Fluid Phase Equilibria 298 (2010) 9296

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Fluid Phase Equilibria
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Modeling of three-phase vaporliquidliquid equilibria for a natural-gas
system rich in nitrogen with the SRK and PC-SAFT EoS

Daimler N. Justo-Garca
a,b
, Fernando Garca-Snchez
a,
, Nstor L. Daz-Ramrez
b
,
Enrique Daz-Herrera
c
a
Laboratorio de Termodinmica, Programa de Investigacin en Ingeniera Molecular, Instituto Mexicano del Petrleo, Eje Central Lzaro Crdenas 152, 07730 Mxico, D.F., Mexico
b
Departamento de Ingeniera Qumica Petrolera, ESIQIE, Instituto Politcnico Nacional, Unidad Profesional Adolfo Lpez Mateos, Zacatenco 07738 Mxico, D.F., Mexico
c
rea de Fsica de Lquidos, Departamento de Fsica, Universidad Autnoma MetropolitanaIztapalapa, Av. San Rafael Atlixco 186, Col. Vicentina, 09340 Mexico, D.F., Mexico
a r t i c l e i n f o
Article history:
Received 21 January 2010
Received in revised form 9 July 2010
Accepted 14 July 2010
Available online 24 July 2010
Keywords:
PC-SAFT equation of state
Liqueed natural gas
Vaporliquidliquid equilibria
Gibbs energy
Stability analysis
Phase envelope
a b s t r a c t
In this work, we present the modeling of three-phase vaporliquidliquid equilibria for a mixture of
natural gas (Hogback gas) containing high concentrations in nitrogen (51.8mol%) with the SRK and PC-
SAFT equations of state. The interest of studying this mixture is due to the experimental evidence of the
occurrence of multiple equilibriumliquid phases for this mixture over certain ranges of temperature and
pressure. The calculation of the multiphase equilibria was carried out by using an efcient numerical
procedure based on the minimization of the system Gibbs energy and thermodynamic stability tests to
ndthe most stable state of the system. The results of the calculatedvaporliquidliquidequilibria (VLLE)
show that the PC-SAFT equation of state predicts satisfactorily the phase behavior that experimentally
exhibits this mixture, whereas the SRK equation of state predicts a three-phase region wider than the
experimentally observed. The two-phase boundary for this mixture was also calculated through ash
calculations, and the results showed that this mixture does not present any gas-liquid critical point.
2010 Elsevier B.V. All rights reserved.
1. Introduction
Natural gas is often liqueed to make the transportation and
storage of this gas more convenient. Notwithstanding, storage and
transportation are not the sole reasons for liquefying natural gas.
The liquefaction process is also important for the separation of
heliumfromthe gas streamas well as to remove most of the nitro-
gen, providing a gas with a much higher heating value.
Animportant eldof liqueednatural gas equilibria work is that
portion dealing in vaporliquidliquid behavior, which is charac-
terizedby the presence of three uidphases inequilibrium. Process
inefciencies are often the result of this multiphase behavior since
the extra phase cancause unexpectedseparationproblems andtray
inefciencies.
The success of the design and operation of separation processes
in the oil and gas industry at low temperatures is critically depen-
dent upon accurate description of the thermodynamic properties
andphasebehavior of theconcernedmulticomponent hydrocarbon

Presented at the Colloquiumto Promote Experimental Work in Thermophysical

Properties for Scientic Research and Industry, in Honor to the 60th Birthday of
Professor Dominique Richon. Paris, France, September 34, 2009.

Corresponding author. Tel.: +52 55 9175 6574.

E-mail address: fgarcias@imp.mx (F. Garca-Snchez).
mixtures with inorganic gases. Therefore, it is important to apply
appropriate models within a thermodynamic modeling framework
to predict, describe and validate the complex phase behavior of
liqueed natural gas mixtures.
The evaluation of equations of state to predict the phase behav-
ior of natural-gas systems has been the subject of some recent
publications. For instance, Aparicio-Martnez and Hall [1] applied
the generalized RedlichKwong/PengRobinson (RKPR) three-
parameter cubic equationof state[2] for predictingthermodynamic
properties of light synthetic natural-gas mixtures using classical
one-uid mixing rules. This equation of state yielded good phase
envelope predictions at low and moderate pressures but was less
satisfactory at high pressures close to the cricondenbar. Subse-
quently, these authors applied the PC-SAFT equation of state [3]
to the prediction of global phase diagrams in binary mixtures rele-
vant to natural gases. In these works, they reported the results for
the binary systems n-alkane +n-alkane [4], n-alkane +non-linear
hydrocarbons such as branched alkanes, cyclic alkanes, and aro-
matic compounds [5], and n-alkane +non-hydrocarbon gases (CO
2
,
N
2
, H
2
S) [6].
Alfadrique and Castier [7] also reported a work concerning the
calculation of the phase equilibria and critical points of natural
gases with the PR (Peng and Robinson [8]) and PC-SAFT equations
of state by using binary interactionparameters equal tozeroinboth
equations of state. In that work, calculations were performed for 19
0378-3812/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.uid.2010.07.012
D.N. Justo-Garca et al. / Fluid Phase Equilibria 298 (2010) 9296 93
synthetic natural gases for which experimental data are available
in the literature. As a result of their calculations, these authors con-
cluded that, for most mixtures, the predictions of the PC-SAFT EoS
are in better agreement with the experimental data.
Multiphase equilibrium calculations at given temperature and
pressure using the SRK equation of state [9] for a hypothet-
ical nitrogen-rich light-hydrocarbon mixture, were carried out
by Michelsen [10]. This mixture of composition 54.79mol%
methane, 7.08mol% ethane, 3.67mol% propane, 2.08mol% n-
butane, 1.98mol% n-pentane, and 30.40mol% N
2
, exhibited,
according to the results reported by this author, a complicated
phase behavior with two separate three-phase regions and a total
of six critical points of which three were located on the two-phase
envelope, two on the upper three-phase boundary and one on the
lower three-phase boundary. This mixture was also studied by
Justo-Garca et al. [11] using the PC-SAFT equation of state but,
contrary to the results reported by Michelsen [10] with the SRK
equation of state, these authors found that, according to the PC-
SAFT model, this mixture only exhibits one three-phase region and
a single critical point on the two-phase envelope.
Recently, Justo-Garca et al. [12] reported the modeling of the
VLLE for the ternary systems nitrogen+methane +n-pentane, nitr-
ogen+methane +n-hexane, and nitrogen+methane +n-heptane
using the PC-SAFT and SRK equations of state. In this work, the
authors compared and analyzed the capabilities of these equa-
tions of state to predict the phase behavior exhibited by the three
systems studied. The results obtained showed that both equa-
tions of state predict with reasonable accuracy the experimentally
observed phase behavior of the ternary systems considered.
The aimof this work is to apply both the SRK and PC-SAFT equa-
tions of state to predict the phase behavior of a natural-gas system
containing high concentrations of nitrogen (N
2
) for which experi-
mental VLLE data at different temperature and pressure conditions
were reported by Stroud et al. [13]. This system was selected in
this study due to that it is, to the best of our knowledge, the only
substantiated evidence of a VLLE in a naturally occurring gas with
high contents of N
2
(51.8mol%), so that this system represents a
challenge to test the capabilities of any equation of state to predict
its experimentally observed multiphase behavior.
2. Numerical procedure
The approach used in this work for solving the isothermal mul-
tiphase ash problem with equations of state, which is based on
the minimization of the system Gibbs energy along with thermo-
dynamic stability tests to nd the most stable state of the system,
has been previously reported [11,12] and will not be repeated in
detail in this report.
Briey, the system is assumed to be initially monophasic. A
stability test, based on the tangent plane criterion [14,15], allows
checking if the systemis stable or not. In the latter case, it provides
an estimation of the composition of an additional phase to take into
account the equilibrium calculation. The number of phases is then
increased by one and equilibrium is achieved by minimizing the
Gibbs energy. This approach, advocated as a stagewise procedure
[10], is continued until a stable solution is found.
3. Thermodynamic models
3.1. The SRK equation of state
The explicit formof the SRK equation of state [9] can be written
as
p =
RT
v b

a(T)
v(v +b)
(1)
where constants a and b for pure-components are related to
a = 0.42747
R
2
T
2
c
p
c
(T
r
) (2)
b = 0.08664
RT
c
p
c
(3)
and (T
r
) is expressed in terms of the acentric factor as
(T
r
) = [1 +(0.480 +1.574 0.176
2
)(1 T
1/2
r
)]
2
(4)
For mixtures, constants a and b are given by
a =
N

i=1
N

j=1
x
i
x
j
a
ij
(5)
b =
N

i=1
x
i
b
i
(6)
and a
ij
is dened as
a
ij
= (1 k
ij
)
_
a
i
a
j
k
ij
= k
ji
; k
ii
= 0 (7)
where k
ij
is an adjustable interaction parameter characterizing the
binary mixture formed by components i and j.
3.2. The PC-SAFT equation of state
Inthe PC-SAFTequationof state [3], the molecules are conceived
to be chains composed of spherical segments, in which the pair
potential for the segment of a chain is given by a modied square-
well potential [16]. Non-associating molecules are characterizedby
three pure-component parameters: the temperature-independent
segment diameter , the depth of the potential , and the number
of segments per chain m.
The PC-SAFT equation of state written in terms of the Helmholtz
energy for an N-component mixture of non-associating chains con-
sists of a hard-chain reference contribution and a perturbation
contribution to account for the attractive interactions. In terms of
reduced quantities, this equation can be expressed as
a
res
= a
hc
+ a
disp
(8)
The hard-chain reference contribution is given by
a
hc
= m a
hs

i=1
x
i
(m
i
1) ln g
hs
ii
(
ii
) (9)
where m is the mean segment number in the mixture
m =
N

i=1
x
i
m
i
(10)
The Helmholtz energy of the hard-sphere uid is given on a per-
segment basis as
a
hs
=
1

0
_
3
1

2
(1
3
)
+

2
3

3
(1
3
)
2
+
_

2
3

3
2

0
_
ln(1
3
)
_
(11)
and the radial distribution function of the hard-sphere uid is
g
hs
ij
=
1
(1
3
)
+
_
d
i
d
j
d
i
+d
j
_
3
2
(1
3
)
2
+
_
d
i
d
j
d
i
+d
j
_
2
2
2
2
(1
3
)
3
(12)
with
n
dened as

n
=

6

i=1
x
i
m
i
d
n
i
n = 0, 1, 2, 3 (13)
94 D.N. Justo-Garca et al. / Fluid Phase Equilibria 298 (2010) 9296
The temperature-dependent segment diameter d
i
of component
i is given by
d
i
=
i
_
1 0.12exp
_
3

i
kT
__
(14)
where k is the Boltzmann constant and T is the absolute tempera-
ture.
The dispersion contribution to the Helmholtz energy is given by
a
disp
= 2I
1
(, m)m
2

3
m
_
1 +Z
hc
+
Z
hc

_
1
I
2
(, m)m
2

3
(15)
where Z
hc
is the compressibility factor of the hard-chain reference
contribution, and
m
2

3
=
N

i=1
N

j=1
x
i
x
j
m
i
m
j
_

ij
kT
_

3
ij
(16)
m
2

3
=
N

i=1
N

j=1
x
i
x
j
m
i
m
j
_

ij
kT
_
2

3
ij
(17)
The parameters for a pair of unlike segments are obtained by
using conventional combining rules

ij
=
1
2
(
i
+
j
) (18)

ij
=
_

j
(1 k
ij
) (19)
where k
ij
is a binary interaction parameter, which is introduced to
correct the segment-segment interactions of unlike chains.
The terms I
1
(, m) and I
2
(, m) in Eq. (15) are calculated by
simple power series in density:
I
1
(, m) =
6

i=0
a
i
( m)
i
(20)
I
2
(, m) =
6

i=0
b
i
( m)
i
(21)
where the coefcients a
i
and b
i
depend on the chain length as given
in Gross and Sadowski [3]. For details of the PC-SAFT equation of
state, the reader is referred to the original literature.
4. Results and discussion
The problem of determining with equations of state the com-
plex phase behavior developing the natural gas mixtures with
high contents of N
2
is due to the occurrence of multiple liquid
phases over certain ranges of temperature and pressure, which
is caused by the large differences existing among the critical
temperatures of the components that form the mixture. For sys-
tems with non-associating components such as N
2
, He, Ar, and
hydrocarbons, the PC-SAFT equationof state requires of three pure-
component parameters (m, , ), which are usually determined
from experimental vapor pressure and liquid density data of the
pure component. Because these parameters are not available in
the literature for He, we have evaluated them from experimental
vapor pressure data between the normal boiling point (T
b
=4.25K)
of He and its critical point (T
c
=5.19K) by minimizing the following
objective function:
S =
Np

i=1
_
P
exp
v,i
P
calc
v,i
(m, , )
P
exp
v,i
_
2
(22)
where Np is the number of experimental points and P
v,i
is the vapor
pressure of component i. Eq. (22) was minimized using the simplex
optimization procedure of Nelder and Mead [17] with convergence
accelerated by the Wegstein algorithm [18]. Table 1 presents the
optimum values of parameters m, and obtained for He. This
table also presents the values of these pure-component parame-
ters reported by Gross and Sadowski [3] for the other components
that form the mixture of natural gas (Hogback gas) studied in this
work. Physical properties (i.e., normal boiling point T
b
, critical tem-
perature T
c
, critical pressure p
c
, and acentric factor ) for all the
components constituting this mixture were taken from Ambrose
[19] and they are also given in Table 1.
The SRK and PC-SAFT equations of state were applied to the
prediction of the phase behavior for this natural gas mixture
constituted of hydrocarbons (methane, ethane, propane, butane,
isobutane, pentane, isopentane, and hexanes+) and gases non-
hydrocarbons (N
2
, He, and Ar). This mixture was experimentally
studiedby Stroudet al. [13] from116.48 to 199.82Kintemperature
and from 0.69 to 3.45MPa in pressure. The mixture composition
reportedby these authors is 51.8mol%N
2
, 7.0mol%He, 0.6mol%Ar,
32.9mol% methane, 3.3mol% ethane, 1.8mol% propane, 0.9mol%
butane, 0.7mol% isobutane, 0.3mol% pentane, 0.4mol% isopen-
tane, and 0.3mol% hexanes+. In their study, Stroud et al. observed
that two stable liquid phases were present at the temperature of
116.48Kandfour different pressures: 1.38, 2.07, 2.76, and3.45MPa.
The same phenomenon occurred at 130.37K and 3.45MPa.
The prediction of the phase behavior for this system was car-
ried out with isothermal multiphase ash calculations through
the minimization of the system Gibbs energy in conjunction with
thermodynamic stability tests to nd the most stable state of the
system. For all the calculations, the binary interaction parameters
Table 1
Physical properties
a
and pure-component parameters of the PC-SAFT equation of state
b
.
Components MW (g/mol) T
b
(K) Tc (K) Pc (MPa) m () /k (K)
He 4.00 4.25 5.19 0.227 0.365 0.2341
c
1.6078
c
32.97
c
N
2
28.01 77.35 126.2 3.39 0.039 1.2053 3.3130 90.96
Ar 39.95 87.28 150.8 4.87 0.001 0.9285 3.4784 122.23
Methane 16.04 111.63 190.58 4.604 0.012 1.0000 3.7039 150.03
Ethane 30.07 184.55 305.42 4.880 0.099 1.6069 3.5206 191.42
Propane 44.10 231.05 369.82 4.250 0.153 2.0020 3.6184 208.11
Butane 58.12 272.65 425.18 3.797 0.199 2.3316 3.7086 222.88
Isobutane 58.12 261.42 408.15 3.648 0.183 2.2616 3.7584 216.53
Pentane 72.15 309.21 469.7 3.369 0.251 2.6896 3.7729 231.20
Isopentane 72.15 301.03 460.43 3.381 0.270 2.5620 3.8296 231.20
Hexanes+
d
86.18 341.88 507.5 3.012 0.299 3.0576 3.7983 236.77
a
Ambrose [19].
b
Gross and Sadowski [3].
c
Estimated in this work.
d
Assumed to be n-C
6
.
D.N. Justo-Garca et al. / Fluid Phase Equilibria 298 (2010) 9296 95
Table 2
Binary interaction parameters for the PC-SAFT equation of state.
N
2
C
1
C
2
C
3
C
4
i-C
4
C5 i-C5 C
6
N
2
0.0000 0.0307 0.0359 0.0851 0.0880 0.0816 0.0697 0.1031 0.0767
C
1
0.0307 0.0000 0.0039 0.0019 0.0192 0.0238 0.0213 0.0297 0.0220
C
2
0.0359 0.0039 0.0000 0.0089 0.0084 0.0020 0.0119 0.0100 0.0094
C
3
0.0851 0.0019 0.0089 0.0000 0.0034 0.0004 0.0157 0.0100 0.0025
C
4
0.0880 0.0192 0.0084 0.0034 0.0000 0.0100 0.0033 0.0100 0.0026
i-C
4
0.0816 0.0238 0.0020 0.0004 0.0100 0.0000 0.0100 0.0100 0.0100
C5 0.0697 0.0213 0.0119 0.0157 0.0033 0.0100 0.0000 0.0100 0.0200
i-C5 0.1031 0.0297 0.0100 0.0100 0.0100 0.0100 0.0100 0.0000 0.0100
C
6
0.0767 0.0220 0.0094 0.0025 0.0026 0.0100 0.0200 0.0100 0.0000
used for the PC-SAFT equation of state were those reported by
Garca-Snchez et al. [20] and by Justo-Garca et al. [21] for the
binaries formed of n-alkanes and N
2
with n-alkanes. The values of
these interaction parameters for the PC-SAFT model are presented
in Table 2, whereas the binary interaction parameters used in the
calculations for the SRK equation of state were those listed in Reid
et al. [22]. For the binaries formed of He and Ar with n-alkanes, N
2
and He with Ar, and N
2
with He, the binary interaction parameters
were set equal to zero (i.e., k
He-alkane
= k
Ar-alkane
= k
N
2
-Ar
= k
He-Ar
=
k
N
2
-He
= 0) in both equations of state.
Results of thephasebehavior predictions for themixtureof Hog-
back gas with the SRK and PC-SAFT equations of state are showed
in Fig. 1. In this gure, it can be seen that the calculated two-phase
envelopes are essentially a locus of dew points with a wide retro-
grade zone. This was veried with direct critical point calculations
performed with the SRK and PC-SAFT models by using the proce-
dures presented by Justo-Garca et al. [21,23]. For the SRK model,
the simulated annealing algorithm[24] was applied for solving the
criticality conditions based on the tangent plane distance in terms
of the Helmholtz energy using temperature and volume as inde-
pendent variables, whereas for the PC-SAFT model, the mixture
critical point calculation was carried out by using the algorithm of
Heidemann and Khalil [25]. In both cases, the calculations showed
that this mixture does not present any critical point on the two-
phase boundary, which is consistent with the results of the ash
calculations used to construct the two-phase envelopes.
Fig. 1. Pressuretemperature phase diagramfor the nitrogen-rich natural gas (Hog-
back gas) system showing the experimental three-phase VLLE conditions and the
calculated two- and three-phase boundaries with the SRK and PC-SAFT equations
of state.
Fig. 1 also presents the experimental VLLE data at the ve condi-
tions of temperature and pressure studied by Stroud et al. and the
calculated three-phase vaporliquidliquid boundaries with the
two thermodynamic models considered here. In this case, the two
three-phase envelopes end at the critical solution temperature (or
the consolute temperature) in which the two liquids become iden-
tical in composition; i.e., the mutual solubilities of the two liquids
increase with increasing temperature up to reach a point in which
the compositions of the two liquids are identical.
An examination of Fig. 1 shows that the calculated three-phase
boundary with the SRK model overpredicts largely the experimen-
tal three-phase data, in particular at the lowest temperatures, with
an estimated critical solution temperature of 152.7K, whereas the
calculated three-phase boundary with the PC-SAFT model is in bet-
ter agreement withthe ve experimental VLLEconditions at 116.48
and 130.37K. In this latter case, the estimated value of the criti-
cal solution temperature is 136.8K, which agrees with the visual
observations carried out by Stroud et al. who indicated that this
temperature should be between 130.4 and 144.3K.
Fig. 2 presents a detailed section of the phase diagram given
in Fig. 1 for the nitrogen-rich natural gas (Hogback gas) mixture
studied. In this gure, it can be seen the experimental three-phase
VLLE conditions reported by Stroud et al. and the two three-phase
boundaries calculated with the SRK and PC-SAFT equations. This
Fig. also shows the experimental two-phase VLE data studied by
these authors at different conditions of temperature and pressure.
Here, it is interesting to note that the experimental VLE data at
Fig. 2. Details of the pressuretemperature phase diagram given in Fig. 1 for the
nitrogen-rich natural gas (Hogback gas) system, including the experimental two-
phase VLE conditions.
96 D.N. Justo-Garca et al. / Fluid Phase Equilibria 298 (2010) 9296
two temperature (116.48 and 130.37K) and pressure (0.69 and
2.76MPa) conditions, are located close to the calculated three-
phase VLLE envelope with the PC-SAFT model but without going
throughit, while for the calculatedthree-phase VLLE envelope with
the SRK model, one of these experimental conditions (130.37K and
2.76MPa) is located inside the three-phase region.
In order to verify the rather high bubble-point locus of the
three-phase boundary obtained with the SRK model through the
isothermal multiphase ash calculations, we have carried out a
series of vaporliquidliquid bubble-point calculations by using
the algorithm proposed by Peng and Robinson [26]. These calcu-
lations were carried out isothermally for both the SRK and PC-SAFT
models and the results were consistent with those obtained from
the multiphase ash procedure. Here, it should be mentioned that
although the SRK equation predicts a wider three-phase region
for the mixture studied than that reported by Stroud et al. at
the ve equilibrium conditions, the predictions of the equilibrium
phases for this mixture could be improved if the congurational
properties of He are described by quantum, rather than classical,
mechanical statistical, so that the properties of this gas cannot be
given by the same corresponding-states treatment as that used
for classical gases when the true critical constants are used in the
reducing parameters [27]. A possible solution to this problem is,
as proposed by Gunn et al. [28], to dene temperature-dependent
effective critical constants with which the properties of quantum
gases (hydrogen, helium, neon) can be made to coincide with those
for classical gases. However, this aspect is outside the scope of this
work and was not considered here.
5. Conclusions
We have applied the SRK and PC-SAFT equations of state
with one-uid mixing rules and temperature-independent binary
interaction parameters to represent the complex phase behavior
experimentally observed in a natural gas (Hogback gas) system
with high contents in N
2
(51.8mol%). The phase equilibrium cal-
culations were carried using an efcient computational numerical
procedure based onthe systemGibbs energy along withthermody-
namic stability tests to nd the most stable state of the system. This
procedure (isothermal multiphase ash) was used to predict two-
and three-phase envelopes. In the case of the two-phase envelope,
both equations of state predicted essentially a locus of dew points,
whereas the predicted three-phase envelopes end at the critical
solution temperatures of 152.7 and 136.8K for the SRK and PC-
SAFT models, respectively. In the latter case, the estimated value of
the critical solution temperature is closer to the experimental one,
which, according to the experimental visual observations carried
out by Stroud et al., should be between 130.4 and 144.3K. Con-
sequently, based on the fact that the predictions with the PC-SAFT
model showedabetter agreement withtheexperimental VLLEdata,
it can be concluded that given the interaction parameters available
andfor this specic mixture, the PC-SAFTmodel appears toperform
better than the SRK equation of state.
Acknowledgments
This work was supported by the Molecular Engineering
Research Program of the Mexican Petroleum Institute under
research project D.00484. The authors would like to acknowledge
the contribution of the anonymous reviewer, whose constructive
criticism led to this improved version of the original manuscript.
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