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Fluid Phase Equilibria, 82 (1993) 361-368

Elsevier Science Publishers B.V., Amsterdam

A COMPREHENSIVE COMPARISON OF MIXING RULES FOR CALCULATION OF PHASE


EQUILIBRIA IN COMPLEX SYSTEMS.

Knudsen, K., Stenby, E.H. and Fredenslund, Aa.


Engineering Research Center IVC-SEP
Department of Chemical Engineering.
DTH, Building 229, DK-2800 Lyngby, Denmark
Keywords: theory, equation of state, cubic, mixing rules, water, complex systems, high
pressure.
ABSTRACT
Five d i f f e r e n t mixing rules for the SRK-EOS have been investigated for phase
equilibrium calculations in chemically complex systems at high pressures. The mixing
rules are those of van der Waals with two binary parameters, the Huron-Vidal rule with
three binary NRTL-paramoters, the MHV2-mode] with UNIFAC-group parameters, the
Schwarzentruber - Galivel-Solasttouk - Renon rule with three binary parameters, and the
density dependent local composition rule with three binary parameters. The mixing rules
are investigated both with and without temperature-dependent parameters. For each mixing
rule the parameters are estimated using binary data for systems containing H~O, CO~, N~,
HzS, CH30H and n-alkanes up to n-decane. With the estimated parameters, mol[tcomp~nefft
data have been predicted and compared with experimental results. Furthermore the
influence of the thermodynamic consistency of the binary data has been investigated.
There is found a large discrepancy in the predicted results for multicomponent phase
e q u i l i b r i a between the d i f f e r e n t mixing rules, although almost the same results are
obtained for the correlation of the binary data. For the investigated systems, the
Huron-Vidal model gives the best overall predictions. I f temperature dependent
parameters are used, i t is necessary to be very careful when extrapolation of
temperature is performed.
INTRODUCTION
In order to calculate phase e q u i l i b r i a in systems containing only non-polar
components, the quadratic mixing rule o r i g i n a l l y proposed by van der Waals performs
adequately. For mixtures with strongly polar components (such as water and methanol),
more complex mixing rules are needed.
At low pressures the t r a d i t i o n a l approach for phase e q u i l i b r i a is to use an equation
of state (EOS) for the vapor phase and reference fugacities and a c t i v i t y coefficients
for the l i q u i d phase. Due to the missing continuity in the c r i t i c a l region, this
approach can not be used for high pressures. I t has therefore become more common to use
the same equation of state for both phases, and then apply a complex mixing rule for
mixtures containing both po]ar and non-polar compounds at high pressures.
During the last decade, several d i f f e r e n t complex mixing rules have been suggested
for various cubic forms of the EOS in order to describe chemically complex systems. Most
of these models are able to correlate most binary mixtures, when t h e i r parameters are
f i t t e d to these systems, especially i f temperature dependent parameters are introduced.
I f the parameters estimated only from binarymixtures are used to predict multicomponent
data, the results are not always as good as could be hoped, and in the present work an
investigation is carried out to check which forms of these mixing rules are the most
appropriate to predict multlcomponent data.
For many applications i t is necessary to use purely predictive models, such as
UNIFAC (Fredenslund et al. , 1977) but for application in transport of o i l in pipelines,
the only strongly polar components present are water and the hydrate i n h i b i t o r , which
could be methanol. In these systems the number of parameters that are necessary to
estimate is quite small.

0378-3812/93/$06.00 1993 Elsevier Science Publishers B.V. All rights reserved


362

THEORY
In this comparison of different mixing rules, the SRK cubic EOS (Soave, 1972) has
been used for all mixing rules investigated. The method of Mathias and Copeman (1983)
has been used to calculate the pure component a-parameter. QI, Q2 and Q3 in equation (I)
have been f i t t e d to pure component vapor pressures, except for H2, CO and N2. Q2 and Q3
are set to O for reduced temperatures greater than 1 to prevent s~range extrapolations.
As a consequence the model can not be used for calculation of heat capacity at the
c r i t i c a l point, but in this investigation the only concern is for phase equilibrium
calculations.
1 + Q , ( 1 - ~ + Q 2 ( 1 - ~ 2 + Q,(I-v/-~ Z<I
a~ : (I)
1 + Q1(1-~-~ ~,>i
The different mixing rules investigated are the one o r i g i n a l l y proposed by Huron and
Vidal (1979), equation (2), the density dependent local composition medel by Mollerup
(1983, 1985), which is extensively described in the references, the original rule byvan
der Waals with a quadratic term also for the b-parameter, equation (3), the model of
Schwarzentruber, Galivel-Solastiouk and Renon (1987), equation (4), and the MHV2-UNIFAC
model (Dahl, Rasmussen and Fredenslund, 1991), equation (5).
MC
I+++
, ~ - ~ m' (2)

k-I

a# = a~+aj(1 - ko) ; b# : b+2b] (1 - l#) QMR (3)

a# = a~j(l - k# - l# mOx, - m~x~) , k# = k#, le = - Iji, m# = 1 - .. SCffW (4)

MHV2-UNIFAC (5)

The different mixing rules and number of parameters are described in table I. The nature
and the number of parameters are indicated by the name shown in the f i r s t column. This
is introduced to simplify the notation. For the MHV2model 4 parameters are used.
TABLE I: The different models used in this comparison:
MIXING RULE DESCRIPTION No. of P/~J~t:TERS

QMRO: k+j - Itj - O. 0


QMRI: Kij estlmated, l j j - O. I
QMR2: k+j and l.. estlmated. 2
QMR4: and I i.
K_ lj linear functlons of temperature. 4
OHV3: *~, ~ anJd ~# estimated. 3
OHV4: ~# and *# linear functions of temperature, ~# constant. 4
OHV5: ~u and ~# linear functions of temperature, ~# estimated. 5
OHV6: ~#, ~ and a# all linear functions of temperature. 6
DDLC3: kij, 1i. and k'ti estimated. 3
DDLC5: kij an~ l i j linear functions of temperature, k'..lj estimated. 5
DDLC6: kU, l+j and k j: all linear functions of temperature. 6
SCHW3: k.., 1i. and m..'estimted. 3
SCHW5: kij, :u :inear functions of temperature, m.- i j estimated. 5
and m+iall linear functions of temperature. 6
MHv2S
:CHW6: Ukij'a ~ aji in UNIFAC linear functions of temperature
a 4
363

SYSTEMS
The different binary systems investigated are all those, where data are available,
including n-alkanes up to n-decane, H20, CO~, Nz, HzS and CH}OH. Furthermore both the H.
and CO interactions with water and methanol~ave been taken into account. For each modet
the parameters are estimated using these binary data. The pressure interval is from ]
to ]000 atm. and the temperature interval from 250 to 600 K. The objective function
which has been minimized is shown in equation (6), where xi, z is the composition of
component i in either the vapor or the second liquid phase.

ea~ ca/

A modified Marquardt algorithm from the Harwell library has been used to minimize the
sum of squares, SSQ. For multicomponentdata, table 2 shows some information about each
data set.
TABLE 2: The different multicomponentdata set used in this comparison.

System Temperature Pressure Numberof Components Calculation


No. Range Range Data performed
(K) (atm) Points
A 310-450 47.6-179 ]6 CH4,CO2,H2S,HzO PT-FLASH
B 3]0-588 3.4-]36.1 ]5 Hz,CO,H20 DEW P
C 308 3.7-93.9 2 CH4,N~,COz,CO,Hz, PT-FLASH
CH3OH,HzO
D 298 2.9-54.0 13 CH3OH,COz,HzO BUBL-P
E 333-393 49.3-246.7 6 CH4,C.He,C3H., PT-FLASH
C4Hlo,~z,COz,~zO
F 273 49.3-123.4 28 N2,COz,CH30H BUBL-P
H 3]] 34-340 lO CH4,C~He,C.H8, PT-FLASH
C4g,o,Hz~
I 313-343 5.0-31.6 54 CtH~,CH~OH,cO7 BUBL-P
References: A:(Robinson e t a ] . , 1985), B:(6tllespte and Wilson, 1980), C:(Pan and Ma, 1985), O:(Chang and Rousseau, 198S).
E:(Zou, 1989), F:(Weber eL a1..1984), H:(Dodson and Standing, 1944), I:(Galivel-Solastiouk eL al.. 1986).

RESULTS FOR BINARY SYSTEMS


The parameters for the quadratic mixing rules (QMRI, QMR2 and QMR4) have been
estimated for all systems, and i t is well known that for systems containing only
hydrocarbons and sour gasses the mixing rule QMRI is adequate (Pedersen, Thomassenand
Fredenslund, 1984). For systems containing hydrocarbons or sour gasses and strongly
polar components like methanol and water, QMRI can not describe the right behavior in
all the phases, (Tsonopoulosand Heidman, 1986). For systems containing either water or
methanol, parameters have been f i t t e d for all models. For the MHV2model, the parameters
obtained by Dahl et al. (1991) w i l l be used. In table 3 results for a few of the systems
investigated are shown. The f i r s t lines show the system, the number of datapoints, and
the temperature and pressure range in that particular system. The average deviations in
the table are described in equation (7):

TI. I~C', - ~ I ~ I--I~ Z; l y " - y " l (7)


A lz~ s = ,.z MDTP$ ' AP/P'~ = ,.t ND~P$ , Ay = .-I MDTPS

Equation (6) has been used in the parameter optimization.


The results shown for the water systems are actually the final estimation results,
because the deviation Aln K is the residue in the optimization. The results for the
methanol systems are obtained from bubble point calculations with temperature and liquid
phase composition as independent parameters.
364

TABLE 3: R e s u l t s f o r some b i n a r ~ s~,stems.

SYSTEM CH4-H=O C3HcH=O C4H,=o-H=O C~H,=-H20 N=-CHsOH CO-CHsOH H=.-CH30H H=S-CHaOH


POINTS 16 24 36 25 21 33 15 22
TEMP. (K) 323-589 311-428 311-478 311-589 273-373 29~473 298-373 248-273
PRES.(atm) 14-167 7-102 1-138 8-204 1-955 43-451 34-323 2-10
DEV. A In K, A In K, A In K, A In K, A P/P*~ A P/P'~ A P/P'~ A P/P~
DEV. AInK 2 Alnl~ AInK 2 AIn~ Ay Ay Ay

OHV3 0.191 0.218 0.330 0.635 0.078 0.028 0.071 0.024


0.057 0.318 0.274 0.629 0.0007 0.0069 0.0083

OHV4 0.032 0.028 0.042 0.039 0.060 0.037 0.029 0.023


0.026 0.061 0.060 0.138 0.0307 0.0368 0.0089

OHV5 0.032 0.021 0.032 0.097 0.034 0.035 0.022 0.024


0.026 0.061 0.061 0.140 0.0008 0.0050 0.0090

OHV6 0.032 0.021 0.023 0.096 0.024 0.027 0.073 0.024


0.026 0.060 0.053 0.140 0.0008 0.0047 0.0093

DDLC3 0.153 0.079 0.184 0.201 0.064 0.095 0.021 0.051


0.031 0.099 0.100 0.312 0.0020 0.0158 0.0088

DDLC5 0.031 0.050 0.089 0.177 0.063 0.044 0.020 0.028


0.023 0.080 0.060 0.134 0.0306 0.0043 0.0086

DDLC6 0.026 0.030 0.088 0.143 0.061 0.036 0.022 0.027


0.023 0.046 0.060 0.125 0.0005 0.0044 0.0083

QMR1 0.751 0.979 1.134 1.462 0.293 0.206 0.176 0.078


0.271 1.618 0.943 1.530 0.0110 0.0104 0.0078

QMR2 0.622 0.718 0.633 0.636 0.070 0.107 0.044 0.550


0.101 0.115 0.196 0.494 0.0020 0.0157 0.0096

QMR4 0.042 0.087 0.088 0.190 0.030 0.061 0.020 0.049


0.024 0.087 0.060 0.144 0.0307 0.0043 0.0086

SCHW3 0.313 0.620 0.890 0.837 0.091 0.155 0.052 0.030


0.027 0.266 0.049 0.174 0.0017 0.0096 0.0084

SCHW5 0.030 0.114 0.029 0.184 0.195 0.055 0.032 0.025


0.026 0.053 0.037 0.388 0.0072 0.0357 0.0093

S~6 0.030 0.116 0.029 0.652 0.039 0.041 0.032 0.024


0.026 0.053 0.037 0.712 0.0307 0.0345 0.0393

REFERENCE: CH4-H20:(6tllespteand Wilson,


1982), C3H8-H20:(Kobayashiand Katz, 1953}, C4Hlo-H20:(Reamer,Sageand Lacey,
195Z), C~H1~-H~O:(6|]|espieand W|]son, 1982),]/~-C~OH:(Brunner et al., 1987), CO-CH3OR:(Brunneret el., 1987),
H2-CH3OH;(B~nn~reta]., 1987), H2S-CH3OH:(Weber,~.,'1-981).

The g e n e r a l c o n c l u s i o n t h a t can be drawn from t a b l e 3 i s t h a t more parameters g i v e


s m a l l e r d e v i a t i o n s . The 95 ~ c o n f i d e n c e l i m i t and the c o r r e l a t i o n between the parameters
g e n e r a l l y i n c r e a s e d r a s t i c a l l y when b e y o n d 3 t o 4 parameters are used, i n d i c a t i n g t h a t
the system then i s as w e l l determined as i t can be w i t h the g i v e n model. A f u r t h e r
i n c r e a s e in the number o f parameters can g i v e wrong e x t r a p o l a t i o n s . The improvement when
gotng from 4 t o 5 o r 6 parameters i s minimal . Among the 3 parameter m i x i n g r u l e s , the
s m a l l e s t d e v i a t i o n s f o r the w a t e r systems are o b t a i n e d w i t h the DDLC-medel. For the
bubble p o i n t c a l c u l a t i o n s o f t h e methanol systems the OHV3 model per f or ms best w i t h
365

regard to the vapor phase composition, while the pressure is equally well determined by
a l l three models with 3 parameters. The hydrocarbon - methanol systems (not shown here)
are best correlated with the SCHWmodels. I f more than 3 parameters are used, the OHV
model performs best for almost a l l the systems. There is no considerable improvementin
going beyond 4 parameters. When 4 parameters are used in the OHV4model, ~# is constant
equal to 0.I for water systems and 0.5 for methanol systems.
The QMRI f a i l s completely for a l l systems, and the qMRZmodel is not able to describe
the equilibrium r a t i o for the hydrocarbon in the hydrocarbon-water systems, because the
s o l u b i l i t y of the hydrocarbon in the water is not well determined; i f ki, and I i, are
both made l i n e a r l y dependent on temperature, the model with 4 parameters ~an describe
a l l the systems with a good accuracy. The performance of QMR4is better than all of the
3 parameter models, but not as good as the OHV4. The QMR4is f u l l y comparable with the
SCHWmodels for the water systems, but somewhatworse for the methanol systems.
On figure I the Henry's constant for ethane at the vapor pressure of water is shown
as a function of the temperature. This dataset from Crovetto et al. (1984) was not used
in the parameter estimation. Both the QMR2 and the SCHW3 are not able to give the
correct maximumin Henry's constant. For this system OHV3 performs better than UDLC3.
I f 4 or more parameters are used a l l mixing rules give the right behavior.
In figure 2 the Pressure-composition diagram is shown for the propane - methanol
system at 313 K. Only the SCHW6model does not give a false l i q u i d - l i q u i d phase s p l i t .
This system is also the one shown in the a r t i c l e by Schwarzentruber et al. (1987). The
OHV6model does only give a wrong l l q u i d - l i q u i d phase s p l i t at the highest pressure, but
the performance is not very good. Both the MHV2and QMR4models calculate a rather large
l i q u i d - l i q u i d s p l i t , which is not present at this temperature. The SCHW3, OHV4and DDLC3
gives the same result as MHV2. The experimental data are from Galivel-Solastiouk et al.
(1986).

PROPANE(1) -ME'rHANOL(Z)
EI'H~ ( 1) - W A I ~ R ( 2 )
iso~eus AT~t3.~ K
HENRY'S CONSTANTS FOR ETHANE F R O M PT-FLASH
120000 3 AT THE VAPOR PRESSURE OF IATER 14.0 "

E 12.0

,,""" "'",, .... EXP


QMR4
DOLC$ .~
~100

80000 0HV4

hi 6.0-
z 600007 /// .~ %
0
U~ 6 . 0 -
IJ
''** EXP
- - OHV6
~ 4.0" .... MHV2
Z
20000 ~ - - - - SCHW6
-- Ot~R4
2.0"

ol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
200 2~ ~do 3~ 4~ 4~ ~o
0.0 ........ ,.........
TEMPERATURE (K) O.00 0.20
,

0.40
. . . . . . . . . f . . . . . . . . .

0.60
,

0.80
. . . . . . . . . ,

1.OO
composition ( x l , y l )
Figure 1 Ethane-water. Henry's constants for Figure 2 Propane-methanol. Isotherms from
ethane at the vapor pressure of water. PT-flash calculations at 313.15 IC

RESULTS FOR MULTICOMPONENT MIXTURES

All t h e r e s u l t s shown in t h i s section have been predicted from the models with the
parameters estimated to binary data points. The d i f f e r e n t systems are described in table
2. The deviations shown in table 4 are as described in equation (7), although A In K
here is an average for both component.
For gas - gas i n t e r a c t i o n , the 03~R1model is used, because both SCHW, DDLC and OHV
models can reduce to t h i s . For RHV2 gas- gas interactions are set to zero as suggested
366

by Dahl et. al., although this is not optimal.


TABLE 4: Results for some of the multicomponent mixtures from table 2.
SYSA SYSB SYSC SYSD SYSE SYSF S Y S H SYSI
A In K AP/P A In K AP/P ax*lO0 AP/P Ay*lO0 AP/P
Ax*lO0 Ay*lO0 aln K Ax*lO0 Ax*lO0 &y*lO0 Ay Ay

OHV3 0.327 0.0853 0.222 0.110 0.0140 0.0594 0.030 0.0592


0.275 0.657 0.0925 0.010 0.062 0.095 0.0340 0.0291

OHV4 0.100 0.0312 0.206 0.035 0.0081 0.0266 0.019 0.0717


0.070 0.292 0.0669 0.007 0.067 0.094 0.0168 0.0298

OHV5 0.I00 0.0305 0.209 0.031 0.0079 0.1149 0.018 0.0494


0.072 0.306 0.0677 0.006 0.059 0.079 0.0239 0.0302

OHV6 0.101 0.0474 0.212 0.047 0.0083 0.2532 0.018 0.0501


0.070 0.321 0.0669 0.006 0.064 0.097 0.0286 0.0305

DDLC3 0.187 0.0428 0.255 0.179 0.0103 0.1982 0.018 0.0941


0.234 0.279 0.0778 0.010 0.110 0.131 0.0477 0.0329

DDLC5 0.116 0.3088 0.557 0.193 0.0101 0.3329 0.017 0.0791


0.079 0.287 0.6387 0.007 0.310 0.219 0.0399 0.0318

DDLC6 0.105 0.0317 0.556 0.099 0.0101 0.3424 0.018 0.0767


0.072 0.281 0.0634 0.007 0.152 0.152 0.0473 0.0314

SCHW3 0.345 0.0261 0.250 0.251 0.0167 0.2304 0.017 0.1375


0.380 0.276 0.2506 0.015 0.074 0.115 0.0171 0.0645

SCHW5 0.134 0.0342 0.253 0.104 0.0080 0.3983 0.019 0.0693


0.094 0.513 0.1117 0.012 0.087 0.074 0.0321 0.0349

SCHW6 0.132 0.0318 0.210 0.138 0.0080 0.1447 0.020 0.0761


0.091 0.504 0.11960.012 0.0690.112 0.0240 0.0345

QMRO 0.870 0.0444 0.812 0.353 0.0307 2.0822 0.101 0.3482


0.838 1.090 1.9221 0.048 0.163 0.300 0.1049 0.0299

QMR1 0.900 0.2985 0.248 0.061 0.0193 0.6061 0.142 0.1083


0.657 0.041 0.34,.060.044 0.056 0.095 0.0224 0.0276

QMR2 0.375 0.2545 0.214 1.337 0.0260 1.0720 0.016 0.2039


0.505 0.242 0.2819 0.046 O.Oa~90.079 0.0671 0.0597

QMR4 0.120 0.0317 0.214 0.781 0.0112 1.9864 0.017 0.2525


0.080 0.284 0.7082 0.008 0.072 0.095 0.0714 0.0485

MHV2 0.126 0.0407 0.104 0.032 0.0071 0.0798 0.018 0.0767


0.076 0.335 0.0734 0.006 0.050 0.079 0.0061 0.0321

The general conclusions are that going from 3 temperature independent parameters to 5
or 6 parameters (3 temperature dependent parameters) does not necessarily improve the
phase equilibrium results. Often the binary systems become overcorrelated and erroneous
predictions result. Of the 3 parameter models the OHV3performs a l i t t l e better than the
DDLC3 model, especially for the methanol systems. Both models perform better than the
SCHW3 model. Again substantial improvement can be obtained, when going from 3 to 4
parameters. For the systems shown the OHV4 and MHV2model perform equally well, and
367

somewhat better than QNR4, which is s t i l l better than the 3 parameter models.
For the multicomponent systems QNRO, QMRI and QMRZdo not give good results. When
linear temperature dependent parameters are taken into account the optimal number of
parameters for each of the investigated models are 4 for OHV (constant a), 4 for QMR,
3 for DDLC and 6 for SCHW. Dahl and Mlchelsen (lg90) found that 4 parameters was
adequate in the MHVZ-UNIFACmodel.
In figure 3, where Henry's constant of nitrogen in a N2-CH3OH-H.Omixture at 313 K
is shown as a function of the liquid phase methanol composition, t~e dangers of using
temperature dependent parameters are clear. I t is actually the methanol - water
parameters which causes the prediction of a very high maximumin Henry's constant for
N2 with the DDLC6model. I f only 3 parameters are used in the DDLC3-model, the curve
16ok more like the OHV6 curve, although a maximum is s t i l l predicted. Both OHV6 and
SCHW6 perform very well, and so do the rest of the investigated models with 3 or more
parameters. The experimental data are from Tokunaga (1975).
Figure 4 shows the maximumpressure where 3 phases exist in equilibrium in the
methane-butane-water ternary system. The experimental data are from Ncketta and Katz
(1948). Here i t can be seen that even the QMROmodel can give a good representation of
this. The reason is that the pressure where the liquid hydrocarbon phase disappears
mostly dependon the methane - butane equilibrium. This calculation can thus not be used
in testing the predictive performance of the different models.

w~u~(1) -BLrr~wg(2)-WAYZR(a)
MAXIMUM p R E S S ~ I R g W H E R E 3 P H J ~ E S
Nrm(~m,f( 1) -wm':.,,.~OlX,~)- v^'r~e(3)
HENRrS CONSTANTS FOR NITROG~q AS k P U N C ~ O N OP THE
ML'IltkNDL COMPOS~I']ONIN ~ U(I'UID
100o00 i AT 293.15 K AND ~ BUBBLE POINT OF TIig

E t2o

z . ',

o 400o0 . '~ ..... EXP

..... EXP ~,
. ~ - - - - SCHW6
I

ZL~J 2OO00 I - - - - OHV3


"1- - -MH~
404

o.oo o.~o o.~ o.~ o.e;o ,.6o


METHANOL COMPOSITION (X2)
2o~.. ~66'"~d' ' M6' ~ 6 ~6" ~" ~,~o
TEMPERATURE(K)
Figure 3 Henry's constants for nitrogen in Figure 4 Maximumpressure where 3 phases
a nitrogen-methanol-wa~er system. exists in equilibrium in amethane-butane-
water system.

For the MHV2 model the accuracy decreases compared with the OHV4 model, when large
molecules are present in the mixture. This is due to the group contribution nature of
the model, which arises from the use of UNIFAC. Reestimation would be necessary to
obtain result of the same accuracy as with OHV4, and furthermore i t would be necessary
to estimate interactions between hydrocarbons.

CONCLUSION
Five different mixing rules for the SRK-EOShave been comparedfor phase equilibrium
calculations in complex chemical systems at high pressures. The mixing rules are those
of van der Waals, the Huron-Vidal-NRTL-medel,the MHVZ-UNIFACmodel, the Schwarzentruber
- Galivel-Solastiouk - Renonmodel, and the density dependent local composition model.
All models are investigated both with and without temperature-dependentparameters. The
368

predictive capability is tested by estimating parameters using binary data for systems
containing H20, CO2, N2, HzS, CH]OHand n-alkanes up to n-decane. The multicomponent data
are then predicted-andcompared-with experimental results with the estimated parameters.
For the investigated systems, the Huron-Vidal mixing rule gives the best overall
predictions. In the multicomponent systems investigated, the MHV2 model predicts the
phase equilibria with the same accuracy as the Huron-Vidal mixing rule with 4
parameters. I f temperature dependent parameters are used, i t is necessary to be very
careful when extrapolation in temperature is performed.
ACKNOWLEDGEMENT

We wish to thank M,L. Michelsen for use of his multiphase flash routine.

REFERENCES
Brunner, E., HOltenschmtdt, W. and Schltoht&rle, 6., 1987. Fluid Mixtures at High Pressures, 4. Isothermal Phase
Equilibria in Binary Mixtures Consisting of Methanol+Hydrogen or Nitrogen or Hothene or Carbon Monoxide or Carbon
Dioxide. J. Chem. Thermodynamics. 19: 273-291.
Chang , T. and Rousseau, R.W., 1985. Solubilities of Carbon Dioxide and Methanol-Water at High Pressures, Experimental
Bate and Medelltng. Flutd Phase Equilibria, 23: 243-258.
Crovetto, R., Fernandez-Prini, R. and Japes M.L., 1984. The Solubility of Ethane In Water ut to 473 K, Bar. Benseoges.
Phys. Chem. 88: 484-488.
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