Fluid Phase Equilibria 147 Ž1998.

343–356

Viscosity and phase behaviour of petroleum fluids with high

asphaltene contents
A. Werner a , F. Behar b , J.C. de Hemptinne a, )
, E. Behar a

a
´
Institut Français du Petrole, Department of Thermodynamics, Transport Processes and Interfacial Phenomena,
´ 92506 Rueil-Malmaison Cedex, France
1-4 aÕ. de Bois-Preau,
b
´
Institut Français du Petrole, ´ 92506 Rueil-Malmaison Cedex, France
Department of Geochemistry, 1-4 aÕ. de Bois-Preau,
Received 12 May 1997; accepted 17 March 1998

Abstract

The aim of this paper is to provide original experimental data on the viscosity of five synthetic crude oils and
of three stock tank oils. This work completes a series of measurements on eight synthetic crude oils that have
been published previously wA. Werner, F. Behar, J.C. de Hemptinne, E. Behar, Org. Geochem. 24 Ž10–11.
Ž1996. 1079–1095x. All fluids are composed of dissolved gases Žexcept the stock tank oils., light and
intermediate hydrocarbons and a heavy oil fraction containing resins and asphaltenes. A large range of
petroleum fluids, from source rock to reservoir fluids are thus modelled. The study of crude oil viscosities first
requires the investigation of the phase behaviour in the same operating conditions. Seven synthetic crudes
precipitated asphaltenes due to their elevated gas and low aromatics concentration. We observed at our
experimental conditions of 35 MPa and 1008C an increased risk of asphaltenes precipitation for petroleum fluids
containing more than 28 wt.% of gas and less than 25 wt.% of aromatics. Viscosity measurements cover a range
of more than two orders of magnitudes from 0.29 to 67.5 mPa s. The crude oil viscosity depends strongly on
composition, especially on the gas and asphaltene concentrations. q 1998 Elsevier Science B.V. All rights
reserved.

Keywords: Gas fraction; Asphaltenes; Heavy oil; Viscosity; Density; Solid–fluid equilibria

1. Introduction
The viscosity of heavy petroleum fluids is important in many different scientific domains. In
geochemistry, the modelling of petroleum migration from source rocks to reservoir rocks w1x is based
on the extended Darcy’s law w2x. This law requires the dynamic viscosity of the migrating phase w3x.
The migrating fluids are often rich in resins and asphaltenes and their viscosity cannot be measured
due to the lack of representative samples.

)
Corresponding author.

0378-3812r98r$19.00 q 1998 Elsevier Science B.V. All rights reserved.

PII S 0 3 7 8 - 3 8 1 2 Ž 9 8 . 0 0 2 4 5 - 3
344 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 343–356

Petroleum viscosity is also important in physical sciences, for example in the production process of
commercial hydrocarbon reservoirs. Gas injection, generally CO 2 , is commonly applied as an
enhanced recovery method. While the CO 2 dissolves in the crude, it lowers the fluid’s viscosity and
allows a better exploitation yield.
Viscosity is also important in the field of refining processes. The exact knowledge of the crude oil
viscosity, whether or not in the presence of gas, is of crucial importance for the design of the units.
The fluid viscosity determines the head losses and thus the pressure within a unit.
Despite the demand for heavy oil viscosity data as a function of composition, pressure and
temperature, only a limited number are available. The few data that can be found have two major
flaws: either no compositional information is available w4,5x, or the fluids contain no dissolved gases
w6x, or both.
Werner et al. w1x stated that studying viscosities of fluids containing gaseous and heavy oil
components in varying proportions first requires the knowledge of the phase behaviour of the mixture.
This behaviour, however, is still badly known for fluids containing gases, intermediate hydrocarbons,
resins and asphaltenes in reservoir conditions of high pressure Ž) 10 MPa. and high temperature
Ž) 508C..

2. Sample characterisation

Experiments have been carried out on synthetic mixtures. Our principal aim was to represent
petroleum fluids from a marine origin at the beginning and at the end of its window in source rocks,
and for a reservoir fluid of the same origin.
The compositions of immature and mature fluids in source rocks were determined from pyrolysis
experiments in a closed system starting from a marine immature reference kerogen Ž Toarcian shales of
the Paris basin w7x.. The compositions of the representative reservoir fluids have been worked out
from a data base of 10 crude oils w8,9x.
Synthetic crude oil composition have been designed by using six different fractions whose internal
compositions are kept constant throughout the study. The complete selection criteria for the sample
compositions along with their ranges of concentration are described in the paper of Werner et al. w1x.
Two vacuum residues obtained from natural heavy crudes represent the heavy oil fractions. The
selected heavy crudes originate from the same basin Ž Athabasca, Alberta, Canada. , but one is
biodegraded leading to a much higher concentration in resins and asphaltenes. Thus, we can obtain
different resinsrasphaltenes ratios in our synthetic crudes by varying the concentrations of these two
vacuum residues. Our aim was to determine the influence of each of the six fractions on synthetic
crude viscosity.
In a first selection, Werner et al. w1x defined 22 potential mixtures Ž No. 1a–16d. and carried out
measurements on eight of them ŽNo. 1a, 1b, 1c, 1d, 2, 3, 9, 13. .

3. Experimental work

The geological conditions of pressure and temperature in sedimentary basins vary generally from
10 to 70 MPa and from 50 to 1508C. Werner et al. w1x thus selected the experimental conditions in the
 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 343–356 345

middle of that range: 35 MPa and 1008C. The experimental work for each synthetic crude oil is
divided into two main parts.

3.1. Preparation of the synthetic oil in the sapphire cell

The well-defined mixture of liquid and gaseous components is prepared at 35 MPa and 1008C. It is
stirred for at least 24 h, as the introduction of the gas can lead to a precipitation of solid asphaltenes
w1x. The phase behaviour of the synthetic crude oil, at 35 MPa and 1008C, is observed in the sapphire
cell, since only a viscosity measurement on a single phase has a physical significance.
Afterwards, the mixture is filtered at 35 MPa and 1008C in order to remove all solid particles. The
pore diameter of the filter is 0.45 m m. It ranges between the average sizes of most source rock pores
Ž0.001–0.003 m m. and most reservoir rock pores Ž50–200 m m. in depths of 1500 m or more. This
way, we try to simulate in the laboratory the filtration by source rocks during the primary migration in
sedimentary basins.

3.2. Viscosity and density measurements

The viscosity measurement on the homogeneous liquid phase is carried out with a rolling ball
viscometer at 35 MPa and 1008C. The relative error is about 5%. Moreover, the liquid density has
been determined at the same experimental conditions using a DMA 512 densimeter Ž PAAR. . The
density measurement has a high accuracy, with a relative error around 0.1%.
Each sample has been analysed twice: a first time after its preparation and a second time after the
viscosity measurement. Complete analytical and experimental procedures together with schemes of
the sapphire cell and the viscometer set-ups have been explained in detail by Werner et al. w1x.

4. Results and discussion

4.1. Study of the phase behaÕiour of the petroleum fluids

We have carried out measurements on five synthetic crude oils Ž Table 1: No. 5, 7, 14, 16c, 16d.
thus completing the series of eight mixtures already investigated by Werner et al. w1x: No. 1a, 1b, 1c,
1d, 2, 3, 9, 13. During the preparation of the mixtures in the sapphire cell we can observe two kinds
of phase splits: formation of a second fluid phase Ž liquid or vapour. and formation of a solid phase.
They can occur separately or simultaneously. Our observations on the additional five mixtures Ž Table
2. complete and confirm the ternary diagram published by Werner et al. w1x.
The compositions of the 13 investigated mixtures Ž i.e., including those reported in Ref. w1x. are
summarised in Table 1. They have been analysed a first time after preparation Ž PREP. and a second
time after filtration ŽVM.. Due to the possibility of asphaltene precipitation, the second analysis can
contain significantly lower amounts of this compound than initially present in the preparation. This
confirms that the solid particles retained by the filter are essentially asphaltenes.
Werner et al. w1x stated that the gas concentration in the fluid is a determining factor for the
presence or absence of asphaltenes precipitation. Above a ‘critical’ gas Ž CO 2 , C 1 q C 3 . content
asphaltenes are expected to precipitate; below this level, the asphaltenes remain in solution. This
346 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 343–356

Table 1
Summary of the complete series of 13 synthetic crudes: compositions Žin wt.%. at preparation ŽPREP. and after filtration
Žand possible loss of asphaltenes. ŽVM.
Mixture no. 1a 1a) 1b 1b) 1c 1c) 1d 1d) 2 2)
PREP VM PREP VM PREP VM PREP VM PREP VM
c
CO 2 3.8 3.9 13.7 12.8 13.9 13.1 13.9 13.7 14.0 14.0
C 1 qC 3 c 28.7 29.1 18.3 19.6 28.1 29.8 28.1 28.2 28.4 28.5
LIN c 29.8 30.4 30.0 30.4 20.0 21.1 30.9 31.3 29.8 30.7
CYC c 20.8 21.0 21.0 21.4 21.0 20.3 20.4 20.5 20.8 21.2
C 20q ŽSATqAROqRES. c 15.2 15.4 15.3 15.5 15.4 15.5 6.1 6.2 5.4 5.5
ASP c 1.7 0.2 1.7 0.3 1.6 0.2 0.6 0.1 1.6 0.1
Ý 100 100 100 100 100 100 100 100 100 100
Mixture no. 3 3)) 5 5 7 7 9 9) 13 13
PREP VM PREP VM PREP VM PREP VM PREP VM
CO 2 c 13.8 9.3 9.2 8.0 14.0 12.8 0 0 0 0
C 1 qC 3 c 28.0 20.0 3.6 5.2 3.0 4.2 28.0 31.5 2.9 2.5
LIN c 6.0 30.2 32.5 32.1 6.9 6.9 29.7 29.7 29.6 28.7
CYC c 20.1 21.2 17.1 16.9 19.1 19.2 21.3 20.7 21.4 22.3
C 20q ŽSATqAROqRES. c 27.3 19.0 32.5 32.1 46.5 46.6 18.3 18.0 38.1 38.3
ASP c 4.8 0.3 5.1 5.7 10.5 10.3 2.7 0.1 8.0 8.2
Ý 100 100 100 100 100 100 100 100 100 100
Mixture no. 14 14 16c 16c 16d 16d
PREP VM PREP VM PREP VM
c
CO 2 0 0 0 0 0 0
C 1 qC 3 c 3.0 3.2 3.0 3.3 2.9 2.4
LIN c 34.2 34.2 16.2 15.5 8.2 8.2
CYC c 17.5 17.5 18.8 19.3 18.0 18.0
C 20q ŽSATqAROqRES. c 35.2 35.1 47.8 47.7 57.1 57.4
ASP c 10.1 10.0 14.2 14.2 13.8 14.0
Ý 100 100 100 100 100 100

Data on mixtures No. 1a, 1b, 1c, 1d, 2, 3, 9, 13 have been measured by Werner et al. w1x.
)Initial fluid shows a liquid–solid equilibrium at 35 MPa and 1008C. It precipitates asphaltenes. Filtration turned it into a
single phase liquid.
))Initial fluid shows a liquid–liquid–solid equilibrium at 35 MPa and 1008C. First, a mixture of 20 wt.% CYC and 80
wt.% LIN was added to the sample, until the two liquid phases merged. Next, filtration removed the solid asphaltenes. For
more details see Werner et al. w1x.
c
The meaning of the symbols is as follows: CO 2 refers to carbon dioxide content; C 2 qC 3: light gas content; LIN: linear
hydrocarbon weight percent up to C 20 ; CYC: cyclic hydrocarbon, including both naphtenes and aromatics, up to C 20 ; C 20q
ŽSATqAROqRES.: heavy fraction of the crude, excluding asphaltenes; ASP: asphaltenes weight percent.

observation is not only important for the phase behaviour of the fluid but consequently also for its
viscosimetric behaviour. We therefore carried out one additional experiment to narrow the range of
this ‘critical’ gas content. We created a liquid of 13.3 wt.%. Linear Hydrocarbons, 47.2 wt.%. Cyclic
hydrocarbons and 39.5% of the vacuum residue with a low asphaltenes content. We called this
experiment ‘L11’, because its liquid composition is identical to that of mixture No. 11 of Werner et
Table 2
Summary of real and synthetic crude oils: gas and aromatic concentrations Žwt.% of the total composition. and indication if a precipitation occurred or not
Source or name of crude; pressurer Nature of CO 2 C 1q C 3 ÝŽCO 2 qC 1 Aromatics Aromatics C 20q Ý aromatics Precipitation?
temperature crude Žwt.%. Žwt.%. qC 3 . Žwt.%. C 6 –C 20 Žwt.%. Žwt.%. Žwt.%.
Behar et al. w10x; 25–34 MPar84.58C real 23.4 4.7 28.1 13.2 19.2 32.4 yes

A. Werner et al.r Fluid Phase Equilibria 147 (1998) 343–356

Lasne et al. w11x; 40 MPar458C synthetic 0 2.0 2.0 63.8 0 63.8 no
40 MPar458C synthetic 73.3 0.5 73.8 16.2 0 16.2 yes
40 MPar558C synthetic 0 2.0 2.0 63.0 0 63.0 no
40 MPar608C synthetic 73.4 0.7 74.1 16.4 0 16.4 yes

Werner et al. w1x; Mixture No. 1a; synthetic 3.8 28.7 32.5 13.9 6.7 20.6 yes
35 MPar1008C
Mixture No. 1b; 35 MPar1008C synthetic 13.7 18.3 32.0 14.1 6.7 20.8 yes
Mixture No. 1c; 35 MPar1008C synthetic 13.9 28.1 42.0 14.0 6.8 20.8 yes
Mixture No. 1d; 35 MPar1008C synthetic 13.9 28.1 42.0 13.7 2.7 16.4 yes
Mixture No. 2; 35 MPar1008C synthetic 14.0 28.4 42.4 13.9 2.4 16.3 yes
Mixture No. 3; 35 MPar1008C synthetic 13.8 28.0 41.8 13.4 11.9 25.3 yes
Mixture No. 9; 35 MPar1008C synthetic 0 28.0 28.0 14.3 8.0 22.3 yes
Mixture No. 13; 35 MPar1008C synthetic 0 2.9 2.9 14.3 16.6 30.9 no

Mixture No. 5; 35 MPar1008C synthetic 10.5 2.3 12.8 11.5 14.2 25.7 no
Mixture No. 7; 35 MPar1008C synthetic 14.0 3.0 17.0 12.8 20.2 33.0 no
Mixture No. 14; 35 MPar1008C synthetic 0 3.0 3.0 11.7 15.2 26.9 no
Mixture No. 16c; 35 MPar1008C synthetic 0 3.0 3.0 12.6 20.7 33.3 no
Mixture No. 16d; 35 MPar1008C synthetic 0 2.9 2.9 12.1 24.7 36.8 no
Mixture L11; 35 MPar1008C synthetic 27.4 0 27.4 23.0 11.5 34.5 no
Mixture L11; 35 MPar1008C synthetic 29.2 0 29.2 22.4 11.2 33.6 yes

347
348 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 343–356

al. The homogenous liquid ‘L11’ was introduced at ambient pressure and temperature into the
sapphire cell, then compressed to 35 MPa and heated to 1008C, exactly in the same way as presented
above. This time, however, the gas Ž pure CO 2 . was injected in small quantities Ž approximately 2
wt.% at a time., rather than all at once.
After each injection, we stirred the mixture for 2 h in order to verify that the fluid was in
equilibrium conditions. No precipitation was observed up to a CO 2 concentration of 27.4 wt.%.
Spontaneous precipitation occurred when we raised its concentration to 29.2 wt.%. Consequently, at
the conditions of 35 MPa and 1008C the ‘critical’ gas content ranges between 27.4 and 29.2 wt%.
This result is consistent with our other experiments, even though the liquid and gas compositions are
not always similar. For example, experiment No. 9 of Werner et al. w1x showed an asphaltene
precipitation at a C 1 q C 3 concentration of 28 wt.%.
Behar et al. w10x have measured multiphase equilibria on a crude oil at 84.58C. They observed in a
pressure range from 25 to 34 MPa a solid precipitation at 28.1 wt.% of gas Ž containing 23.4 wt.%
CO 2 .. This result goes in the same direction as our experiments. Lasne et al. have demonstrated in an
investigation on synthetic crudes that precipitation not only depends on the gas concentration but also
on the aromaticity of the petroleum fluid.
Table 2 lists the results of Behar et al. w10x, Lasne et al. w11x and Werner et al. w1x, as well as the
new observations of this work as a function of gas concentration and aromaticity of the petroleum
fluid. The aromatics content of a fluid is calculated as follows:
Ý Aromaticss Aromatic concentration Ž 67% . in cyclic hydrocarbons Ž CYC.
q Aromatic concentration Ž 35–40% . in C 20q saturatesq Aromaticsq Resins
Table 2 states whether or not precipitation occurred. Fig. 1 shows all the crudes of Table 2 positioned
in a diagram as a function of gas and aromatics concentration. The precipitating fluids are marked by
a closed symbol, not precipitating ones by an open symbol. Fig. 2 can help to evaluate approximately
the risk of precipitation for petroleum fluids close to the pressure and temperature conditions
mentioned in Table 2. One notices that a precipitation is likely for crudes containing 28 wt.% of gas
Žeither CO 2 or hydrocarbon gas. or more. In addition, all the crudes containing less than 25 wt.% of
aromatics wsum of light Ž C 6 q C 20 . and heavy Ž C 20q . aromaticsx precipitated. Unfortunately, data in
the region of low gas Ž- 28 wt.%. and low aromatics Ž- 25 wt.%. concentrations were not available.
Therefore we marked an ‘?’ in the concerned region of Fig. 1.
It must be noticed that not all the points of Table 2 and Fig. 1 have been measured at the same
conditions of pressure and temperature. Especially pressure has an important influence on the
flocculation phenomenon w12x. Nevertheless, we can conclude that a crude, close to the mentioned
experimental conditions, with less than about 28 wt.% of gas and more than about 25 wt.% of
aromatics is likely not to precipitate asphaltenes. Fig. 1 can be helpful for future experiments at
similar conditions in order to estimate rapidly if a petroleum fluid mixture is supposed to flocculate or
not.
Several authors have developed flocculation models for petroleum fluids, for example Hirschberg
et al. w13x, Cimino et al. w14x, Park and Mansoori w15x, Nghiem et al. w16x or Izquierdo and Rivas w17x.
However, those models can not be used directly for our experiments since they require unknown
thermodynamic parameters or do not apply to the given experimental conditions.
Since the main objective of this work is related to viscosity measurements, our contribution to the
phase behaviour analysis is limited to reporting our experimental observations Ž Table 2 and Fig. 1. .
 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 343–356 349

Fig. 1. The real and synthetic crudes of Table 2 positioned in a binary diagram as a function of gas and aromatics
concentration Žwt.% of total composition.. The precipitating fluids are marked by a closed symbol; not precipitating fluids
by an open symbol.

Fig. 2. Measured dynamic viscosities ŽmPa s; values are rounded off. as a function of composition Žwt.%. in a ternary
diagram; based on measurements on 13 synthetic crude oils Žmonophasic liquids after filtration. at 35 MPa and 1008C.
350 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 343–356

Other researchers in the same laboratory work on the data acquisition and modelling of asphaltenes
flocculation w18x. Our data will be integrated in their investigations.

4.2. Viscosity and density measurements

4.2.1. First experimental series

In a first series, we have measured the dynamic viscosities of two basic liquid fractions. At 35 MPa
and 1008C, we obtained 0.55 mPa s for the linear hydrocarbons and 0.72 mPa s for the cyclic
hydrocarbons. The low viscosities of the gas fractions can be determined from existing tables w19x:
0.062 mPa s for CO 2 and 0.036 mPa s for C 1 q C 3 at the same pressure Ž35 MPa. and temperature
Ž1008C.. The viscosities of the vacuum residues have not been measured because their melting points
are above 1008C.

4.2.2. Second experimental series

In a second series, we have carried out five viscosity and density measurements on synthetic crude
oils which add to the above mentioned eight mixtures measured previously by Werner et al. w1x. These
five additional measurements extend significantly the experimental domain towards more heavy
liquids. We are now able to analyse the results of the integral series of 13 measurements, No. 1a),
1b), 1c), 1d), 2), 3)), 5, 7, 9), 13, 14, 16c, 16d.
All 13 measured fluids were single phase liquids. The experimental results are given in Table 3.
The highest value Ž61.2 mPa s, mixture No. 16d. is more than 200 times greater than the lowest
measured value Ž0.29 mPa s, mixture No. 2). . We thus covered a range of viscosity of more than two
orders of magnitude.
A correlation between composition and viscosity can be found when comparing Tables 1 and 3. In
order to better visualise this relationship, we have equally completed the ternary diagram Ž Fig. 2. of
Werner et al. w1x which represents dynamic viscosity as a function of composition. The figure has
been motivated by Werner et al. w1x in view of the following observations.
v Fluids No. 1a and No. 1b have equivalent viscosities Ž0.36 and 0.37 mPa s. , while their
compositions differ only by the different ratios CO 2rC 1 q C 3 Ž Table 1.. One can assume that at
elevated gas concentrations ŽCO 2 andror C 1 q C 3 . the gas phase composition has no influence on
viscosity. This allows us to group CO 2 and C 1 q C 3 together and represent them in one pseudo-frac-
tion ‘GAS’.
v The linear hydrocarbons Ž LIN. may be put together with the cyclic hydrocarbons Ž CYC. into
one fraction, because their measured viscosities are very similar. The fraction called ‘C 6 –C 20’
represents thus all intermediate hydrocarbons between C 6 and C 20 .
The variation of dynamic viscosity as a function of composition has been studied along four
principal directions, A, B, C and D as indicated by the arrows in Fig. 2.
ŽA. The successive substitution Ž in the crude compositions. of intermediate hydrocarbons Ž C 6 –C 20 .
by the C 20q heavy fraction at a constant elevated gas content Ž CO 2 and C 1 q C 3 : about 42 wt.%. is
described by the line of samples No. 2)r1d)–1c). A small increase of viscosity is observed.
ŽB. The parallel arrow on the right side of the diagram indicates the second investigated direction:
the successive substitution Ž in the crudes compositions. of intermediate hydrocarbons by the C 20q
heavy fraction at a low gas content Ž about 3 wt.% of C 1 q C 3 .. It is described by the line of mixtures
 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 343–356 351

Table 3
Summary of the complete series of 13 synthetic crudes: experimental results of dynamic viscosity ŽmPa s. and densities
Žkgrm3 . at 35 MPa and 1008C
Mixture no. Dynamic viscosity Density
1a) 0.36 585
1b) 0.37 658
1c) 0.43 569
1d) 0.30 556
2) 0.29 548
3)) 0.39 604
5 1.08 790
7 7.05 897
9) 0.34 577
13 3.66 844
14 4.45 847
16c 28.8 907
16d 61.2 935

Data on mixtures No. 1a), 1b), 1c), 1d), 2), 3)), 9), 13 are taken from Werner et al. w1x.
),))See Table 1 for the meaning of these symbols.

No. 13r14–16c–16d. When little gas is present the increase of the heavy oil fraction increases
considerably the viscosity from 3.66 to 61.2 mPa s.
ŽC. The successive substitution Žin the crudes compositions. of gas Ž CO 2 and C 1 q C 3 . by the
C 20q heavy fraction at an elevated constant intermediate hydrocarbons ŽC 6 –C 20 . content is described
by the line of liquids No. 2)r1d)-1a)r1b)-9)-3))-5-13r14. The decrease of the gas fraction
results in a steep increase of viscosity from 0.29 to 4.45 mPa s.
ŽD. The parallel arrow on the bottom of the diagram shows the fourth investigated direction: the
successive substitution Žin the crudes compositions. of gas Ž CO 2 and C 1 q C 3 . by the C 20q heavy
fraction at a low and constant intermediate hydrocarbons Ž C 6 –C 20 . concentration of about 26 wt.%. It
is described by the crudes No. 7 and 16d. The dynamic viscosity is already large Ž mixture No. 7: 7.05
mPa s. due to the low content of gaseous, light and intermediate components. The increased content
of heavy oil, especially of the asphaltenes, leads to the largest viscosity observed Ž No. 16d: 61.2 mPa
s. .
The 13 viscosity measurements thus cover the whole composition range of petroleum fluids that we
have considered above Žwith both low and high asphaltene concentrations. . On closer examination of
the viscosity behaviour along the directions C and D it appears that two particular aspects deserve a
more profound analysis: the gas concentration and the asphaltene concentration.

4.2.2.1. The influence of gas on Õiscosity. Fig. 3 shows the measured dynamic viscosities of the
integral series of 13 synthetic crude oils as a function of their GAS Ž CO 2 and C 1 q C 3 . fraction. At
low gas content, the increase of the gas concentration leads to a steep decrease of viscosity. On one
hand, this result confirms the observations of Simon and Graue w20x who have investigated the
viscosity variations of real crude oils as a function of an added CO 2 fraction. They found a viscosity
reduction of one magnitude between the oil without gas and the oil containing of 30 mol% dissolved
352 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 343–356

Fig. 3. Measured dynamic viscosities ŽmPa s. of the synthetic crude oils Žsingle phase liquids after filtration. as a function of
the GAS ŽCO 2 and C 1 qC 3 . concentration. The letters C and D correspond to the directions indicated in figure 2.

CO 2 . Viscosity was further reduced of one magnitude when the gas content of the oil reached 68
mol% CO 2 . On the other hand, the corresponding curves of directions C and D ŽFig. 3. are not
superposed. Thus, the representation of crude oil viscosities only as a function of their gas
concentration is not sufficient.

4.2.2.2. The influence of asphaltenes on Õiscosity. One can recognise from Fig. 4 that the liquid’s
asphaltene concentration is a deciding factor for its viscosity. All the experimental points can be
represented by only one curve.

Fig. 4. Measured dynamic viscosities ŽmPa s. of the synthetic crude oils Žsingle phase liquids after filtration. as a function of
the asphaltene ŽASP. concentration.
 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 343–356 353

Table 4
Compositions and measured dynamic viscosities ŽmPa s. of three stock tank oils, AX 1, AX 2 and AX 3, at two different
pressure and temperature conditions
Stock tank GAS C 6 –C 20 C 20q Žsaturates, Asphaltenes Pressure Temperature Dynamic
oil Žwt.%. Žwt.%. aromatics, resins. Žwt.%. ŽMPa. Ž8C. viscosity
Žwt.%. ŽmPa s.
AX 1 0 33.5 66.4 0.1 0.1 25 2.39
35 100 1.05
AX 2 0 50.4 46.2 3.4 0.1 25 8.21
35 100 2.33
AX 3 0 35.9 59.9 4.2 0.1 25 67.5
35 100 8.19

4.2.3. Third experimental series

In a third experimental series, we have measured the dynamic viscosities of three stock tank oils
called AX 1, AX 2 and AX 3. AX 1 is a very light oil from Northern Africa. AX 2 comes from North
America and AX 3 is a heavy oil produced in Central America. We have analysed their compositions
and measured their dynamic viscosity at two different pressure and temperature conditions: at 0.1
MPa and 258C and at 35 MPa and 1008C. Viscosity measurements must be performed on single phase
fluids. As a result, in order to use the same fluid in the two mentioned conditions, no gas could be
added to the oil. All three tank oils were single phase liquid in both operating conditions Žat 0.1 MPa,
258C and at 35 MPa, 1008C.. The experimental results are presented in Table 4.
The three stock tank oils have larger dynamic viscosities at 0.1 MPa and 258C than at 35 MPa and
1008C. The viscosity measurements confirm that the viscosity reduction with temperature Ž from 258C
to 1008C. is not compensated by the pressure increase from 0.1 to 35 MPa. Moreover, we find again
that the dynamic viscosity of oils increases with the asphaltene concentration.

5. Modelling perspectives
The gas and asphaltene concentrations with their opposed effects are thus the key parameters of
crude viscosity as a function of composition. The other chemical families can be grouped in order to
further simplify the analytical representation. Only four fractions are thus proposed:
1. GAS ŽCO 2 and hydrocarbon gas. ,
2. C 6 –C 20 Žlight and intermediate hydrocarbons. ,
3. C 20q saturatesq aromaticsq resins,
4. Asphaltenes.
A following paper will deal with the modelling of crude oil viscosities, based on the analytical
representation of the fluid.

6. Conclusions
We present experimental measurements on the phase behaviour, dynamic viscosity and density of
five synthetic crude oils and three stock tank oils. They complete a first series of eight measurements
presented in a previous paper w1x.
354 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 343–356

Our principal aim was to get viscosity measurements on petroleum fluids as a function of chemical
composition. It was our target to cover the whole composition range from petroleum immature fluids
in source rocks up to reservoir oils. The totally 13 measurements on synthetic crude oils represent an
integral series because they cover the complete compositional range.

6.1. Phase behaÕiour

It has been demonstrated that studying the viscosity of a heavy petroleum fluid containing gas, e.g.,
a source rock fluid, first requires an investigation of its phase segregations. In our experiments, we
have established two kinds of fluid behaviour which can appear simultaneously or separately: the
formation of a solid phase and the formation of a second fluid phase. Seven of the 13 studied mixtures
precipitated asphaltenes at the chosen pressure Ž 35 MPa. and temperature Ž 1008C. conditions, due to
the presence of an important dissolved gas content and a poor aromatics concentration. As already
mentioned by Werner et al. w1x, such precipitated asphaltenes cannot take part in primary migration
because the particles are too large to leave the pore structure. This was demonstrated in our
experiments by the use of a filter with a pore diameter in-between the pore sizes of source rocks and
reservoir rocks. Those observations lead to an important parameter in the modelling of petroleum
migration: besides geochromatography and compositional fractionation during migration one also has
to consider precipitation of asphaltenes in the source rock itself w1x.
At the selected experimental conditions Ž 35 MPa, 1008C. we identified an elevated risk of
asphaltenes precipitation for petroleum fluids when the gas concentration is larger than about 28 wt.%
and when the aromatics content remains below 25 wt.% Ž Fig. 1.. However, these concentration limits
should be only considered as indications. In the future, a systematic investigation of precipitation as a
function of pressure, temperature and composition would be very useful to understand better the
flocculation limits in other operating conditions.

6.2. Dynamic Õiscosity

For the first time a relatively high number of dynamic viscosity data of heavy petroleum fluids with
exactly identified compositions, measured in reservoir conditions, cover large compositional ranges.
All of the fluids contain resins and asphaltenes, sometimes in high concentrations. Experimental
results prove that crude oil viscosity depends directly on composition. This has been illustrated by a
ternary diagram of viscosity ŽFig. 2. .
The gradual increase of the gas fraction leads to a viscosity reduction. This decrease is particularly
steep in the region of small gas concentrations Ž Fig. 3. , i.e., the strongest viscosity reductions have
been found for the very first gas quantities injected into the liquid. Moreover, we observed that the
internal composition of the gas fraction ŽCO 2 andror hydrocarbon gas. does not play a significant
role on crude viscosity.
The viscosity of crude oils increases strongly ŽFig. 4. with the asphaltene concentration.
Additional viscosity measurements on three stock tank oils have proven the strong influence of
temperature and pressure on viscosity.
The aim of this paper is to furnish new, original experimental viscosity data. The complete
modelling of dynamic viscosity will be published later.
 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 343–356 355

7. Nomenclature

LIN linear hydrocarbons

C 20q SAT C 20q saturates
C 20q ARO C 20q aromatics
CYC cyclic hydrocarbons
RES resins
ASP asphaltenes

Acknowledgements

We thank J.P. Courcy, M. Munier and N. Berton for technical assistance.

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