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Correlation
G. Galliro, C. Boned, and A. Baylaucq, University of Pau, and F. Montel, SPE, Total
Summary
Acid gases containing hydrogen sulfide (H2S) are often encountered in the petroleum industry. However, reliable experiments on
their thermophysical properties in reservoir conditions, on viscosity in particular, are scarce. From a modeling point of view, H2S
and carbon dioxide (CO2) are polar compounds and as such are
often considered rather difficult to model accurately.
In this work, we propose a correlation with a strong physical
background based on a corresponding-states (CS) approach to predict the viscosity from the temperature and the density of a large
variety of systems for all stable thermodynamic states (gas, liquid,
and supercritical). In particular, this correlation is applicable to predict the viscosity of sour/acid-gas mixtures, whatever the thermodynamic conditions. This approach is based on the Lennard-Jones (LJ)
fluid model, which has been studied extensively thanks to moleculardynamics (MD) simulations over a wide range of thermodynamic
conditions. This fluid model can be extended to deal with polar
molecules such as CO2 or H2S without a loss of accuracy.
First, we demonstrate that the proposed physically based correlation is able to provide an excellent estimation of the viscosity
[with average absolute deviations (AADs) below 5%] of pure
compounds, including normal-alkanes, CO2, or even H2S, whatever
the thermodynamic conditions (gas, liquid, or supercritical).
Then, using a one-fluid approximation and a set of combining
rules, the correlation is applied to various fluid mixtures in a fully
predictive way (i.e., without any additional fitted parameters).
Using this scheme, the deviations between predictions and measurements are as low as those on pure fluids using temperature and
density as inputs. The viscosity of natural- and acid-gas mixtures
at reservoir conditions is shown to be very well predicted by the
proposed scheme. In addition, it is shown that this correlation can
also be applied to predict reasonably the viscosity of asymmetric
high-pressure mixtures, even in the liquid phase.
This physically based approach is easy to include in any simulation software as long as, apart from temperature and density,
the only inputsthe molecular parameters of each speciescan
be estimated from the critical temperature and the critical volume
when not known.
Introduction
Natural gases containing CO2 or H2S, the so-called acid/sour gases,
are often encountered in the petroleum industry (Ungerer et al.
2005). Nevertheless, reliable experiments on their thermophysical
properties are scarce. In the case of H2S, practically no data exist
because of its high toxicity. This lack of information is even more
pronounced concerning transport properties, such as viscosity
(Galliro and Boned 2008; Liley et al. 1988; Schmidt et al. 2008),
at typical petroleum-reservoir conditions (i.e., high pressures and
high temperatures). A predictive, physically based model is highly
required as long as high-pressure viscosity is one of the key physical properties for the design of acid-gases disposal.
Molecular simulation, which can be considered a numerical
experiment on a model fluid, is one of the valuable alternatives to
experiments for gathering physical information on such systems of
682
k BTc
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (1)
1.2593
and
v
= 0.305 c
NA
1/ 3
, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (2)
and
ijpol = ij F 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (3)
and
ijpol =
ij
F1 6
, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (4)
with
3 + 3
ij = ii ii 3 jj jj . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (10)
2 ij
T* =
k BT * x3
, =
, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (11)
x
Mx
i2 2j
F = 1+
, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (5)
12 k BT ij ij6
where i is the dipole moment of Molecule i that is provided for
some compounds in Poling et al. (2000). When a dipole moment
is known in Debyes, it should be multiplied by 3.1622761025
to be used in Eq. 5.
Mixtures. The scheme proposed in this work is based on the
CS law (i.e., it is assumed that, with adequate scaling that we will
discuss in the next subsection, all fluids follow the same trend in
the scaled/reduced space). The LJ fluid model applied on a pure
fluid respects two-parameter CS behavior exactly. In LJ mixtures,
a single set of molecular parameters representing the mixture
should be defined to use a CS approach. To do so, a simple van
der Waals one-fluid approximation (vdW1) has been used in this
work. The vdW1 is known to provide generally reasonable results
(Vidal 2003; Galliro et al. 2005a) even if, in some asymmetric
mixtures, it may exhibit deficiencies (Galliro et al. 2005b, 2006b).
In an N-components LJ mixture, the vdW1 is
N
M x = xi Mi , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (6)
i =1
x3 = xi x j ij3 , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (7)
i =1 j =1
* =
* ( T * , * ) = 0* ( T * ) + * ( T * , * ) , . . . . . . . . . . . . . . . . . . (13)
where 0* represent the low-density viscosity (function of T * only)
and * is the residual viscosity (function of T * and *). At the
critical point, the viscosity diverges (Vesovic et al. 1990). Nevertheless, in this work, we have not taken into account this contribution because its effect is limited to a very small area close to the
critical point (Vesovic et al. 1990).
Low-Density Contribution. The first-order approximation of
the Chapman-Enskog approach (Poling et al. 2000) applied to
the LJ fluid provides an excellent estimation of the low-density
reduced viscosity. This relation is
and
0* =
N
x2
, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (12)
Mx x
5 Ac
16 v
T*
, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (14)
( )
v = a1 T *
a2
1/ 3
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (9)
ai
1.16145
0.14874
0.52487
bi
0.062692
4.095577
8.743269 10
) (
) (Tb ) (e
* = b1 e b2 1 + b3 e b4 1 +
*
5
* 2
b6 *
1 , . . . . .(16)
* =
4.75
*
) (
T*
+ b1 e b2 1 + b4 e b5 1 +
*
b5 b6*
e 1 , . . . . . . . . (17)
T *2
0.7732
6
11.12492
2.16178
2.542477 10
2.43787
6
14.863984
(10
10
m)
(Jmol )
TminTmax (K)
pminpmax (MPa)
AAD (%)
max
(%)
Database
C1
3.6325
1258.1
200500
0.1100
1.3
3.6
C2
4.2093
2015.8
200500
0.160
3.4
8.6
C3
4.6717
2442
200450
0.130
6.5
10.7
C4
5.0741
2806.7
250450
0.130
5.2
8.7
C5
5.4009
3101
303383
0.1100
5.5
10.4
C6
5.7051
3351.2
303348
0.1250
4.9
9.9
9.4
C7
5.9916
3566.4
293343
0.1100
4.5
C10
6.7285
4078.1
293373
0.1140
3.3
9.6
C16
7.9044
4773.3
298348
0.1150
5.4
9.9
(10
10
m)
(Jmol )
TminTmax (K)
pminpmax (MPa)
AAD (%)
max
(%)
Database
H2S +dipole
3.688
2320
200500
0.16
2.9
11.9
H2 S
3.667
2355
200500
0.16
4.5
18.7
CO2
3.6641
2007.9
250500
0.1100
4.3
8.7
684
N2
3.5734
833.1
200500
0.1100
1.3
2.5
O2
3.3269
1020.6
200500
0.180
2.1
4.0
C6 H6
5.1202
3710.7
283393
0.1200
4.7
11.5
C7 H8
5.3897
3906.8
293373
0.1140
2.6
6.5
15
Methane
Carbon dioxide
Hydrogen sulfide
100*(1-corr/exp)
10
5
0
5
10
15
0
200
400
600
800
1000 1200
Density (kgm )
Fig. 1Deviations provided by the proposed correlation for the
major compounds appearing in acid gas.
100*(1-corr/exp)
100*(1-corr/exp)
Nabizadeh and
Mayinger (1999)
0
0
(a)
20
40
60
50
100
Density (kgm )
150
200
250
300
350
Density (kgm3 )
(b)
Fig. 2Deviations provided by the proposed scheme for different natural gases.
10
20
10
0
5
10
15
20
25
xC1=0.25
xC1=0.37
xC1=0.5
xC1=0.64
xC1=0.95
Density (kgm )
100*(1-corr/exp)
100*(1-corr/exp)
0
10
xC0 =0.15
20
xC0 =0.3
2
xC0 =0.5
30
xC0 =0.85
2
40
550
(b)
600
650
700
750
800
850
900
Density (kgm3 )
Fig. 3Deviations provided by the proposed scheme for (a) methane/toluene mixture and (b) CO2/decane mixture.
686
Mi
N
NA
p
T
v
xi
i
v
Acknowledgments
We gratefully acknowledge Total S.A. for allowing us to publish
this work.
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