3.5 Properties of Natural Gases at High Pressure: 3. Fluid Phase Equilibria and Fluid Properties

162 3.
Fluid Phase Equilibria and Fluid Properties

miscibility of water and H
2
S. From the simulation results, it is expected that the ternary sys-
tem is monophasic for methanol concentrations of over 25%, whatever the relative propor-
tions of water and H
2
S. This kind of information is particularly useful for the preliminary
design of methanol-based gas treatment processes.
3.5 PROPERTIES OF NATURAL GASES AT HIGH PRESSURE
3.5.1 Possible Contribution of Molecular Simulation to Industrial Needs
The composition of the natural gases of industrial interest is generally dominated by methane
(60-95%) which may be accompanied by numerous other hydrocarbons and variable amounts
of non-hydrocarbon gases (CO
2
, N
2
, etc.). The heavier hydrocarbons follow a distribution
that decreases more or less exponentially with carbon number [Pedersen et al., 1989;
Sportisse et al., 1997] and the details of this distribution strongly influence the thermody-
namic properties of the gas. When the distribution contains significant amounts of hydrocar-
bons with more than 7 carbon atoms, the gas often exhibits a retrograde dew point, i.e. phase
separation when its pressure is decreased at constant reservoir temperature. When it displays
this behaviour, it is referred to as a condensate gas.
In a general way, the production of a condensate gas entails problems because liquid phase
condensation in the reservoir has to be avoided for economic reasons (the valuable liquid
hydrocarbons are recovered less efficiently) and for fluid flow reasons (the condensed liquid
Figure 3.69 Ternary phase diagram of the methanol-water-H
2
S system
obtained by simulation in the Gibbs ensemble at 343 K and 7 MPa.
H
2
S
MeOH H
2
O
0
0
0 20 40 60 80 100
20
20
40
40 60
60
80
80
100
100
Liquid
Liq 1-Liq 2
3750_ Page 162 Mercredi, 15. juin 2005 1:10 13 > Apogee FrameMaker Noir
3. Fluid Phase Equilibria and Fluid Properties 163
phase hinders gas flow in the vicinity of the well). Therefore, it is always important that phase
behaviour and volumetric behaviour are well characterised in condensate gas fields. The pre-
diction of this behaviour is difficult because the exact composition across the entire range is
seldom known, the analysis being generally limited to 10 carbon atoms and below (and often
7 carbon atoms and below). Moreover, the presence of this unknown heavy fraction is not the
only difficulty because the lack of thermodynamic data about many hydrocarbon families
would also prevent the application of engineering equations of state even if a full analysis
were available. Also, equations of state require fine tuning of binary interaction coefficients
between methane and heavy hydrocarbons to represent their phase equilibrium, whereas the
necessary experimental information is unavailable for several families of heavy hydrocar-
bons. The prediction of condensate gas behaviour with equations of state in the industry is
generally based on the use of pseudo-components (i.e. hydrocarbons of undefined molecular
structure) whose thermodynamic properties are regressed to match the phase behaviour of the
condensate gas under consideration. It is thus necessary to take large samples of the gas and
perform systematic volumetric and phase behaviour measurements before field development
can be planned (or abandoned).
Apart from phase behaviour, volumetric properties are very important for gas production,
as illustrated by the systematic use of the compressibility factor (Z = PV/RT) variations ver-
sus pressure to evaluate reserves. More recently, the discovery of deep, high pressure gas
wells has also triggered a need for a deeper understanding of thermal properties. In these
fields, it has been observed that the gas tends to heat up in the production tubing as its pressure
drops. This behaviour may be attributed to the Joule-Thomson effect (Fig. 3.70). In a very
first approximation, the expansion of the gas in the production tubing may be assimilated to
isenthalpic expansion when the production rate is high enough so that any heat exchange with
the surroundings can be ignored. In this case, the thermal regime is governed by the Joule-
Thomson coefficient which describes temperature changes in the course of isenthalpic expan-
sion. Depending on temperature and pressure conditions, the Joule-Thomson effect may be
positive or negative. In most gas reservoirs, the pressure is below 50 MPa and the gas tends
to cool down as a result of the Joule-Thomson effect. Then the thermal regime is not a major
industrial concern. In high pressure gas reservoirs, the Joule-Thomson effect tends to heat up
the gas, and this makes additional demands on production equipment (tubes, valves, etc.). For
this reason, the effect needs to be characterised although this is difficult using experimental
methods: measuring the Joule-Thomson coefficient of gases in the laboratory requires both
large amounts of sample and very good thermal insulation, both conditions which are difficult
to fulfill at pressures which can reach 110 MPa. Predictions with classical equations of state
are possible in principle [Kortekaas et al., 1997] but they have not been validated by system-
atic comparisons with high pressure Joule-Thomson coefficient measurements, either for
pure compounds or mixtures. In contrast, this type of validation was presented in Section 3.2,
supporting the relevance of Monte Carlo simulation methods when it comes to predicting
Joule-Thomson coefficients at high pressures.
The long-term challenge for molecular simulation in the natural gas industry is to be able
to provide reasonably reliable predictions of the thermodynamic behaviour of a gas as long
as a complete analysis of the mixture is available. The need for a complete analysis may seem
unrealistic but much more information can be extracted from a chromatographic analysis than
164 3. Fluid Phase Equilibria and Fluid Properties
is routinely extracted today, e.g. standard analytical techniques are available for molecules
containing up to 20 carbon atoms [Durand et al., 1989], and high temperature chromatography
extends the analysis up to the highest molecular weights present in condensate gases, i.e. 35
carbon atoms. Mass spectrometry is also a technique that can be used to complement chroma-
tography to provide a fuller evaluation of a hydrocarbon family. The advantage of coupling
full analysis with molecular simulation is that a smaller amount of gas sample is needed, allow-
ing a sooner prediction for new gas discoveries. The costly experiments conducted at reservoir
pressure could be then focused on those natural gases that are most likely to be produced.
How far is molecular simulation from meeting this challenge? The answer differs depend-
ing on whether it is phase equilibria or monophasic properties which are under consideration.
Monophasic properties are investigated by using the NPT or NVT statistical ensembles, and
it is then possible to introduce a detailed account of the molecular composition of the gas, as
it will be discussed in this section. Concerning phase equilibria, the problem is more complex
because dew points cannot be determined directly from a Gibbs ensemble simulation, for the
same reason as discussed in the context of bubble points in Section 2.3.7. Indeed, a dew point
calculation requires that the vapour composition be imposed, while it is the global composi-
tion that is imposed in the Gibbs ensemble. Very encouraging dew point calculations have
been reported in the literature [Escobedo, 1998; Escobedo, 1999] but, in these investigations,
a full analysis of the natural gases under consideration was not available. Extension of these
techniques to well-analysed gases is still open to further research.
As a consequence, only monophasic properties will be considered in the applications
described in this section, including volumetric properties and the Joule-Thomson coefficient.
Figure 3.70 Influence of the Joule-Thomson effect in the thermal
regime of deep gas wells.
P
P
T
H
P
T
JT
=
JT
> 0
JT
< 0
Cooling
Heating
T up to 200C
P up to 120 MPa
depth up to 6 km
Cooling
or heating?
In the preliminary study of Neubauer et al. [1999b], it was shown on the basis of natural
gas examples taken from the literature that the volumetric properties of natural gases can
be simulated using Monte Carlo methods. The purpose of this section is to go a step further
in this direction, based on the results of more recent research [Lagache et al., 2004a]. We will
look at, not only a classical gas example from the literature a San Joaquin gas characterised
by Sage et al. [1947], but also a condensate gas from a very deep North Sea reservoir charac-
terised by Arnaud [1995]. This second fluid will be named HP-HT fluid in reference to the
very high pressures (up to 110 MPa) and temperatures (up to 190 K) of the gas reservoirs
found in this region [Ungerer et al., 1995 and 1998]. A full analysis of the gas is provided to
allow a representative modelling of the HP-HT gas, so that a large set of predictions are
obtained about volumetric properties, its Joule-Thomson coefficient and thermodynamic
derivative properties.
3.5.2 Representation of Natural Gas Composition
in Monte Carlo Simulation
In applying molecular simulation to the property prediction of natural gases, it is obvious that
there is a large advantage in benefiting from the availability of well-tested intermolecular
potentials. The Lennard-Jones potential of Mller et al. [1993] which has been applied with
success in Section 3.2 and the AUA potential of hydrocarbons tested in many instances
(Sections 3.1 and 3.2) provides a firm basis for this purpose. In Figure 3.71, the compressibil-
ity factor predicted for methane at high pressure is shown for two temperatures, confirming
that very good predictions can be obtained. These intermolecular potentials will be used in
this section for natural gases.
It is worth pointing out that such intermolecular potentials can only be used if every com-
ponent of the simulated system has a well-defined molecular structure. It is thus uneasy to
introduce pseudo-components, i.e. components of undefined molecular structure, as it is com-
monly done when modelling the heavy fraction of natural gases with equations of state.
Non-hydrocarbon gases like CO
2
and N
2
are also taken into account when modelling the
simulation of gas. Generally, the intermolecular potentials used for these molecules comprise
electrostatic charges [Harris and Yung, 1995; Delhommelle, 2000], and electrostatic interac-
tions are an important part of the interaction energy. However, the contribution of electrostatic
energy to the whole interaction energy is negligible in this case, because CO
2
and N
2
are mostly
surrounded by non-polar molecules, e.g. the contribution of electrostatic energy to the interac-
tion energy of the HP-HT gas discussed in this section was found to be only 0.02%. In these
circumstances, ignoring the electrostatic energy did not have any significant influence on any
property derived by molecular simulation. This is an interesting example of a more general rule,
i.e. that the important interaction terms for a given molecule depend on the polarity of its envi-
ronment. In this case, it could be used to speed up the simulations of the natural gases shown.
The way to represent the composition of a gas is illustrated by the example of the San
Joaquin gas investigated by Sage et al. [1947]. The composition is given as fractions by car-
bon number up to seven carbon atoms. The distinction between n-alkanes and branched
alkanes is provided for the C
4
and C
5
fractions, but not for C
6
or C
7
as shown in Figure 3.72.
No indication is given about the chemical family of the heavy fraction (C
8
+). For the purpose
of our simulations, the fluid is represented by 1 000 molecules, as indicated in Table 3.13. As
a consequence of the total number of molecules, the molar fractions are reproduced within
0.1%, which is probably less than the experimental uncertainty on the hydrocarbon distribu-
tion. In the absence of specific information, the C
6
and C
7
fractions are represented by n-hex-
ane and n-heptane respectively, although it is suspected that they contain a significant amount
of cyclic alkanes and aromatics. The heavy fraction C
8
+ is also represented by normal
alkanes. In order to match the experimentally determined average molecular weight of the
fluid, the C
8
+ fraction is simulated as 50% n-nonane and 50% n-decane.
When a detailed analysis of the gas is available, the use of well-defined components raises
two problems. First, the number of identified individual components in a natural gas exceeds
200 with recent chromatographic methods, so that it is practically impossible to account for
all the different hydrocarbons in simulation. This problem is illustrated by the composition of
the HP-HT fluid shown in Figure 3.73 [Lagache et al., 2004a]. The detailed composition of
the HP-HT fluid is in fact even more complex than shown in this figure because some frac-
tions like C
8
isoalkanes or C
9
aromatic compounds contain several isomers which are
resolved from one another in the chromatographic analysis. Second, the analysis is not avail-
able at the molecular level for heavy fractions, but it is expressed in fractions by molecular
Figure 3.71 Compressibility factor of methane determined from NPT
simulations at 294.25K (o) and 377.55 K (). The lines represent
experimental observations [Lagache et al., 2001], reproduced by per-
mission of the PCCP Owner Societies.
0 20 40 60 80 100
P/MPa
0.8
1
1.2
1.4
1.6
1.8
2
C
o
m
p
r
e
s
s
i
b
i
l
i
t
y

f
a
c
t
o
r

Z
Figure 3.72 Molar composition of the San Joaquin gas [fluid C of Sage
and Olds, 1947]. Methane is not drawn to scale. Reprinted from
[Lagache et al., 2004], 2004 with permission from Elsevier.
Table 3.13 Composition of the San Joaquin Valley natural gas [fluid C of Sage and Olds, 1947]
and representation by a discrete number of molecules [Lagache et al., 2004a].
Component
Experimental mole
fraction
NPT simulation
Number of molecules Molar fraction
Carbon dioxide 0.0021 2 0.002
Methane 0.8074 807 0.807
Ethane 0.0494 49 0.049
Propane 0.0477 48 0.048
Isobutane 0.0132 13 0.013
n-butane 0.0191 19 0.019
Isopentane 0.0097 10 0.010
n-pentane 0.0092 9 0.009
Hexanes 0.0185 19 nC
6
0.019
Heptanes 0.0056 6 nC
7
0.006
Octane+ 0.0181 9 nC
9
+ 9 nC
10
0.018
Total 1 1 000 1
Average molar mass (g/mol) 24.38 24.47
0.06
0.8074
CO
2
Isoalkanes
Normal alkanes
0.05
0.04
0.03
0.02
0.01
0
CO
2
C
1
C
2
C
3
C
4
Carbon number
C
5
C
6
C
7
C
8
+
M
o
l
a
r

f
r
a
c
t
i
o
n
number and chemical family (for instance C
14
aromatics). The precise nature of the mole-
cules making up the fraction is then unknown. In order to circumvent these problems, it is
proposed to proceed in two steps.
In a first step, the detailed analysis is simplified by division into in a manageable number
of fractions (typically 10 to 20 fractions) keeping paraffins, cyclic alkanes and aromatic com-
pounds in separate fractions when the breakdown is known (note that paraffins refers to n-
alkanes and branched alkanes). The hydrocarbons belonging to a given family (either paraf-
fin, cyclic or aromatic) are divided into fractions grouping together hydrocarbons of similar
carbon numbers (for instance C
11
to C
15
aromatics).
In a second step, a representative component is selected for each fraction. Paraffins are rep-
resented either by n-alkanes or by branched alkanes. Cyclic alkanes lower than 10 carbon
atoms are represented by alkylated cyclohexanes, the most abundant type of hydrocarbons in
this family. Similarly, aromatics lower than 10 carbon atoms are simulated by alkylated ben-
zenes. As condensed polyaromatics are known to be major aromatic components above 10
carbon atoms [Petrov, 1984; Tissot and Welte, 1984], it is more realistic to use molecules like
alkyl-naphthalenes (2 cycles) or alkyphenanthrene (3 cycles) rather than n-alkylbenzenes to
represent heavy aromatic fractions.
Figure 3.73 Molar composition of the HP-HT fluid after Arnaud
[1995] and Lagache et al. [2004a], 2004 with permission from
Elsevier. Methane is not drawn to scale.
8
7
26.89
N
2
, CO
2
Aromatics
Cycloalkanes
Normal + isoalkanes
Saturates + aromatics
Saturates
6
5
4
3
2
1
0
%

W
e
i
g
h
t
Carbon number
N
2
C
O
2
C
1
C
2
C
3
C
4
C
5
C
6
C
7
C
8
C
9
C
1
0
C
1
1
C
1
2
C
1
3
C
1
4
C
1
5
C
1
6
C
1
7
C
1
8
C
1
9
C
2
0
C
2
1
C
2
2
C
2
3
C
2
4
C
2
5
C
2
6
C
2
7
C
2
8
C
2
9
C
3
0
C
3
1
C
3
2
C
3
3
C
3
4
C
3
5
C
3
6
C
3
7
The corresponding procedure is illustrated by Table 3.14, in which 19 fractions have been
used to represent the gas. These fractions comprise not only n-alkanes, but also branched
alkanes, cyclic alkanes and aromatics. A total of 500 molecules is used to define the simu-
lated system. As a consequence, the simulated molar fractions are multiples of 1/500 i.e.
0.2%. The molar fractions are thus represented in an approximate way, especially for the
heavy fractions.
In addition to the simplifications introduced by the discretization of the composition, care
must be taken that the analysis of the gas may contain some errors. In Figure 3.73, it may be
noticed that the distribution exhibits two maxima at 7 and 21 carbon atoms in a globally
decreasing trend. The first of these maxima is likely to be real, since it corresponds to the
appearance of cyclic alkanes and aromatics, which are absent below 6 carbon atoms. On the
opposite, the second maximum is probably an artifact of the analysis, as the molar fractions
for molecules containing more than 20 carbon atoms have been obtained from a more approx-
imate mass balance than the lighter part of the distribution.
Table 3.14 Composition of the HP-HT fluid [Arnaud, 1995; Lagache et al., 2004a] and
representation by a discrete number of molecules.
Lumped fraction
Mole
fraction
(%)
Representative
molecule
Number
of molecules
Simulated
mole fraction (%)
N
2
0.543 N
2
3 0.6
CO
2
2.642 CO
2
13 2.6
C
1
65.568 C
1
328 65.6
C
2
8.882 C
2
44 8.8
C
3
4.602 C
3
23 4.6
n + iC
4
2.792 nC
4
14 2.8
n + iC
5
1.686 nC
5
8 1.6
n + iso C
6
-C
7
1.972 iC
7
10 2.0
n + iso C
8
-C
10
1.839 nC
9
9 1.8
Cyclic alkanes C
5
-C
10
2.120 methyl-cyclohexane 11 2.2
Aroatics C
6
-C
10
1.422 p-xylene 7 1.4
Saturates C
11
-C
14
2.281 nC
12
11 2.2
Aromatics C
11
-C
15
0.805 dimethyl-naphtalene 4 0.8
Saturates C
15
-C
18
1.083 nC
16
6 1.2
Aromatics C
16
-C
20
0.418 dimethyl-phenanthrene 2 0.4
C
19
-C
21
0.495 nC
20
3 0.6
C
22
-C
27
0.673 nC
25
3 0.6
C
28
-C
37
0.178 nC
30
1 0.2
Total C
1
-C
37
100 Total C
1
-C
37
500 100
The pattern for the simulated HP-HT fluid (Fig. 3.74) reveals that the gaseous hydrocar-
bons (C
1
to C
4
) are not dominating the composition as strongly as might be expected from
the distribution of Figure 3.73. The heavier hydrocarbons (C
5
and above) are minor in terms
of the number of moles present, but they are approximately equivalent in terms of mass and
absolute numbers of carbon atoms. This provides a qualitative explanation of why this fluid
displays liquid-like properties at high pressure, as will be seen later.
3.5.3 Volumetric Properties
On the basis of the 1 000 molecule representation shown in Table 3.13, simulations of the San
Joaquin gas have been conducted in the NPT ensemble at three different temperatures for
which experimental measurements of the compressibility factor Z = PV/RT were available
[Sage and Olds, 1947]. These simulations have been conducted only at pressures greater than
the retrograde dew point pressure, which is 20.7 MPa. The results (Fig. 3.75) indicate that the
influence of pressure and temperature on Z is correctly reproduced, but the compressibility
factor appears systematically underestimated compared with measurements. Nevertheless,
the discrepancy between the result obtained by the Monte Carlo simulation method and the
experimental measurement does not exceed 3%. This discrepancy is significantly greater than
the estimated uncertainty for a mixture of known composition, which is inferred to be lower
than 2% on the basis of the tests performed on pure components (see Figure 3.71). The devi-
ation may be explained at least partly by the approximate analysis on which the modelled
composition is based. Another possible cause of error might be the representation of the
Figure 3.74 Example of a configuration of the HP-HT fluid under res-
ervoir conditions (463 K and 110 MPa), simulated with 500 molecules
belonging to 19 different molecular types.
heavy fraction. In order to test this, simulations have been performed in which the heavy frac-
tion has been represented by n-decane alone instead of n-decane and n-nonane. The com-
pressibility factor is not significantly changed, indicating that the representation of the heavy
fraction was not a major issue for this particular gas.
In the case of the HP-HT gas, volumetric measurements in reservoir conditions have been
made by Arnaud [1995]. The Monte Carlo simulation of this gas was carried out using the
NPT ensemble at the reservoir temperature with the composition shown in Table 3.14.
Although the large number of components might be an obstacle to satisfactory convergence,
it is observed that density converges in a reasonable number of Monte Carlo steps: after
20 millions of iterations, the limiting value is obtained within 2% (Fig. 3.76). The density of
the HP-HT fluid is particularly high as it reaches 500 kg/m
3
at 110 MPa (Fig. 3.77), i.e.
greater than the densities of methane and ethane in the same conditions. This high density can
be explained by the predominance of heavy hydrocarbons in the gas, as mentioned above
when discussing the image of a configuration box (Fig. 3.74). Experimental gas density mea-
surements agree closely with simulation predictionswhich is not surprising when considering
the good representation of the densities of methane and ethane, which are the most abundant
compounds in the fluid. There is however a difference in temperature with respect to the mea-
surements of Arnaud [1995] which were made at the reservoir temperature as estimated at that
time, i.e. 453 K, whereas the simulations were made at a more recently estimated reservoir
temperature, i.e. 463 K. If the simulation had been conducted at 453 K, a slight overestima-
tion of the density would have been found. Nevertheless, the results are extremely encourag-
ing because the HP-HT fluid is a particularly challenging example of a gas condensate.
Figure 3.75 Compressibility factor of the San Joaquin gas from NPT
simulations at 277.57K (
), at 310.93K (o), at 344.26K () after

Lagache et al. [2004a]. The lines represent the experimental measure-
ments of Sage and Olds [1947]. Reprinted from [Lagache et al., 2004],
2004 with permission from Elsevier.
0.9
24 25 26
P(MPa)
C
o
m
p
r
e
s
s
i
b
i
l
t
y

F
a
c
t
o
r
27 28
0.85
0.8
0.75
0.7
Figure 3.76 Convergence of the running density average (continuous
line) and of the Joule-Thomson coefficient (dotted line) of the HP-HT
fluid in a typical simulation in the NPT ensemble [Lagache et al. 2004a]
at T = 463.15 K and P = 30 MPa.
Figure 3.77 Density of methane (---), ethane (
..
) and of the HP-HT
fluid (
____
) obtained by NPT simulation at 463.15 K, compared with the
recommended values of IUPAC for methane (
) at 463.15 K, with the val-

ues of Friend et al. [1991] for ethane () at 463.15 K, and with the values
of Arnaud [1995] for the HP-HT fluid (o) at 452.65 K [Lagache et al.,
2004a]. Reprinted from [Lagache et al., 2004], 2004 with permission
from Elsevier.
0 10 20 30 40 50 60 70 80
Monte Carlo step (millions)
310
315
320
325
330
335
340
/
k
g
3
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
/
K
M
P
a
1
600
20 30 40 50 60
P(MPa)
D
e
n
s
i
t
y

(
k
g
3
)
70 80 90 100 110 120
500
400
300
200
100
0
3.5.4 Joule-Thomson Coefficient and Derivative Properties
As seen in Sections 2.4.8 and 3.2, the derivative properties and the Joule-Thomson coeffi-
cient can be obtained by combining simulation results in the NPT ensemble with the ideal
heat capacities of pure components. In this study, the ideal heat capacities have been deter-
mined from the correlations available in the Dortmund Data Bank. In Figure 3.76, the con-
vergence of the Joule-Thomson coefficient is shown to require longer simulations than the
density, and the statistical uncertainty on this property is approximately 0.05 K MPa
1
. The
computed Joule-Thomson coefficients have been plotted as continuous curves which repre-
sent the raw simulation results to within this degree of accuracy.
In the case of the San Joaquin gas, the Joule-Thomson has been computed by this method
in a large range of pressures at 310.9 K, i.e. one of the temperatures at which the volumetric
behaviour has been tested in Section 3.5.3. This allows to determine the Joule-Thomson
inversion pressure at this temperature. The same determination is also shown for methane and
ethane (Fig. 3.78). These results show that the behaviour of the natural gas is intermediate
between methane and ethane. This is not surprising, as methane and ethane account for more
than 85% of the gas. The Joule-Thomson inversion pressure is approximately 39 MPa, while
it is 47 MPa for methane and 24 MPa for ethane at the same temperature. At high pressure,
the Joule-Thomson coefficient tends to the same limiting value of 0.4 K/MPa for the San
Joaquin gas and the two pure hydrocarbons.
In the case of the HP-HT gas, the same type of calculation has been performed at the res-
ervoir temperature, i.e. 463 K (Fig. 3.79). In the same way as for the density of the same fluid,
Figure 3.78 Joule-Thomson coefficient of the San Joaquin gas (
____
),
of methane (---) and of ethane (
..
) at 310.93 K, compared with the rec-
ommended values of IUPAC [Wagner, 1996] for methane (
) at the
same temperature [Lagache et al., 2004a]. Reprinted from [Lagache et
al., 2004], 2004 with permission from Elsevier.
3
0 10 20
P(MPa)
J
o
u
l
e
-
T
h
o
m
s
o
n

c
o
e
f
f
i
c
i
e
n
t

(
K
M
P
a
1
)
30 40 50 60 70 80 90 100 110
2
1
0
1
the Joule-Thomson coefficient of the gas no longer falls between those of methane and
ethane, e.g. the Joule-Thomson inversion pressure for the gas as obtained by simulation is
42 MPa, while it is 51 MPa for ethane and 58 MPa for methane. Although no direct measure-
ments of the Joule-Thomson coefficient have been made on the HP-HT fluid, the inversion
conditions are known from its volumetric behaviour. Indeed, the density has been measured
at several pressures and temperatures, allowing a good estimate of the thermal expansivity
and of the molar volume. From these informations, it is possible to estimate the conditions
for which the product (T 1) is zero. This indirect determination of the Joule-Thomson
inversion pressure is 42.6 MPa, a value in excellent agreement with simulation results. Here
again, it is likely that such an agreement is partly fortuitous, as the deviation is lower than the
estimated statistical uncertainty (approximately 2 MPa), but it is a likely indication that no
major bias is involved in the predictions of this natural gas.
The trend of isothermal compressibility is given in Figure 3.80 for the HP-HT fluid. There
is no experimental validation for this property, so the computed values are pure predictions
which are indirectly supported by the correct prediction of the other properties. With increas-
ing pressure, the isothermal compressibility decreases significantly, confirming that the fluid
tends to behave like a liquid in the upper part of the pressure range.
As a concluding remark, it may be said that the detailed composition of condensate gases
may now be addressed by molecular simulation and that the prediction of various thermody-
namic properties appears feasible. More detailed investigations are needed to define how sen-
sitive the outputs are to the way in which fluid composition is modelled. Nevertheless, the
results are encouraging enough to envisage extending this type of prediction to phase equi-
librium behaviour with a reasonable expectation of success in the years to come.
Figure 3.79 Joule-Thomson coefficient of the HP-HT fluid (
____
), of
methane (---) and of ethane (
..
) obtained by NPT simulation at 463.15 K,
compared with the recommended values of IUPAC [Wagner, 1996] for
methane (
) at the same temperature [Lagache et al., 2004a]. Reprinted

from [Lagache et al., 2004], 2004 with permission from Elsevier.
0.8
20 30 40 50 60
P(MPa)
70 80 90 100 110 120
0.6
0.4
0.2
0
0.2
0.4
J
o
u
l
e
-
T
h
o
m
s
o
n

c
o
e
f
f
i
c
i
e
n
t

(
K
M
P
a
1
)
3.6 THERMODYNAMIC PROPERTIES OF ACID GASES
AT HIGH PRESSURE
The production of acid gases (i.e. natural gases containing carbon dioxide or hydrogen sul-
phide) raises particular operational problems for H
2
S concentrations above 10%. These prob-
lems correspond to the cost of the amine separation unit which is necessary to reduce the H
2
S
concentration to the specified level (which is very low) and of the Claus unit in which the sep-
arated H
2
S must be converted to elementary sulphur. The overall cost of this treatment makes
exploiting several important natural gas deposits unfeasible.
In order to reduce production costs, a preliminary simple separation step may be consid-
ered so that most of the H
2
S in the gas is recovered in the liquid state and can be reinjected
into a deep reservoir. This reduces considerably the size of the amine separation unit (which
is still necessary to comply with the H
2
S specification) and of the associated Claus unit. The
lower investment and operational costs of these units compensates largely for the additional
cost of the proposed preliminary separation. This preliminary separation step is achieved
using a stripper in which the natural gas stream is brought into contact with the refrigerated
recycled stream which contains mostly H
2
S and water separated in the cold tank. The whole
preliminary treatment operation proceeds at a pressure which is high enough (typically
7 MPa) to ensure that the H
2
S-rich effluent is in liquid form so that, if necessary, it can be
pumped for the purposes of reinjection (Fig. 3.81). In addition to H
2
S and hydrocarbon gases,
attention must be paid to the fate of water and CO
2
in the process. As much as possible of
these undesirable components of the natural gas should be pumped into the reservoir together
with the H
2
S.
Figure 3.80 Isothermal compressibility of the HP-HT fluid (
____
), of
methane (---) and of ethane (
..
) obtained by NPT simulation at
463.15 K. Reprinted from [Lagache et al., 2004], 2004 with permis-
sion from Elsevier.
3e 08
2.5e 08
2e 08
1.5e 08
1e 08
5e 09
0
20 30 40 50 60
P(MPa)
70 80 90 100 110 120
I
s
o
t
h
e
r
m
a
l

c
o
m
p
r
e
s
s
i
b
i
l
i
t
y

(
P
a
1
)

3.5 Properties of Natural Gases at High Pressure: 3. Fluid Phase Equilibria and Fluid Properties

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3.5 Properties of Natural Gases at High Pressure: 3. Fluid Phase Equilibria and Fluid Properties

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162 3.

Fluid Phase Equilibria and Fluid Properties

), at 310.93K (o), at 344.26K () after

) at 463.15 K, with the val-

) at the same temperature [Lagache et al., 2004a]. Reprinted

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