Fluid Phase Equilibria 147 Ž1998.

319–341

A new viscosity model for petroleum fluids with high asphaltenes

content
a, )
A. Werner , J.C. de Hemptinne a , F. Behar b , E. Behar a , C. Boned c

a
´
Institut Français du Petrole, ´
Department of Thermodynamics and Transport Processes, 1-4 aÕ. de Bois-Preau,
92506 Rueil-Malmaison Cedex, France
b
´
Institut Français du Petrole, ´ 92506 Rueil-Malmaison Cedex, France
Department of Geochemistry, 1-4 aÕ. de Bois-Preau,
c
High Pressure Laboratory, AÕ. de l’UniÕersite,´ UniÕersite´ de Pau et des Pays de l’Adour, 64000 Pau, France
Received 12 November 1997; accepted 26 March 1998

Abstract

A compositional model for predicting the viscosity of petroleum fluids as a function of temperature and
pressure has been developed. It is based on a mixing rule that takes into account the compositional information,
and on the model of Kanti et al. w1x for the dependence on pressure and temperature. The approach of Grunberg
and Nissan w2x is used in order to take into account the fluids composition. Four different fractions are used:
Gas, C 6 –C 20 , C 20q Žsaturatesq aromaticsq resins., and C 20q Žasphaltenes.. This model is designed so as to be
valid in a large compositional range, especially for liquids containing large amounts of asphaltenes. The model
of Kanti uses a single viscosity value for predicting fluid viscosity at any pressure and temperature. Its universal
parameters have been fitted on a large database ranging up to 100 MPa in pressure and up to 1208C in
temperature. The validation of this new model on 76, so far, unpublished experimental data points of crude oils,
covering a dynamic viscosity range from 2 to 23,298 mPa s, led to an absolute mean deviation of 24%. q 1998
Elsevier Science B.V. All rights reserved.

Keywords: Viscosity; Petroleum liquid; Asphaltenes; Model; Mixing rule

1. Introduction

Viscosity of petroleum fluids is a very important parameter for the description of all processes
where these fluids are transferred from one place to another. A strong demand in the upstream
petroleum industry concerns the modeling of petroleum migration processes. Primary, secondary and
tertiary migrations of petroleum fluids from the source rocks to the reservoir rocks are described by
the extended Darcy’s law w3x.

)
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 5 2 - 0
320 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341

However, the lack of experimental data that provide compositional information results in a very
poor knowledge of the behavior of the dynamic viscosity as a function of composition, particularly for
very heavy fluids. Indeed, most authors focus on the effect of only one parameter Ž usually either
pressure or temperature. , but neglect the effect of the others Ž usually composition. . During the
migration process, the composition changes simultaneously with pressure and temperature, and a
correct description of the combined effect of the three parameters is essential.
Published models which aim at such a description Žw4–6x. require the knowledge of the critical
parameters of mixture components. In the case of crudes containing heavy «continuous» fractions,
such as resins and asphaltenes, these parameters cannot be evaluated as they have no physical
meaning. In addition, several studies w7–9x indicate that the Lohrenz–Bray–Clark correlation w4x is not
suited for fluids containing large amounts of CO2 w7x, or heavy fluids
In a recent paper w10x, we have presented a large number of experimental viscosity measurements
whose choice is based on the method of experimental design w11x. It is our object in this work to
develop a predictive relationship based on these experimental data, and other data collected in the
literature.
The effect of temperature on liquid viscosity is well known, and the law developed by Andrade
w12x is generally accepted below 1508C. Likewise, the effect of pressure can be described by an
exponential law, as proposed by Kashiwagi and Makita w13x. Kanti et al. w1x have combined these two
laws, and express the dynamic viscosity h Ž P,T . of any liquid as follows:

h Ž P ,T . 1 1 DqP
ln
h Ž P0 ,T0 .
sa
ž T
y
T0 / q E ln
ž D q P0 / Ž1.

where P stands for the pressure, P0 being a reference pressure Ž usually atmospheric. , and T
represents the absolute temperature, with T0 a reference temperature. In order to make their model
predictive, Kanti et al. propose relationships for the parameters a , E and D as a function of the
viscosity in the reference conditions Žh Ž P0 , T0 ... These relationships have been established by fitting
a database containing 216 experimental points of crude oil viscosities, for pressures ranging from 0.1
to 100 MPa and temperatures from 20 to 1008C. Tests by Et-Tahir w14x have demonstrated that the
model of Kanti et al. w1x can describe viscosity behavior up to pressures of 500 MPa.
The power of the model of Kanti et al. w1x is obvious, since it appears that the knowledge of one
reference viscosity, whatever is the fluid composition, is enough for describing the viscosity behavior
in a very large range of pressures and temperatures.
However, this model is limited for describing fluids whose composition vary during migration. In
order to solve this problem, Et-Tahir w14x suggests to use mixing rules which allow to calculate the
viscosity of a mixture of known composition based on the viscosities of the pure components. A large
number of mixing rules exist. Kanti w15x, Et-Tahir w14x and Boned et al. w16x have evaluated them on
the basis of a large number of binary mixtures, some ternaries, quaternaries and a five-component
mixture. They concluded that the mixing rule of Grunberg and Nissan w2x offers the best compromise
between accuracy and complexity. The viscosity of a mixture, hm , is described by the generalization
of this rule as a function of the molar fractions, x i , of the components w17x:

ln hm s Ý ln hi q Ý Ý x i x j li j q Ý Ý Ý x i x j x k l i jk q . . . Ž2.
xi i j/i i j/i k/i , j
 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341 321

where the parameters l i j , l i jk , . . . are binary, ternary, . . . interaction coefficients. Grunberg and
Nissan only use binary interaction coefficients and Et-Tahir w14x propose a group contribution method
in order to determine these coefficients.
The combination of the model of Kanti et al. w1x given by Eq. Ž 1. , and the generalized mixing rule
of Grunberg and Nissan w2x presented in Eq. Ž 2. , can provide a predictive model of the viscosity of a
petroleum fluid as a function of pressure, temperature and composition. An additional problem arises,
however, when looking at the true composition of a reservoir fluid. The viscosities of the pure
components of reservoir fluids are impossible to determine individually. In particular, we have shown
in our previous paper w10x that the presence of dissolved asphaltenes has a very large influence on the
fluid viscosity. As a result, we have proceeded in two steps for improving the above model.
In a first step, we have extended the database used for fitting the parameters of the model of Kanti
et al. w1x. While the original database was limited to viscosities up to 14 mPa s, we have extended it to
viscosities up to 14,200 mPa s.
In a second step, we have described reservoir fluids as mixtures of four pseudo-components, as
suggested by our previous paper w10x. Using experimental measurements on 18 synthetic and real
fluids, we have adapted the generalized model of Grunberg and Nissan.

2. The modified model of Kanti

The parameters of the model of Kanti et al. w1x as presented in Eq. Ž 1. depend on the reference state
chosen. We decided to keep the same reference state as that proposed by the authors: P0 s 0.1 MPa
and T0 s 258C s 298.15 K. The « viscosity» at this reference state, h Ž P0 , T0 ., must be computed for
any fluid as an intermediate step for applying this model. The numerical value thus obtained should
not be considered as a true viscosity since the fluid most likely will flash into a liquid and a vapor
phase under these conditions. We therefore will avoid using the term « viscosity» for this calculation
intermediate. Only for stock tank oils does this quantity have the physical significance of a viscosity.
According to Kanti et al. w1x, the parameter a of Eq. Ž 1. is a function of the parameter, h Ž P0 , T0 . ,
while the parameters E and D are functions of the viscosity at the reference pressure, but at the actual
temperature of the mixture, h Ž P0 , T .. As a result, instead of fitting all parameters simultaneously, we
propose to look in a first step at the influence of temperature only on the viscosity.
When the pressure is equal to the reference pressure Ž0.1 MPa., the model of Kanti et al. w1x is
limited to a function of temperature:
1 1
h Ž P0 ,T . s h Ž P0 ,T0 . exp a
ž T
y
T0 / Ž3.

where the parameter a is a function of z 0 s ln h Ž P0 , T0 . .

The data used for performing the fitting w1,18–20x are all measured at the reference pressure
Žexcept for two fluids for which the viscosity at reference pressure was extrapolated linearly. and
contain for the same fluid several viscosity values as a function of temperature. The viscosity at
reference conditions, h Ž P0 s 0.1 MPa; T0 s 258C., is known for almost all data sets. The regression
procedure has been explained more in detail by Werner w21x.
We thus established a total number of 13 pairs of a and z 0 values which are represented in
Table 1. The 63 experimental data points that have been used for the regression cover a temperature
322 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341

Table 1
Regression of a values from 13 isobaric data sets
No. Origin of data Number of Pressure of Reference viscosity z 0 s ln h a wKx
data points the isobar h Ž0.1 MPa, 258C. Ž0.1 MPa, 258C.
wMPax wmPa sx
1 Mehrotra and Svrcek w18x 5 0.1 96,119 a 11.4733 10,016
2 Mehrotra and Svrcek w19x 5 0.1 30,842 a 10.3366 9349
3 Al-Besharah et al. w20x 4 0.1 6.91 1.9330 2152
4 4 0.1 58.6 4.0707 3914
5 4 0.1 595 6.3890 6383
6 Kanti et al. w1x 3 0.1 0.69 y0.3711 1064
7 5 0.1 0.84 y0.1744 1394
8 4 0.1 1.1 0.0953 1279
9 5 0.1 1.43 0.3577 1527
10 4 0.1 1.86 0.6206 1653
11 5 0.1 2.37 0.8629 1762
12 5 0.1 3.0 1.0986 1877
13 5 0.1 3.84 1.3455 2040
Ý 63
a
The value is obtained by linear extrapolation of high pressure data.

range from 25 to 119.88C and a viscosity range from 0.295 to 14,200 mPa s. Fig. 1 demonstrates the
strong correlation between the a and the corresponding z 0 values. Practically, it expresses that the
influence of temperature on viscosity is stronger when the value of h Ž P0 , T0 . is greater. A second
order polynomial has been used for the regression:

a s 16.07z 02 q 634 z 0 q 1190.3 Ž4.

In a second step, the effect of pressure only on viscosity is evaluated by taking the actual
temperature T as the reference temperature. Eq. Ž 1. can then be written as:

h Ž P ,T . DqP
ln
h Ž P0 ,T .
s E ln
ž D q P0 / Ž5.

Kanti et al. w1x have defined the parameters D and E as functions of z s ln h Ž P0 , T ..

In order to determine these functions, we used isothermal data sets from literature which can be
divided into two classes: stock tank oils w1,18–20x and crude oils containing dissolved gas w22,23x.
The viscosity h Ž P0 , T . is known for all the stock tank oils. However, for the gas containing crude
oils, the viscosity cannot be measured at ambient pressure Ž0.1 MPa. because the fluid would flash
into a vapor and a liquid phase. In this case, «pseudo viscosities» h Ž P0 , T . at P0 s 0.1 MPa have
been obtained by linear extrapolation from the other data points which is a fair approximation. The
regression procedure has been explained more in detail by Werner w21x.
We regressed a total number of 92 combinations of D, E and z. They are presented in Table 2.
The 524 data points that have been used for the regression of D and E cover a pressure range from
0.1 to 100 MPa and a viscosity range from 0.096 to 21,200 mPa s.
 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341 323

Fig. 1. Correlation between a and the corresponding z 0 values. The dots represent the data from Table 1, the continuous
line represents Eq. Ž4..

Figs. 2 and 3 represent the 92 values of D and E, respectively, as functions of z. Fig. 2 indicates
that even though an important scatter subsists, a relationship can be drawn between the parameters D
and z. On the other hand, Fig. 3 shows that E is always close to 1, independently of z, except very
near to z s 0. A more detailed analysis shows that the pressure variations for those data around z s 0
are the most elevated Žup to 100 MPa. . Most other data sets have smaller pressure intervals and
therefore the influence of pressure can be expressed by a linear relationship. In addition, the higher
the temperature, the closer E is to one. As a result, we can simplify the relationship by stating that
E f 1 either when the pressure interval is small Ž i.e., limited to 70 MPa. or when the temperature is
elevated. Under these conditions, Eq. Ž5. is written as:

DqP
h Ž P ,T . s
ž D q P0 / h Ž P0 ,T . Ž6.

Since in all cases P ) P0 , we can state that the influence of pressure on viscosity is higher for
smaller D values because it increases the ratio D q PrD q P0 . In practice, according to Fig. 2, this
means that the influence of pressure is larger for higher viscosities h Ž P0 , T . .
We propose to express the parameter D as an exponential function of z. It guarantees a safer
extrapolation beyond the adjustment range, in opposition to a polynomial function, as suggested by
Kanti et al. w1x. The new expression for D is:

D MPa s 60.9 exp Ž y0.192 z . Ž7.

Two different tests have been performed on the above modified Kanti model in order to validate it
for any petroleum liquid.
Table 1 summarizes 63 data points, originating from 13 petroleum fluids, which we have used for
fitting the temperature dependence of the viscosity. A total of 325 data points are available for these
fluids when including the high pressure data points. Table 3 and Fig. 4 summarize how the modified
Kanti model performs on these 325 data. We observe some large maximum deviations for the first
two data sets which are explained by very broad viscosity ranges. The maximum deviations on the
other data sets never exceed 37.5%. We obtain a mean deviation of 12.7% on all 325 points that cover
324 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341

Table 2
Regression of D and E values from 92 isothermal data sets
No. Origin of data Number of Temperature of Viscosity z s ln h D wbarx E
data points the isotherm w8Cx h Ž0.1 MPa, T . Ž0.1 MPa, T .
wmPa sx
1 Mehrotra and Svrcek w18x 6 43 14,200 9.5610 196.7 0.998
2 6 58.3 3250 8.0864 207.3 0.996
3 6 80.5 580 6.3630 228.4 0.998
4 6 103.7 159 5.0689 375.3 0.998
5 6 119.6 79 4.3694 311.4 1
6 Mehrotra and Svrcek w19x 6 37.2 9100 9.1160 289.4 0.999
7 6 46.1 3800 8.2428 356.9 1
8 6 58.7 1390 7.2371 384.2 0.996
9 6 89.4 190 5.2470 396.9 1
10 6 115.2 64 4.1589 475.7 1.001
11 Quail et al. w22x 6 28 1430 7.2654 269.4 0.999
12 5 28.3 139a 4.9378 296.6 1.001
13 4 28.3 24.2 a 3.1857 218.9 1
14 3 110 14a 2.63911 451.7 1.002
15 4 110 3.4 a 1.2384 119.2 1.021
16 3 28.3 456a 6.1223 274.9 1
17 4 28.3 121a 4.7992 451.8 1
18 4 28.3 42.7 a 3.7542 340.4 1
19 4 28.3 32.5a 3.4812 317.8 1
20 Al-Besharah et al. w20x 5 25 6.91 1.9330 420 0.971
21 5 30 5.95 1.7834 403.9 0.961
22 5 40 4.93 1.5953 518.9 0.975
23 5 50 3.98 1.3813 606 0.981
24 5 25 58.6 4.0701 242.4 0.97
25 5 30 46.4 3.8373 277.7 0.978
26 5 40 30.8 3.4271 286 0.976
27 5 50 22.0 3.0927 354.3 0.982
28 5 25 595 6.3890 133.8 0.963
29 5 30 408 6.0117 139.7 0.962
30 5 40 212 5.3583 137.3 0.954
31 5 50 123 4.8095 155.2 0.96
32 Ghassan et al. w23x 6 76.7 1.94 a 0.6661 451 1.008
33 6 82.2 2.28 a 0.8253 386.7 1.007
34 4 77.2 1.20 a 0.1840 868.1 1.017
35 5 82.2 0.575a y0.5534 400.6 1
36 5 76.7 1.99 a 0.6907 428.1 1.007
37 6 76.7 0.867 a y0.1427 285.1 1.009
38 4 87.8 1.64 a 0.4959 679.2 1.016
39 4 81 0.889 a y0.1177 500.5 0.999
40 6 93 1.41a 0.3436 608.5 1.02
41 6 93 0.678 a y0.3888 339.9 0.998
42 8 93 1.10 a 0.0998 789 1.149
43 6 90 4.18 a 1.4308 490.3 1
44 Ghassan et al. w23x 5 91.1 0.49 a y0.7072 436.4 0.999
45 5 82.8 1.43 a 0.3556 544.4 0.997
 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341 325

Table 2 Žcontinued.
No. Origin of data Number of Temperature of Viscosity z s ln h D wbarx E
data points the isotherm w8Cx h Ž0.1 MPa, T . Ž0.1 MPa, T .
wmPa sx
46 3 91.1 0.23 a y1.4653 794.5 0.997
47 4 91.1 0.26 a y1.3509 1395.1 0.998
48 8 89.9 1.44 a 0.3639 559.3 1
49 9 104.4 0.392 a y0.9365 570.8 1
50 4 97 0.096 a y2.3434 1006.6 0.999
51 12 82.2 4.4 a 1.4770 481.4 0.998
52 9 87.8 0.93 a y0.0726 452.6 1.053
53 11 37.8 16.9 a 2.8249 899.6 1
54 5 71.1 18.2 a 2.9053 487 1.002
55 5 49 14.0 a 2.6391 479.6 1.001
56 5 60 9.5a 2.2513 350.8 1.003
57 Kanti et al. w1x 6 25 0.69 y0.3711 822 1.066
58 6 40 0.58 y0.5447 809.4 1.06
59 6 60 0.48 y0.7444 825.1 1.047
60 6 25 0.84 y0.1744 891.4 1.34
61 6 40 0.69 y0.3711 768.9 1.078
62 6 60 0.55 y0.5978 801.1 1.076
63 6 80 0.40 y0.9163 639.5 0.989
64 6 100 0.30 y1.2208 555.6 0.95
65 6 25 1.1 0.0953 1074 1.34
66 6 40 0.91 y0.0998 1105.9 1.423
67 6 60 0.55 y0.5978 401.7 0.736
68 6 80 0.54 y0.6255 724.2 1.026
69 6 25 1.43 0.3577 591.2 1.006
70 6 40 1.11 0.1044 898.9 1.265
71 6 60 0.84 y0.1744 850.8 1.25
72 6 80 0.64 y0.4541 690.4 1.055
73 6 100 0.52 y0.6539 715.2 1.043
74 6 25 1.86 0.6206 467.2 0.923
75 6 40 1.42 0.3507 572.1 0.967
76 6 60 1.03 0.0296 1905.9 2.187
77 6 80 0.80 y0.2294 811.6 1.186
78 6 25 2.37 0.8629 416.8 0.931
79 6 40 1.75 0.5596 477.8 0.953
80 6 60 1.26 0.2311 629.8 1.043
81 6 80 0.95 y0.0513 960.5 1.412
82 6 100 0.75 y0.2877 690.8 1.092
83 6 25 3.0 1.0986 365.8 0.929
84 6 40 2.15 0.7655 427.9 0.946
85 6 60 1.50 0.4055 521.9 0.995
86 6 80 1.13 0.1222 948.7 1.383
87 6 100 0.93 y0.0726 1118.5 1.546
88 6 25 3.84 1.3455 331.2 0.942
89 6 40 2.67 0.9821 365.4 0.948
90 6 60 1.81 0.5933 455.1 0.977
326 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341

Table 2 Žcontinued.
No. Origin of data Number of Temperature of Viscosity z s ln h D wbarx E
data points the isotherm w8Cx h Ž0.1 MPa, T . Ž0.1 MPa, T .
wmPa sx
91 6 80 1.32 0.2776 611.1 1.077
92 6 100 1.1 0.0953 939.9 1.266
Ý 524
a
The value is obtained by linear extrapolation of high pressure data.

pressures from 0.1 to 100 MPa, temperatures from 25 to 119.88C and viscosities from 0.295 to 21,200
mPa s.
A second validation has been carried out on viscosity measurements of Werner et al. w10x on three
crude oils: AX 1, AX 2 and AX 3. The viscosities of all three crudes had been measured under two
different conditions Ž0.1 MPa, 258C and 35 MPa, 1008C.. These data have not been used for fitting
the modified model of Kanti et al. The results are presented in Table 4 and Fig. 5. The mean deviation
of 6.8% confirms that the modified model of Kanti et al. can be applied to crude oils with very
different reference viscosities.

3. The modified generalized model of Grunberg and Nissan

As mentioned above, one major problem arises when trying to apply Eq. Ž 2. to a petroleum
mixture, in particular, when it is rich in asphaltenes. The number of pure components and their
identification is a challenge. In addition, it is almost impossible to determine their individual
viscosity. Based on the conclusions of a sensitivity analysis in our previous paper w10x, we propose to
consider the petroleum fluid as a mixture of only four pseudo-components:
1. GAS ŽCO 2 and hydrocarbon gases. ,
2. C 6 –C 20 Žlight and intermediate hydrocarbons. ,

Fig. 2. Correlation between D and the corresponding z values. The dots represent the data from Table 2, the continuous line
represents the exponential fit ŽEq. Ž7...
 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341 327

Fig. 3. Correlation between E and the corresponding z values. The dots represent the data from Table 2, the continuous line
represents Es1.

3. C 20q Ž saturatesq aromaticsq resins.,

4. Asphaltenes.
A second difficulty is found because Eq. Ž 2. is based on molar fractions. The molar mass of the
asphaltene fraction being difficult to determine with accuracy w24x, the molar fractions are unknown.
We have therefore investigated the possibility to use weight fractions rather than molar fractions. The
performances of the mixing rule of Grunberg and Nissan w2x have been tested, first expressed in molar
fractions, x i , second expressed in mass fractions, wi . In order to keep this test ‘pure’, we did not use
any adjustable parameter. The two mixing rules are thus:

ln hm s Ý x i ln hi and ln hm s Ý wi ln hi
i i

The database used for this test has been published by Kanti et al. w1x and contains three binaries and
one ternary mixture made of the following pure components: n y C 7 , n y C 10 , n y C 14 , butylben-
zene, nonylbenzene. All data have been measured at 40 MPa and 808C which are close to the
conditions that we have used for establishing the mixing rule parameters Ž 35 MPa and 1008C,
w10,11x.. We obtained an average deviation of 5.6% between measured and calculated viscosities for
the mixing rule expressed in molar fractions and an average deviation of 3.1% for the mixing rule
expressed in mass fractions. We cannot exclude that for other samples the expression using molar
fractions might give slightly more accurate values than the expression using the mass fractions.
Nevertheless, one can conclude from these results that the application of the Grunberg and Nissan w2x
mixing rule expressed in mass fractions is legitimate. The new mixing rule is thus written for four
components, as follows:

ln hm s w 1 ln h1 q w 2 ln h 2 q w 3 ln h 3 q w4 ln h4

q w 1w 2 l12 q q w1w 3 l13 q w 1w4 l14 q w 2 w 3 l23 q w 2 w4 l24

q w 3 w4 l34 q w 1w 2 w 3 l123 q w 1w 2 w4 l124 q w 1w 3 w4 l134

q w 2 w 3 w4 l 234 q w 1w 2 w 3 w4 l1234 Ž8.

 328
Table 3
First validation of the modified model of Kanti et al.: properties of 13 data sets from the literature
No. Origin of data Number of Reference Pressure Temperature Viscosity Mean Maximum

A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341

data points viscosity range range range deviation deviation
h Ž0.1 MPa, 258C. wMPax w8Cx wmPa sx w%x w%x
wmPa sx
1 Mehrotra and Svrcek w18x 30 96,119a 0.1–10.18 42.7–119.8 79–21,200 37.4 77.0
2 Mehrotra and Svrcek w19x 30 30,842a 0.1–10.32 36.8–115.6 64–12,100 31.1 68.9
3 Al-Besharah et al. w20x 19 6.91 0.1–54.77 25–50 3.98–14.9 6.9 13.1
4 19 58.6 0.1–54.77 25–50 22–170 7.2 16.2
5 19 595 0.1–54.77 25–50 123–2371 15.0 32.4
6 Kanti et al. w1x 17 0.69 0.1–100 25–60 0.475–1.585 10.0 14.1
7 29 0.84 0.1–100 25–100 0.295–2.21 12.2 37.5
8 23 1.1 0.1–100 25–80 0.535–2.86 8.6 12.5
9 29 1.43 0.1–100 25–100 0.52–4.04 6.9 10.9
10 23 1.86 0.1–100 25–80 0.795–5.37 7.1 12.5
11 29 2.37 0.1–100 25–100 0.75–7.39 3.8 11.1
12 29 3.0 0.1–100 25–100 0.93–9.93 5.0 11.1
13 29 3.84 0.1–100 25–100 1.1–13.86 5.9 13.8
TOTAL Ýs 325 0.1–100 25–119.8 0.295–21,200 12.7 77.0

Mean and maximum deviations between experimental and calculated viscosities.

a
The value is obtained by linear extrapolation of high pressure data.
 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341 329

Fig. 4. First validation of the modified model of Kanti et al.: The 325 experimental data points identified in Table 3 are
plotted vs. their calculated viscosities. The straight, diagonal line indicates where the calculated and the measured viscosities
are identical.

The determination of the four ‘pseudo-component’ viscosities and of the interaction parameters is
based on our experimental work published recently w10x. The viscosity measurements are all made at
35 MPa and 1008C. The values are therefore only valid for these conditions.
The viscosity of the «GAS» and of the «C6–C20» fractions at 35 MPa and 1008C can be evaluated
with a mixing rule ŽGrunberg and Nissan, without interaction coefficients. , knowing the exact
composition of these fractions. The viscosity of the ‘GAS’ fraction, h1, is the log mean value of the
dynamic viscosity of CO 2 Ž 0.062 mPa s. and of the mixture viscosity of C 1 q C 3 Ž0.036 mPa s.; thus
h1 s 0.0472 mPa s. The ‘C 6 –C 20’ fraction is a mixture of two fractions whose dynamic viscosity has
been measured: a Linear hydrocarbons fraction Ž 0.55 mPa s. and a Cyclic hydrocarbons fraction Ž 0.72
mPa s.. We take the log mean of the two values, i.e., h 2 s 0.63 mPa s.
The viscosity of the heavy fractions, h 3 and h4 , and the values of the interaction parameters remain
unknown and are therefore determined by fitting to the experimental data. Eighteen experimental data

Table 4
Second validation of the modified model of Kanti et al.: measured and calculated viscosities of three crude oils
Measured Measured Calculated Absolute
reference dynamic dynamic deviation
viscosity at 0.1 viscosity at 0.1 viscosity at 0.1 w%x
MPa and 258C MPa and 1008C MPa and 1008C
wmPaPsx wmPaPsx wmPaPsx
Crude AX 1 2.39 1.05 1.13 7.3
Crude AX 2 8.21 2.33 2.30 1.2
Crude AX 3 67.5 8.19 7.22 11.8
Mean deviation w%x 6.8
330 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341

Fig. 5. Second validation of the modified model of Kanti et al.: Comparison ŽTable 4. between the experimental viscosities
Žmeasured at 0.1 MPa, 258C and 35 MPa, 1008C. of three crude oils wtrianglesx which possess different viscosimetric
behaviors Žlight, medium, heavy. with the model’s predictions wcontinuous curvex that have been calculated at 35 MPa and
1008C from reference viscosities at 0.1 MPa and 258C.

points, ranging in viscosity from 0.29 to 311 mPa s, are available for this purpose. They are presented
in Table 5, in the order of increasing viscosity:
Ø 13 synthetic crude oils measured by Werner et al. w10x
Ø 3 real crude oils ŽAX 1, AX 2 and AX 3. measured by Werner et al. w10x
Ø 2 data points Ža real Boscan crude oil and an Athabasca vacuum residue. measured by Cohen et al.
w25x at 0.1 MPa and 1008C. The data have been extrapolated to 35 MPa and 1008C using the
modified model of Kanti et al. described here above.
The heavy ends of all the fluids used originate from type II organic matter.
Eq. Ž8. must fit all of these data points, but should also support extrapolation to pure components
or to other petroleum mixtures. We should expect the following behavior:
Ø The viscosity of the pseudo-components 1 and 2 should be close to the ones given above
Žh1 s 0.0472 mPa s and h 2 s 0.63 mPa s..
Ø The viscosity of all pseudo-components must follow a given order: h1 - h 2 - h 3 - h4 .
Ø The effect of the binary interaction parameters must be small.
Ø The ternary interaction parameters must play a minor role. Only the interaction between the gas Ž 1.
and the heavy ends Ž3 and 4. is considered.
Ø The quaternary interaction parameter is expected to be negligible: l1234s0 .
Various trials have been done regarding the influence of the parameters on the quality of the
predictions. Our final choice is summarized in Table 6. Six coefficients l are equal to zero and five l
are different from zero. The values of h1 and h 2 are almost identical to those estimated before, h 3 is
greater and h4 is extremely high. These values should not be considered as «universal» values
corresponding to the viscosity of the respective fractions of all petroleum fluids. They are parameters
to be used with the model, when computing viscosities of petroleum mixtures containing asphaltenes.
In particular, h4 cannot be taken as the real viscosity of asphaltenes but only as the parameter that
Table 5
Results of the regression of the modified mixing rule of Grunberg and Nissan on 18 data points originating from Werner et al. w1x and Cohen et al. w2x
Crude name GAZ C6–C20 C 20q Asphaltenes Dynamic Dynamic Absolute
wwt.%x wwt.%x Saturates wwt.%x viscosity viscosity deviation
qAromatics measured at calculated at w%x
qResins 35 MPa and 35 MPa and
wwt.%x 1008C 1008C by the
wmPa sx modified mixing

A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341

rule of Grunberg
and Nissan
wmPa sx
Synth. crude no. 2) 42.5 51.9 5.5 0.1 0.29 0.24 19.0
Synth. crude no. 1d) 41.9 51.8 6.2 0.1 0.30 0.24 19.4
Synth. crude no. 9) 31.5 50.4 18.0 0.1 0.34 0.39 16.0
Synth. crude no. 1a) 33.0 51.4 15.4 0.2 0.36 0.36 0.4
Synth. crude no. 1b) 32.4 51.8 15.5 0.3 0.37 0.36 2.0
Synth. crude no. 3)) 29.3 51.4 19.0 0.3 0.39 0.42 8.1
Synth. crude no. 1c) 42.9 41.4 15.5 0.2 0.43 0.28 35.2
Real crude AX 1 0.0 33.5 66.4 0.1 1.05 2.29 118
Synth. crude no. 5 13.2 49.0 32.1 5.7 1.08 1.28 18.4
Real crude AX 2 0.0 50.4 46.2 3.4 2.33 2.79 19.6
Synth. crude no. 13 2.5 51.0 38.3 8.2 3.66 3.96 8.2
Synth. crude no. 14 3.2 51.7 35.1 10.0 4.45 4.07 8.6
Synth. crude no. 7 17.0 26.1 46.6 10.3 7.05 5.41 23.3
Real crude AX 3 0.0 35.9 59.9 4.2 8.19 6.06 26.0
Synth. crude no. 16c 3.3 34.8 47.7 14.2 28.8 30.1 4.6
Synth. crude no. 16d 2.4 26.2 57.4 14.0 61.2 82.2 34.3
Athabasca vacuum residue 0.0 0.0 91.6 8.4 233a 202 13.11
Real Boscan crude 0.0 18.0 69.0 13.0 311a 218 30.1
Mean deviation w%x 22.5
a
Viscosities had been initially measured by Cohen et al. w2x at 0.1 MPa Žand 1008C.. We extrapolated these data points to 35 MPa Žand 1008C. using the
modified model of Kanti et al.

331
332 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341

Table 6
Parameters obtained as a result of the fitting with Eq. Ž8. of the experimental dataset of Table 3
h1 s 0.049 mPa s h 2 s 0.646 mPa s h 3 s 4.68 mPa s h4 s8.589 mPa s
l12 s 0 l13 s 0 l14 sy43.3 l23 s 0.355
l24 s 26.25 l34 s 33.21
l123 s 0 l124 s 0 l134 sy16.64 l234 s 0
l1234 s 0

represents the influence of asphaltenes in our model. As shown in Table 3, the mean deviation after
fitting is 22.5%.

4. Proposed W3BH model

Using the above modifications to the model of Kanti et al. w1x and the mixing rule of Grunberg and
Nissan w2x, we propose the following procedure for predicting the viscosity of any petroleum fluid at
any pressure or temperature ŽW3BH model..
Ž1. The composition of the fluid is first grouped into four fractions. All gases are grouped into a
first fraction; all remaining C20- components into a second fraction; the heavy C 20q end is split
between a third fraction, which contains all the saturates, aromatics and resins Ž SAR. and the fourth
fraction made of asphaltenes.
Ž2. Eq. Ž8. with the parameters proposed in Table 6 is used for calculating the fluid viscosity at 35
MPa and 1008C.
Ž3. The modified Kanti model is used a first time in order to determine, from the given viscosity at
35 MPa and 1008C, the value of h Ž P0 , T0 . at 0.1 MPa and 258C. This step corresponds to the inverse
function shown on Fig. 5. Since the viscosity at 35 MPa and 1008C is a continuous and monotone
function of the parameter h Ž P0 , T0 ., the inverse value can be obtained without ambiguity. We stress
again the fact that the numerical value h Ž P0 , T0 . that is thereby obtained is merely a calculation
intermediate. It has no physical meaning when the fluid contains gases.
Ž4. Finally, using the same modified Kanti model, the viscosity at the required pressure and
temperature is calculated.
This procedure needed for the computation of an oil viscosity starting from compositional
information is sketched in Fig. 6. Note that if the composition of the fluid is not known, but one
viscosity datum is available at a given pressure and temperature, it is possible to skip the first and
second steps, and use only the modified Kanti model in order to compute the viscosity at any pressure
and temperature.

5. Validation of the W3BH model

The W3BH model has been validated on 76 so far unpublished experimental data points coming
from four PVT investigations on real crude oils Ž Behar, personal communication, 1980, 1983, 1984;
Tindy, personal communication, 1962. . The first crude stems from a Central American reservoir and
 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341 333

Fig. 6. Sketch of the procedure needed for using the proposed W3BH model.

is called ‘AW 1’. The origin of its kerogen is marine Ž type II. . The second oil, called ‘AW 2’, is
produced in South West France. Its initial kerogen is also derived from marine organic matter. The
fluid ‘AW 3’ is a South American Crude that stems equally from an organic matter of type II. The
crude ‘AW 4’ is produced in France but from a different reservoir than crude ‘AW 2’. These crude
compositions and viscosities are given by Tables 7–10.
The compositional variations of these fluids are not sufficiently large in order to use them for the
development of a compositional model. However, they constitute a good data base for an independent
validation because half of them contain gas and 45% of them contain at least 11 wt.% of asphaltenes.
Additionally, these data cover a large range of viscosity Ž 1.9–23,298 mPa s. , pressure Ž 0.1–29 MPa.
and temperature Ž31–84.58C..
To our knowledge, published viscosities of crude oils w26,27x cannot be used for increasing this
data base, the detailed composition Žin particular asphaltenes content. not being available.
The results of the W3BH model have been compared in Table 7 through 10 with the results of the
corresponding states model of Pedersen and Fredenslund w4x, using their correlation for estimating
 334
Table 7
Crude AW 1: compositions, pressures, temperatures, measured dynamic viscosities, viscosities calculated by the corresponding states model w3x plus their
absolute deviations and viscosities calculated by the W3BH model plus their absolute deviations
No. CO 2 C 6 –C 20 C 20q Asphaltenes S Pressure Temp. Measured Dynamic Absolute Dynamic Absolute
wwt.%x wwt.%x Saturates, wwt.%x wwt.%x wMPax w8Cx dynamic viscosity deviation viscosity deviation
Aromatics, viscosity calculated w%x calculated w%x
Resins wmPaPsx by the by the

A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341

wwt.%x corresponding W3BH
states model model
wmPaPsx wmPaPsx
1 0.0 25.5 62.5 12.0 100 0.1 50 1650 16.1 99.0 1343 18.6
2 0.0 32.0 57.0 11.0 100 6.63 35 1123 26 97.7 1236 10.0
3 0.0 32.0 57.0 11.0 100 9.18 35 1185 27.3 97.7 1372 15.8
4 0.0 32.0 57.0 11.0 100 11.73 35 1324 28.6 97.8 1508 13.9
5 0.0 32.0 57.0 11.0 100 14.28 35 1413 29.9 97.9 1644 16.3
6 0.0 32.0 57.0 11.0 100 0.1 50 312 13.4 95.7 315 0.9
7 0.0 32.0 57.0 11.0 100 6.63 50 375 15.3 95.9 416 10.9
8 0.0 32.0 57.0 11.0 100 9.18 50 401 16.1 96.0 456 13.6
9 0.0 32.0 57.0 11.0 100 11.73 50 422 16.8 96.0 495 17.3
10 0.0 32.0 57.0 11.0 100 14.28 50 449 17.6 96.1 535 19.1
11 0.0 32.0 57.0 11.0 100 6.63 65 163 9.83 94.0 155 4.8
12 0.0 32.0 57.0 11.0 100 9.18 65 172 10.3 94.0 168 2.3
13 0.0 32.0 57.0 11.0 100 11.73 65 182 10.8 94.1 181 0.6
14 0.0 32.0 57.0 11.0 100 14.28 65 193 11.3 94.1 194 0.4
15 11.9 28.2 50.2 9.7 100 6.63 35 56.9 2.90 94.9 64.9 14.1
16 15.4 27.1 48.2 9.3 100 9.18 35 49.3 2.18 95.6 33.4 32.2
17 17.1 26.5 47.3 9.1 100 11.73 35 43.6 1.97 95.5 25.4 41.7
18 17.7 26.3 46.9 9.1 100 14.28 35 39.8 1.95 95.1 24.2 39.1
19 9.6 28.9 51.6 9.9 100 6.63 50 36.7 2.86 92.2 50.9 38.7
20 13.8 27.6 49.1 9.5 100 9.18 50 29.2 2.02 93.1 24.9 14.8
21 16.3 26.8 47.7 9.2 100 11.73 50 25.4 1.74 93.1 16.8 33.8
22 17.4 26.4 47.1 9.1 100 14.28 50 23.5 1.67 92.9 14.8 37.1
23 8.2 29.4 52.3 10.1 100 6.63 65 19.6 2.63 86.6 33.2 69.4
24 11.5 28.3 50.5 9.7 100 9.18 65 14.9 2.63 82.3 20.2 35.6
25 14.5 27.4 48.7 9.4 100 11.73 65 11.2 1.66 85.2 13.2 17.9
26 16.7 26.7 47.4 9.2 100 14.28 65 9.3 1.49 84.0 10.0 7.1
27 0.0 24.8 62.2 13.0 100 6.63 35 16,598 34.7 99.8 16,074 3.2
28 0.0 24.8 62.2 13.0 100 9.18 35 19,590 36.7 99.8 18,479 5.7
29 0.0 24.8 62.2 13.0 100 11.73 35 21,134 38.7 99.8 20,885 1.2
30 0.0 24.8 62.2 13.0 100 14.28 35 23,298 40.7 99.8 23,291 3.1
31 0.0 24.8 62.2 13.0 100 0.1 50 1975 16.9 99.1 2425 22.8
32 0.0 24.8 62.2 13.0 100 6.63 50 6523 19.7 99.7 3578 45.2
33 0.0 24.8 62.2 13.0 100 9.18 50 7021 20.8 99.7 4028 42.6
34 0.0 24.8 62.2 13.0 100 11.73 50 7738 22 99.7 4478 42.1
35 0.0 24.8 62.2 13.0 100 14.28 50 8358 23.1 99.7 4928 41.0
36 0.0 24.8 62.2 13.0 100 6.63 65 948 12.3 98.7 922 2.7
37 0.0 24.8 62.2 13.0 100 9.18 65 1012 13 98.7 1020 0.8
38 0.0 24.8 62.2 13.0 100 11.73 65 1065 13.7 98.7 1118 4.9

A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341

39 0.0 24.8 62.2 13.0 100 14.28 65 1748 14.4 99.2 1215 30.5
40 9.9 22.3 56.1 11.7 100 6.63 35 283 3.93 98.6 526 85.9
41 12.4 21.7 54.5 11.4 100 9.18 35 238 3.06 98.7 282 18.6
42 15.9 20.9 52.3 10.9 100 11.73 35 199 2.30 98.8 117 41.4
43 16.9 20.6 51.7 10.8 100 14.28 35 168 2.19 98.7 98.1 41.6
44 8.0 22.8 57.2 12.0 100 6.63 50 194 3.77 98.1 333 71.8
45 11.1 22.0 55.3 11.6 100 9.18 50 161 2.75 98.3 164 2.1
46 14.3 21.3 53.3 11.1 100 11.73 50 130 2.14 98.4 79.1 39.1
47 15.2 21.1 52.7 11.0 100 14.28 50 101 2.06 98.0 68.6 32.0
48 6.7 23.2 58.0 12.1 100 6.63 65 125 3.42 97.3 168 34.1
49 9.2 22.5 56.5 11.8 100 9.18 65 94 2.67 97.2 105 12.0
50 12.1 21.8 54.7 11.4 100 11.73 65 68.5 2.12 96.9 60.1 12.2
51 13.3 21.5 53.9 11.3 100 14.28 65 52.7 1.99 96.2 50.6 4.0

335
 336
Table 8
Crude AW 2: compositions, pressures, temperatures, measured dynamic viscosities, viscosities calculated by the corresponding states model w3x plus their
absolute deviations and viscosities calculated by the W3BH model plus their absolute deviations
No. CO 2 C 6 –C 20 C 20q Asphaltenes S Pressure Temp. Measured Dynamic Absolute Dynamic Absolute
wwt.%x wwt.%x Saturates, wwt.%x wwt.%x wMPax w8Cx dynamic viscosity deviation viscosity deviation

A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341

Aromatics, viscosity calculated w%x calculated w%x
Resins wmPaPsx by the by the
wwt.%x correspon- W3BH
ding states model
model wmPaPsx
wmPaPsx
52 6.6 49.4 32.9 11.1 100 16.5 84.5 4.5 2.12 52.9 3.91 13.1
53 6.6 49.4 32.9 11.1 100 20 84.5 4.7 2.21 53.0 4.12 12.4
54 6.6 49.4 32.9 11.1 100 20.6 84.5 4.7 2.23 52.6 4.15 11.6
55 6.6 49.4 32.9 11.1 100 24.3 84.5 4.85 2.33 52.0 4.37 9.8
56 6.6 49.4 32.9 11.1 100 29 84.5 5.05 2.46 51.3 4.65 7.9
57 10.8 47.2 31.4 10.6 100 20 84.5 2.6 1.61 38.1 2.63 1.2
58 16.4 44.2 29.5 9.9 100 24.3 84.5 2.1 1.23 41.4 1.60 23.9
59 23.0 40.7 27.1 9.2 100 29 84.5 1.9 0.920 51.6 0.93 51.2
Table 9
Crude AW 3: compositions, pressures, temperatures, measured dynamic viscosities, viscosities calculated by the corresponding states model w3x plus their
absolute deviations and viscosities calculated by the W3BH model plus their absolute deviations

A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341

No. CO 2 C 6 –C 20 C 20q Asphaltenes S Pressure Temp. Measured Dynamic Absolute Dynamic Absolute
wwt.%x wwt.%x Saturates, wwt.%x wwt.%x wMPax w8Cx dynamic viscosity deviation viscosity deviation
Aromatics, viscosity calculated w%x calculated w%x
Resins wmPaPsx by the by the
wwt.%x correspon- W3BH
ding states model
model wmPaPsx
wmPaPsx
60 0.0 14.2 74.6 11.2 100 3.5 80.6 635 7.92 98.8 436 31.3
61 0.0 14.2 74.6 11.2 100 7 80.6 703 8.72 98.8 502 28.5
62 0.0 14.2 74.6 11.2 100 10.5 80.6 790 9.53 98.8 569 28.0
63 0.0 14.2 74.6 11.2 100 14 80.6 874 10.4 98.8 635 27.4
64 0.0 14.2 74.6 11.2 100 17.5 80.6 965 11.2 98.8 701 27.3
65 0.0 14.2 74.6 11.2 100 21 80.6 1084 12 98.9 767 29.2
66 3.3 13.7 72.1 10.9 100 3.5 80.6 260 4.03 98.4 219 15.7
67 6.8 13.2 69.5 10.5 100 7 80.6 113 2.67 97.6 121 7.0
68 10.2 12.7 67.0 10.1 100 10.5 80.6 78 2.03 97.4 69.0 11.5
69 12.9 12.3 65.0 9.8 100 14 80.6 54 1.74 96.8 45.8 15.1
70 14.7 12.1 63.6 9.6 100 17.5 80.6 44 1.62 96.3 35.7 18.9
71 16.1 11.9 62.5 9.5 100 21 80.6 40 1.56 96.1 30.4 24.1

337
 338
A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341
Table 10
Crude AW 4: compositions, pressures, temperatures, measured dynamic viscosities, viscosities calculated by the corresponding states model w3x plus their
absolute deviations and viscosities calculated by the W3BH model plus their absolute deviations
No. CO 2 C 6 –C 20 C 20q Asphaltenes S Pressure Temp. Measured Dynamic Absolute Dynamic Absolute
wwt.%x wwt.%x Saturates, wwt.%x wwt.%x wMPax w8Cx dynamic viscosity deviation viscosity deviation
Aromatics, viscosity calculated w%x calculated w%x
Resins wmPaPsx by the by the
wwt.%x correspond- W3BH
ing states model
model wmPaPsx
wmPaPsx
72 0.0 8.8 91.1 0.1 100 0.1 31 36.7 20.8 43.3 17.8 51.6
73 0.0 8.8 91.1 0.1 100 1.49 31 36.6 21.8 40.4 18.5 49.5
74 0.0 8.8 91.1 0.1 100 3.58 31 37.5 23.3 37.9 19.5 47.9
75 0.0 8.8 91.1 0.1 100 7.17 31 40.5 26 35.8 21.3 47.3
76 0.0 8.8 91.1 0.1 100 10.76 31 43 28.7 33.3 23.2 46.1
 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341 339

Fig. 7. Validation of the W3BH model: Comparison ŽTable 7Table 8Table 9Table 10. between measured viscosities,
viscosities calculated by the corresponding states model, and viscosities calculated by the W3BH model on 76 data points
from E. Behar Žpersonal communication, 1980, 1983, 1984. and Tindy Žpersonal communication, 1962.. The straight,
diagonal line indicates where the calculated and the measured viscosities are identical.

parameters. We obtained an overall mean deviation on the 76 data points of 88% for the correspond-
ing states model and of 24% for the W3BH model.
Fig. 7 illustrates the calculated viscosities compared to the 76 measured ones. It shows on the one
hand that the corresponding states model underestimates viscosity systematically. Its predictions are
better for light liquids with low viscosities than for heavy crudes whose viscosities are underestimated
by up to three orders of magnitudes. On the other hand, the W3BH model estimates well viscosities of
petroleum fluids in the whole range from 1.9 through 23,298 mPa s. No systematic deviation is
observed: viscosities of light crudes are predicted as well as those of heavy ones.

6. Conclusion

A new viscosity model, called W3BH, which gives dynamic viscosity as a function of composition,
pressure and temperature, is proposed. It is intended to be applied to petroleum liquids with high gas
concentrations as well as on heavy crude oils with high asphaltenes content for a large range of
pressure and temperature. The W3BH model is based on the combination of the modified mixing rule
of Grunberg and Nissan and the modified model of Kanti et al. Each of these can be used
independently.
The modified Grunberg and Nissan mixing rule proposes an original solution to the prediction of
the viscosity of complex petroleum fluids. Four fractions are identified and considered as pseudo-
components. Component and interaction parameters for these fractions were determined at 35 MPa
and 1008C.
The modifications that were brought to the model of Kanti increase the domain of applicability of
this powerful model to very viscous fluids Žviscosities up to 23,300 mPa s at 258C and 0.1 MPa. . It
340 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341

thus allows to determine the viscosity of a petroleum fluid at any pressure or temperature, when one
viscosity value is known.
The W3BH model can therefore be applied, either starting from compositional information, or from
the knowledge of the viscosity of the fluid at a given set of pressure and temperature.
This model has been validated on 76 data points from various crudes. The obtained mean deviation
is 24% over a viscosity range from 2 to 23,298 mPa s.
However, regression and validation have been carried out in a well defined experimental field. The
asphaltenes considered in this work originate from organic matter of type II, which is the most
common type of organic matter in sedimentary basins. Due to the lack of literature viscosity data, we
have not been able to prove with certainty that the W3BH model applies with the same accuracy on
crudes deriving from organic matter of type I or III. Nevertheless, a lot of data points used for the
regression of the Grunberg and Nissan mixing rule parameters stem from crudes for which we do not
know the original kerogen type. It is therefore very possible that the model applies equally well to
crudes deriving from other types of organic matter than type II.
The targeted application field in pressure and temperature is limited to 70 MPa and 1508C.
However, the validation of the W3BH model has been carried out in a pressure domain from 0.1 to 29
MPa and a temperature domain from 31 to 84.58C. It seems to be reasonable that extrapolations to
pressures higher than 29 MPa Žhighest validation pressure. are possible when the temperature is above
84.58C. At low temperatures and high pressures Ž above 70 MPa. , one has to be cautious for a possible
nonlinear pressure effect on viscosity.

7. List of symbols

D, E Parameters that determine the variation of viscosity as a function of pressure Ž in the

model of Kanti et al. w1x.. They depend on z and on the temperature T.
P Actual pressure ŽMPa.
P0 Reference pressure Žs 0.1 MPa.
T Actual temperature ŽK.
T0 Reference temperature Žs 298.15 K.
w Mass fraction
x Molar fraction
z s ln h Ž P0 , T .
z0 s ln h Ž P0 , T0 .
a Parameter that determines the variation of viscosity as a function of temperature Ž in the
model of Kanti et al. w1x.. It depends on z 0 .
h Dynamic viscosity Ž mPa s.
li j Binary interaction coefficient between fraction i and fraction j
l i jk Ternary interaction coefficient
l i jk l Quaternary interaction coefficient
Index
m Mixture
i Fraction
 A. Werner et al.r Fluid Phase Equilibria 147 (1998) 319–341 341

Acknowledgements

The authors acknowledge the technical support of K. Gaillard, J.-P. Courcy and G. Moracchini
during the experimental part of this work. The financial support was provided by IFP.

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