare the efficiency of diluents at different
temperatures independently of the variation of the viscosity of
the crude with temperature. This parameter is defined as:
 η (c, T ) 
vis cos ity reduction (c, T ) = 100 × 1 − 
 η (0, T ) 
where
η is the viscosity (Pa.s) ;
c is the concentration of diluent (% vol) ;
T is the temperature (K)
4 J-F. ARGILLIER, L. BARRE, F. BRUCY, J-L. DOURNAUX, I. HENAUT, R. BOUCHARD,
Evolution of the viscosity reduction at 15% dilution as a
function of temperature shows the same trend for the other
low viscosity hydrocarbon diluents (Figure 9). Diluent
efficiency is stronger at low temperature. Let us note that
when comparing the effect of diluents the viscosity reduction
still depends on the diluent viscosity.
* Interpretation of dilution
We have defined (in part 1) the crude as: “asphaltenes in
maltenes”. Here, let us make the assumption that when
diluting a heavy oil by a hydrocarbon cut, the structure of the
asphaltene particles do not change. Then we may consider that
the diluted crude is defined either as: “(asphaltenes in
maltenes) in diluent”, or “asphaltenes in (maltenes in
diluent)”.
By measuring the viscosity of the mixture (maltenes in
diluent), that is diluted maltenes in naphtha , we can determine
the relative viscosity of the diluted crude and compare the
curves obtained when recombining asphaltenes in maltenes
and when diluting the original crude. Results are presented in
Figure 10. The superimposition of the curves confirm that
dilution by hydrocarbon cuts does not modify the structure of
the solvated asphaltenes and reduce the viscosity only by an
effect of dilution.
Influence of diluent chemistry
In order to further investigate the role of diluent chemistry,
and in particular polarity properties, alcohols have been tested
as diluent. It is however obvious for economical and
availability reasons, that dilution by alcohols can not be
envisaged as such on sites. Dilution tests have been performed
with alcohols of various Carbon chain lengths. For alcohols
lighter than butanol, miscibility problems have been observed
so results will be presented only for butanol up to octanol for
which is has been checked that no phase separation occurs.
Figure 11 shows that the viscosity decreases exponentially
with the percentage of alcohol. This evolution is similar to the
one observed for low viscosity hydrocarbons diluent. Note that
hexanol and HCO have a same efficiency although the alcohol
is 5 times more viscous than the HCO.
To compare dilution efficiency of alcohols and hydrocarbons,
results are presented using the relative viscosity defined as:
η (c, T )
η rel (c, T ) =
η diluent (T )
where:
− η(c,T) is the viscosity of the diluted crude at a concentration
c and temperature T (Pa.s),
− ηdiluent(T) is the viscosity of the diluent at the temperature T
(Pa.s).
This representation allows to take no account of the simple
dilution effect and on the contrary to emphasis the eventual
contribution of organization and structural modifications.
SPE 69711
Results presented in Figure 12 show that besides a effect of
dilution an other mechanism of viscosity reduction exists with
alcohols. At this point we think that this may be due to
interactions between the chemical OH functions of the alcohol
and the polar function of the asphaltenes.
From the results above we have studied dilution with a blend
of a an hydrocarbon cut and an alcohol, precisely hexanol in
naphtha. Results are presented in Figures 13 and 14 and show
that adding a small percentage of hexanol in the naphtha
improves the dilution efficiency. For example addition of 10%
of hexanol in the naphtha improves the dilution efficiency by a
factor of almost 2 when 10% of diluent is used in the crude.
Increasing the percentage of alcohol is detrimental as it is a
compromise between the contribution of the alcohol viscosity
(the alcohol is more viscous than the naphtha) and specific
interactions between alcohols and asphaltenes.
Conclusion
From rheological and structural measurements heavy oils can
be described as entangled solvated asphaltene particles in a
solvent constituted of the maltenes. High viscosities of this
type of crudes are due to the entanglement of solvated
asphaltenes particles. Any ways that will limit the
entanglement will likely reduce the viscosity. Modifications
of the initial state of asphaltene aggregation by changing the
quality of the original maltene solvent (temperature, resins
content,...) of the asphaltenes, may influence the rheological
properties of the system.
Concerning dilution we have shown that when using low
viscosity hydrocarbons, like light crude oil or naphtha, the
viscosity reduction efficiency is controlled by the sole
viscosity of the diluent and not by its aromaticity. The
colloidal description of a natural heavy oil can be extended to
the diluted heavy oil when viewed as a solution of asphaltene
particles solvated in diluted maltenes. When blending with
more polar solvents like alcohols polar interactions are
possible and enhancements of viscosity reduction have been
observed. Solvent efficiency can be tailored taking into
account availability and cost aspects.
Acknowledgements
The authors thank P. Gateau, V. Ruffier-Méray (IFP),
C. Schranz (TotalFinaElf) for interesting discussions and the
FSH (Fond de Soutien aux Hydrocarbures) for financial
support.
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 6 J-F. ARGILLIER, L. BARRE, F. BRUCY, J-L. DOURNAUX, I. HENAUT, R. BOUCHARD, SPE 69711

40
SARA SARA (% weight) on C20+
dilute system semi-dilute system
(% weight) pentane heptane heptane SARA fractions C*
30

Realtive viscosity
C20+ C H N O S

Asphaltenes 17 14.1 83.8 7.5 1.3 1.7 4.8 20

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 10

Saturates 12 11.4 86.6 13 <0.3 <0.2 <0.1

0
Table 1: Properties of the Venezuelan heavy oil sample 0 0,05 0,1 0,15 0,2
Weight fraction of asphaltenes

Hydro- Viscosity (% weight)

carbon cut at 20°C
Figure 2: Colloidal interpretation, evolution of relative
(mPa.s) n- isoparaffi aro- napht- olefins viscosity as a function of asphaltenes weight fraction, T=20°C
paraffins ns matics enes

Naphta 0,6 26,8 29,8 12,8 30,6 80

Kerosene 0,94 3,6 17,9 57,5 4,3 16,7 3°C

60

Relative Viscosity
HCO 1,23 21,2 26,6 26,9 24,2
LCO 5,7 4,9 11,5 58,1 1,1 2,8
40
20°C
Table 2: Properties of the low viscosity hydrocarbon diluents
40°C
20
60°C
Alcohol Formula Viscosity at 80°C
20°C (mPa.s) 0
0 0,05 0,1 0,15 0,2
Butanol-1 C4H9OH 2,88
Weight fraction of asphaltenes
Hexanol-1 C6H13OH 5,21
Octanol-1 C8H15OH 9,04 Figure 3: Thermal dependence of the relative viscosity of
maltenes recombined with various amounts of asphaltenes
Table 3: Properties of the alcohols used as diluents
1000
1000
18%
17%
Viscosity (Pa.s)

15% 100
12%
Viscosity (Pa.s)

10%
100 8%
5% 10
2%
1%
0%
1
0 20 40 60 80 100
10
0,1 1 10 100 % resins weight fraction

Shear rate (s-1)

Figure 4 : Influence of resins on viscosity (T=40°C)

Figure 1: Flow curves of maltenes recombined with various

weight percentages of asphaltenes, T=20°C
SPE 69711 INFLUENCE OF ASPHALTENES CONTENT AND DILUTION ON HEAVY OIL RHEOLOGY 7

10000
1000
viscosity 20°C
1000
(Pa.s)

100 100

viscosity (Pa.s)
10
10
1

1 0,1

0,01
1 10 100
0,1
w eight fraction of diluent (%)
0 5 10 15 20 25
weight fraction of diluent (%) 80°C 60°C 40°C 20°C 3°C

naphtha HCO LCO kerosene

Figure 8: Influence of temperature on dilution with naphtha
Figure 5: Influence of dilution on the viscosity of the
Venezuelan crude at 20°C
120
100

viscosity reduction factor at 15%wt (%)

20°C, 15% dilution
viscosity of the diluted crude (Pa.s)

100

10

80

1
0,1 1 10 60
0 20 40 60 80 100
viscosity of the diluent (mPa.s)
temperature (°C)

naphtha HCO LCO kerosene

Figure 6: Relationship between dilution efficiency and
viscosity of light hydrocarbon diluents Figure 9: Influence of temperature on viscosity reduction of
different low viscosity hydrocarbons
35
1000 20°C
20°C recombined crude
30
diluted crude
100
25
viscosity (Pa.s)

relative viscosity

20
10

15
0%
1 10
11,8%

5 23,1%
0,1
0 5 10 15 20 25 30 82,8%
0
w eight fraction of diluent (%) 0 5 10 15 20

pure naphtha naphtha + toluene 75/25 asphaltenes w eight fraction (%)

naphtha + toluene 50/50

Figure 10: Comparison of relative viscosities of recombined
Figure 7: Influence of diluent aromaticity on dilution and diluted crude
efficiency
8 J-F. ARGILLIER, L. BARRE, F. BRUCY, J-L. DOURNAUX, I. HENAUT, R. BOUCHARD, SPE 69711

1000 20

Sincor
15 Sincor
100 + hexanol
+ naphtha
viscosity (Pa.s)

vicosity (Pa.s)
10
10

1
20°C, diluted at 10% wt
0 5 10 15 20 25
0
w eight fraction of diluent (%)
0 20 40 60 80 100
hexanol octanol 1-butanol 2-butanol
volume fraction of hexanol (%)
Figure 11: Dilution by alcohols (20°C)

Figure 13: Influence of addition of hexanol in naphta on the

viscosity (20% diluent)
1,E+04

100

light crudes 50
relative viscosity

viscosity reduction factor (%)

0
alcohols
1,E+03 0 20 40 60 80 100 120
-50

-100

20°C, diluted at 15%w t -150

1,E+02 -200
0,1 1 10
volume fraction of hexanol (%)
viscosity of diluent (mPa.s)
diluted at 10% w t diluted at 20% w t

Figure 12: Comparison between alcohols and hydrocarbon Figure 14: Influence of of addition of hexanol in naphtha on
diluents the viscosity reduction factor (10 and 20% diluent)