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ELSEVIER Fluid Phase Equilibria 101 (1994) 187-210

Application of the LCVM model to multicomponent systems:


Extension of the UNIFAC interaction parameter table and
prediction of the phase behavior of synthetic gas condensate
and oil systems
Nikolaos Spiliotis, Christos Boukouvalas, Nikolaos Tzouvaras, Dimitrios Tassios*
Laboratory of Thermodynamics and Transport Phenomena, Dept. of Chemical Engineering,
National Technical Unirjersity of Athens, 9, Heroon Poiytechniou Str., Zographou Campus, 15773 Athens, Greece

Received 2 August 1993; accepted in final form 7 June 1994

Abstract

The LCVM model of Boukouvalas et al. (1994) uses the translated and modified Peng-Robinson equation of state
(EoS) coupled with the Original UNIFAC excess Gibbs energy (G”) model and introduces a new mixing rule (a linear
combination of the Vidal and Michelsen ones) for parameter a in the attractive term of the EoS. The UNIFAC
parameter table is here extended to include several gas/CH,, gas/ACH, gas/ACCH,, and gas/gas pairs. Correlation
and prediction results for binary systems are very satisfactory, including systems with large size differences of their
components - where other EoS/GE models fail - as well as at very high pressures (up to 2000 bar).
These parameters are then applied to the prediction of bubble- and dew-point pressures, K values and volume
percent liquid (VPL) of synthetic gas condensate and oil systems. Very satisfactory results are again obtained except,
as expected, in the high pressure section for VPL of gas condensates. The results are comparable with models using
conventional mixing rules with regressed binary parameters, and again superior to other EoS/GE models.

Keywords: Theory; Application; Equation of state; Mixing rules; Cubic; Empirical; Group contribution; Excess
functions

1. Introduction

A recently developed equation of state/excess Gibbs energy (EoS/GE) model, LCVM (Bouk-
ouvalas et al., 1994) provides successful vapor-liquid equilibrium (VLE) prediction of systems
containing components with considerable size differences, where previously proposed models
(MHV2, Dahl et al., 1991; PSRK, Holderbaum and Gmehling, 1991; Fischer, 1993) fail, while

* Corresponding author.

037%3812/94/$07.00 0 1994 - Elsevier Science B.V. All rights reserved


&YDI0378-3812(93)02556-G
188 IV. Spiliotis et al. / Fhid Phase Equilibria 101 (1994) 1X7-210

it matches the performance of the latter ones in predicting the VLE behavior of (polar and
nonpolar) systems with components of similar size, at low and high pressures.
Appendix A provides a brief presentation of the LCVM model, which couples the translated
and modified Peng-Robinson (t-mPR) (Magoulas and Tassios, 1990) EoS with the original
UNIFAC GE model. LCVM features a mixing rule for the EoS parameter CL(= a/bRT) which
is a linear combination of the Vidal (V) and Michelsen (M) mixing rules (Boukouvalas et al.,
1994). Whereas the EoS parameter b is given by a linear mixing rule, parameter x is obtained from:

with 3, = 0.36, Av = - 0.623 and AM= - 0.52.


The LCVM model has been applied to VLE description in polar systems at high and low
pressures as well as in systems containing gases (C02, CH, and C,H,) with n-alkanes. For this
purpose, UNIFAC interaction parameters for the pairs COZ/CH2, CH&H2 and &H&H2 were
determined for use with LCVM.
The purpose of the present work is to enhance the gas-related UNIFAC interaction parame-
ters currently available for the LCVM model, aiming at the prediction of the phase behavior of
multicomponent systems. The pertinent pairs include N&H,, gas/gas, gas/ACH and gas/
ACCH?, so that systems containing gases (CO?, CH,, C2H6, N2) together with various types of
hydrocarbons can be handled. Bubble- and dew-point pressures, K values and VPL of synthetic
oils and gas condensates have been predicted. LCVM results are presented and they are
compared with those obtained through the MHV2 and PSRK models as well as through the use
of conventional mixing rules,

2. Interaction parameter table extension

2.1. Interaction parameters

In addition to the CO&H2, CH,/CH, and C2H,/CH, pairs for which interaction parameters
are already available (Boukouvalas et al., 1994), UNIFAC interaction parameters for use with
LCVM are here determined for 16 more pairs: N2/CH2, C02/CH4, CO&H,, COZ/N2, CH,/
CzHs, CH,/N,, C1H6/NZ, CO,/ACH, COJACCH2, CHJACH, CHJACCH,, C,H,/ACH, C2H6/
ACCH,, N,/ACH, NJACCH 2 and H2S/CH2. Pure component parameters used for the gases
considered here are shown in Table 1 and those for the aromatic compounds in Table 2.
Interaction parameter values are presented in Table 3 along with the temperature range covered
by the data base for each pair. The matrix of available parameter values (UNIFAC Revision V;
Hansen et al., 1991) is shown in Fig. 1, which is revised to include the parameters estimated in
this study.
Temperature-dependent interaction parameters are introduced and the UNIFAC expression
(Fredenslund et al., 1975) is replaced by:

A,+B,.(T-298.15)
!?, = exp - (2)
T
N. Spiliotis et al. / Fluid Phase Equilibria 101 (1994) 187-210 189

Table 1
Pure compound parameters used in the LCVM model: gases

Gas T, (IQ p, (bar) w K’ Q

N2 126.10 33.94 0.0403 0.9340 0.985


H,S 373.55 90.07 0.0814 1.1665 1.163
CO* 304.19 73.82 0.2276 1.2960 1.261
CH, 190.55 45.99 0.0110 1.1290 1.124
CZH, 305.42 48.80 0.0990 1.8022 1.696

Table 2
Pure compound parameters used in the LCVM model: aromatics

Compound T, (K) P, (bar) w Cl c2 c3

Benzene 562.16 48.98 0.210 0.712993 -0.396127 1.369983


Toluene 591.80 41.06 0.262 0.769212 -0.181845 0.705585
n-Pentylbenzene 679.90 26.00 0.437 -
I-Methylnaphthalene 112.04 36.60 0.348 0.794445 0.702066 -1.197180

Table 3
UNIFAC interaction parameters for the LCVM model

i T(K) A>j(K) A,,W B, B,i

NV CO* 218-298 29.41 214.96 0.0 0.0


N* CH, 89-189 13.25 53.23 0.0 0.0
N2 C,H, 120-290 -2.93 157.Y8 0.0 0.0
N* CH2 273-423 19.81 179.93 - I .7517 2.3079
NZ ACH 348-398 114.75 249.24 - 1.4886 0.8773
K ACCHz 313-392 143.60 152.36 - 1.9868 2.5958
H2S CH2 278-423 188.51 112.78 0.4882 -0.5823
co2 CH, 153-283 154.35 108.47 0.0 0.0
co2 W, 222-298 144.29 122.91 0.0 0.0
co2 CH2 273-423 110.6 116.7 0.5003 -0.9106
co2 ACH 213-414 2.21 145.49 - 1.6639 1.7330
co* ACCH, 311-422 - 17.14 223.21 - 1.7754 1.1093
CH, C,H, 130-283 9.78 7.92 0.0 0.0
CfL CH2 213-428 -25.0 88.0 -0.3000 0.3000
CH, ACH 313-421 - 13.57 105.64 -0.4534 0.2566
CH, ACCH, 255-422 -1.39 91.07 - 1.5894 0.1498
C2H, CH2 255-430 120.0 - 87.0 2.3500 - 1.3900
W, ACH 273-433 -4.10 58.13 -0.9188 0.7691
W4 ACCH, 298-318 75.16 18.74 - 0.7926 -0.9362
N. Spiliotis et al. I Fluid Phase Equilibria 101 (1994) 187-210

1
2

ii& 3
4

Fig. I. Original UNIFAC interaction parameter matrix available for use with the LCVM model.

For the NJCH, pair, the data base consists of N,/n-alkane systems, including propane
through n-decane, n-dodecane and n-hexadecane, in the temperature range 273-423 K. The
values R’ = 0.934 and Q = 0.985 were used for NZ, whereas for the other gases the correspond-
ing R’ and Q values are the same as in Boukouvalas et al. (1994; see Table 1).
For the gas/gas pairs, each data base includes the corresponding binary system. Temperature-
independent UNIFAC interaction parameters were determined since they gave a satisfactory
description of the available data in the whole temperature range. With such parameters,
furthermore, we avoid the uncertainties of extrapolation with respect to temperature, greater
than 100 K in many cases, when applied to multicomponent data.
For the gas/ACH pairs, each data base includes binary systems with benzene and the
corresponding gas, and for the gas/ACCH, pairs, the data base consists of binary systems with
N. Spiliozis et nl. / Fluid Phase Equilibria 101 (1994) 187-210 191

toluene, except for C,H,/ ACCH2, where C2H6/ n-pentylbenzene and &H,/l-methylnaphthalene
data were used.
In all cases, parameter values were determined by minimizing the average absolute percent
deviation in bubble-point pressure.

2.2. Results

Table 4 presents details on the data base and results for the N,/CH, pair, including
temperature and pressure ranges, literature references, deviations in bubble-point pressures and
predicted vapor phase mole fractions. Results with the MHV2 and PSRK models are also
included for comparison purposes. In addition to the n-alkanes used in the parameter determi-
nation procedure, prediction results for the N2/nC4 and two N,/i-alkane systems are included
in Table 4. Fig. 2 shows typical results for N&r-alkane systems. Table 5 presents similar
information for the H,S/n -alkane systems.
Table 6 presents information on the data base used for the gas/gas interaction parameters
determined in the present work, as well as results with the LCVM model and, in addition, results
with the PSRK and MHV2 models. Fig. 3 shows results for the system CH4/C02 that are typical
of the performance of the three models. The poor results with the MHV2 model are due to the
use of zero interaction parameters for these gas pairs, suggested by Dahl et al. (1991).
Table 7 presents information on the data bases and results for the systems that were used for
the determination of gas/ACH and gas/ACCH, interaction parameters.
In these tables, errors in AP% greater than 30%, are presented by the symbol > 30, since they
would not assist the comparison between the models any further.

Table 4
Results for NJn-alkane systems

N: T(K) P (bar) Data NDP MHV2 PSRK LCVM


with range range reference
APO/o Ay AP% By APO/o By
(XlW ( x 100) (x100)

C3 273-353 13.8-159.0 W, 621 40 21.9 4.0 6.3 1.8 5.4 2.4


nC, 273-41 I 7.8-234.6 [5, 41. 61, 641 61 28.0 3.1 6.5 1.3 6.8 1.8
nG 277-344 2.5-207.8 [251 31 5.3 0.6 4.2 1.0 5.3 0.4
nC6 311-411 17.2-344.7 I571 44 10.5 2.5 11.2 1.4 6.1 0.9
nG 305-413 19.6-998.5 [1, 23. 35, 381 119 21.5 1.3 10.4 0.9 6.2 1.1
nC8 322-344 32.3-350.4 [381 12 10.9 - 1.3 6.8 -
nc, 322-344 37.2-347.4 [381 12 14.3 - 3.4 6.0 -
nG0 311-411 17.2-344.7 151 59 18.6 0.3 17.3 0.2 8.6 0.2
42 328-367 31.0-346.9 [381 16 21.5 - 22. I 9.0 -
nC14 321-434 84.3-2137.0 [91 84 >30 a >30 a 4.6 b -
nG6 373-423 49.0~~490.0 ~231 11 230 a >30 a 6.4 -
iC, 255-395 4.2-207.7 ~241 50 10.7 I.6 4.6 1.7 4.9 b 1.8
iC, 278-317 1.8-207.8 ~321 47 8.0 I.0 4.5 1.7 5.8 b 1.1

a AP% greater than 30 (do not apply).


b Binary not used for the parameter estimation (prediction).
192 IV. Spiliotis et al. /Fluid Phase Equilibria 101 (1994) 187-210

Fig. 2. The P-X-J) diagram for the system N,,W,, at 378 K.

Table 5
Results for H,S/n-alkane systems

H2S T WI P ( bar) Data NDP MHV2 PSRK LCVM


with range range reference
AP% Ay AP% Ay AP% Ay
( x 100) ( x 100) ( x 100)

G 366-418 14.8-78.9 [371 6.6 2.3 3.4 2.4 2.2 2.1


nC, 278-411 1.4-89.6 [59] i: a 7.1 1.5 3.9 1.4 1.9 1.7
nC, 323-423 8.4-75.5 [33] 24 4.4 0.5 2.0 0.3 1.8 0.8
G 311-394 6.1-95.5 [5ll 16 4.1 0.5 2.7 b 0.4 3.1 b 0.6
G 278-411 1.4-110.3 [60] 35 7.8 0.2 4.7 0.2 4.1 0.3
Go 323-423 4X-76.7 iI41 28 >30 c 28.8 - 4.5 ~

a Bubble point pressure calculation not possible for 16 data points with all models.
b Binary not used for the parameter estimation (prediction).
’ AP% greater than 30 (do not apply).

2.3. Discussion

The gas/gas and gas/CH,, ACH, ACCH, UNIFAC interaction parameters presented here
allow the prediction of a large number of binary systems. Next, we present our observations on
the performance of the LCVM model for these binary systems, and compare LCVM with other
models.
N. Spiliotis et al. 1 Fluid Phase Equilibria 101 (1994) 187m210 193

Table 6
Results for gas/gas systems

System T(K) P ( bar) Data NDP MHV2 a PSRK LCVM


range range reference
AP% Ay APO/o Ay AP% Ay
( x 100) ( x 100) (x 100)

N,/COz 218-298 12.8 167.3 a 200 130 b 2.8 1.0 3.6 1.2
N,/CH, 89-189 1.0-50.3 b 436 13.1 3.1 1.1 0.7 0.9 0.6
N&H, 120-290 3.5-134.7 c 159 >30 9.0 1.2 5.1 1.0
CWCH, 153-283 6.9-85.2 d 299 20.0 6.1 2.2 0.8 2.1 0.7
CO&H6 222-298 6.2-66.3 e 242 21.8 6.4 1.2 0.9 2.1 0.9
CH,/C,H, 130-283 1.2266.6 f 248 4.9 0.7 3.1 0.7 1.4 0.5

a. [Z-4, 27: 47, 65, 71-731.


b. [6, 7, 30, 31, 42, 44, 56, 661.
c. [16, 18, 31, 671.
d. [2, 4, 8, 11, 26, 46, 50, 651.
e. [g, 15, 17; 20, 21, 48, 541.
f. [8, 18, 45, 58, 68-701.

a MHV2 uses zero interaction parameters for all gas/gas systems and, therefore, bubble-point pressure calculation is
not possible for many data points.
b AP% greater than 30 (do not apply).

Fig. 3. The P-x-y diagram for the system CH,/CO, at 270 K.


Table I
Results for gas/aromatics systems

System T(K) P (bar) Data reference NDP MHV2 PSRK LCVM


range range
AP% Ay AP% Ay AP% Ay
( x 100) ( x 100) ( x 100)

NJbenzene 348-398 62.1-307.1 1431 18 2.0 0.1 8.4 0.5 1.2 0.1
N, /toluene 313-392 29.0- 1000.0 [341 15 >30” 5.2 0.7 4.0 0.5
CO,/benzene 273-414 6.2- 153.9 [lo, 19, 22, 128 5.0 1.3 4.0 1.4 2.5 1.4
28, 49, 531
COJtoluene 311-422 3.3-152.9 [52, 631 35 6.6 0.8 3.4 0.5 2.8 0.5
CH,/benzene 313-421 6.9-374.2 [ 12, 36, 391 38 >30 5.6 1.7 4.5 1.8
CH,/toluene 255-422 3.5-487.5 [ 12, 36, 39, 401 78 >30 14.8 0.9 8.4 1.2
C,H,/benzene 213-433 7.8-82.7 129, 551 53 1.5 0.6 6.4 0.7 1.5 0.3
C,H,/n-pentyl benzene 298-318 5.1-53.9 [I31 42 14.7 - 9.1 - 3.8 -
C,H,/l-methyl napthalene 298-318 7.1-55.5 [131 24 >30 1.4 ~ 5.4 -

a AP% greater than 30 (do not apply).


N. Spiliotb et al. / Fluid Phase Equilibria IO1 (1994) 187-210 195

(1) The successful performance of the LCVM model, despite increasing asymmetry of the
components in a mixture and the corresponding difficulties with the MHV2 and PSRK models
under such conditions, shown initially in the original paper, are demonstrated again here (see
e.g. Tables 4, 5, and 7 and Fig. 2).
(2) The LCVM model appears to give satisfactory results up to very high pressures as
suggested by the results for N&CT (Table 4) and N,/toluene (Table 7) systems that were
involved in the parameter estimation. However, for the system N2/nCi4 (de Leeuw et al., 1992),
this was not the case. Here, the estimated parameters have been used for prediction of
bubble-point pressures up to 2140 bar. Although PSRK performs poorly, the LCVM model
yields extremely good results (AP% = 4.5 only). Figs, 4(a) and 4(b) display the generally good
performance of the LCVM model through selected isopleths of the system; the somewhat poorer
results obtained with LCVM in the lower temperatures are surprising considering the tempera-
ture range of the data base used for the N&H2 parameter evaluation. On the other hand,
PSRK shows good results at low mole fractions of nitrogen, but its behavior deteriorates as this
quantity increases. Note, for example, that in Fig. 4(a) the curve for PSRK, corresponding to
nitrogen liquid phase mole fraction x,., = 0.697, is not included due to the large deviation from
the experimental bubble-point pressures.
The error in bubble-point pressure with LCVM is only slightly higher than that obtained
through regression of the data with the PR EoS using quadratic mixing rules for the parameters
a and b and temperature-dependent coefficients k, and 1,in the combining rules (AP% = 3.4), i.e.
an EoS model with a total of four parameters regressed from the data (de Leeuw et al., 1992).
A similar behavior is observed with the prediction of the system Cl/nCi4 (up to 489 bar),
where LCVM gives results with APO!= 9.4, whereas the regression with the previous method
gives AP% = 3.4 (de Leeuw et al., 1992).
(3) The MHV2 model sets all gas/gas interaction parameters equal to zero (Dahl et al., 1991).
This fact explains its rather poor performance in describing most of the gas/gas systems as
shown, for example, in Fig. 3. It is also noted that the PSRK model considers ethane as two
CH3 groups and not a gas with separate interaction parameters; however, its performance with
the gas/C,H, systems is rather good, probably because the pertinent gas/CH, pairs have been
correlated with four or six parameters.
(4) Very good results are obtained for gas/aromatics systems with LCVM (Table 7). PSRK
results are generally good, but somewhat worse than LCVM. On the other hand, the perfor-
mance of MHV2 is erratic. Note. however, that the temperature range involved in some of the
parameter estimation is limited and caution should be exercised when extrapolating with respect
to temperature.

3. Prediction for synthetic gas condensate and oil systems

3.1. Results

The multicomponent mixtures used in the present work are synthetic oils and gas condensates
(Yarborough, 1972) and COJsynthetic oil systems (Turek et al., 1980). The experimental data
include bubble- and dew-point pressures as well as equilibrium constants from isothermal flash
196 N. Spilioru et al, I Fluid Phase Equilibria 101 (lYY4) 187-210

(4

5017 I I / rrrrT-rrrm-&--+
300 350 450

(b) -v>
Figs. 4. (a) and (b). Prediction of bubble-point pressures at selected isopleths for the system N,/nC,,(de Leeuw et al.,
1991).

calculations, together with volumetric data (VPL). Tables 8(a) and (b) present the compositions
of the multicomponent systems used.
Table 9 presents bubble-point pressure prediction results and Table 10, the same for
dew-point pressure, along with the available experimental data. Results from the PSRK model
IV. Spiliotis et al. / Fluid Phase Equilibria 101 (1994) 187-210 197

Table 8(a)
Composition (% mol) of Yarborough mixtures
_~
Mix/T (OF) %N, %CO, %C, o/UC, %C, ?&/on
C, %nC, %tol

*3/200 76.35 5.68 2.95 5.29 3.13 3.04 2.96


4/200 63.38 4.70 2.35 10.50 7.42 5.88 5.11
5/200 85.11 6.91 3.11 I .69 1.30 0.94 0.94
*6/150 80.69 6.02 3.04 3.56 2.65 2.02 2.02
61200 81.59 5.95 2.98 3.39 2.49 1.87 1.73
61250 81.72 6.00 2.94 3.44 2.42 1.70 1.78
7,‘200 82.52 5.45 2.92 2.04 1.36 1.08 4.63
8/200 80.97 5.66 3.06 4.57 3.30 2.44
K/200 0.48 0.16 80.72 5.92 2.98 4.29 3.04 2.42
*8E/loo 0.48 0.19 80.32 6.02 3.07 4.38 3.11 2.43
SE/l50 0.49 0.21 81.34 6.01 3.00 4.10 2.78 2.08
*20/100 15.00 0.17 64.38 4.15 3.01 3.05 2.06 1.59 6.56
*20A/lOO 12.70 15.06 54.90 3.59 2.58 2.56 1.73 1.35 5.48
231250 15.20 0.19 63.88 4.22 3.08 3.09 2.13 1.59 6.64

* Near critical mixture.

Table 8(b)
Composition (% mol) of Turek synthetic oil

%CO, %C, D/UC, %C, %nC, %n c, %n C, %C, %n C, SK,,

0.00 a 34.67 3.13 3.96 5.95 4.06 3.06 4.95 4.97 30.21 5.04

a The amount of CO1 that is mixed with the synthetic oil is defined in each case (see Table 9). The relative amounts
of the other components are fixed.

are also included, in addition to those with the LCVM model for comparison purposes. In Table
10, results for t-mPR EoS with conventional mixing rules (k,) are included as well (from
Anastasiades et al., 1994). The saturation pressure results for the two Turek mixtures are shown
graphically in Figs. 5 and 6. Results with the MHV2 are poor, again because of the zero gas/gas
interaction parameters, and are not included.
Table 11 presents results from isothermal flash calculations, for the LCVM model as well as
for the PSRK one. In this table, the overall error in the equilibrium ratios for each mixture and
temperature is presented.
The error in K values is given by:

average d 1nK = NC, &p.yf,g Iln&,rxp - lnKii,,,l(

where the summations extend over all the components and data points (various pressures at
each isotherm), NC and NDP being their respective numbers.
The results presented in Fig. 7 are typical of the performance of the LCVM model in
predicting equilibrium ratios of the systems studied and composed of a synthetic oil containing
dissolved CO,. Fig. 8 present equilibrium ratios, for a synthetic gas condensate, for selected
198 ,V. Spiliotti et al. 1 Fluid Phase Equilibria 101 (1994) 187-210

Table 9
Bubble-point pressure predictions for multicomponents mixtures

Turek oil T (K) Pexp. APO/u


%CO, (bar)
PSRK LCVM
,-
00.00 101.97 3.0 2.7
19.89 114.80 2.4 3.3
39.73 121.35 2.9 0.8
49.69 121.49 2.6 0.4
59.70 119.28 2.2 1.1
322.0
69.52 115.07 1.1 2.2
74.82 112.25 2.8 0.5
79.85 109.08 3.4 1.7
84.87 105.56 3.7 2.6
89.68 101.84 3.5 2.8
00.00 107.49 3.1 1.9
20.22 123.69 0.8 1.3
40.35 134.93 1.9 1.0
60.44 338.7 136.38 0.3 4.8
79.96 131.21 1.1 2.7
85.30 128.38 B z

Yarborough 366.5 217.53 2.7 3.1


4/200

a Calculation failure

Fig. 5. Prediction of the saturation pressure curve for a synthetic oil (Table S(b)) at 322.0 K from Turek et al. (1980).
N. Spilioris et al. /Fluid Phase Equilibria 101 (1994) 187-210 199

Table 10
Dew-point pressure predictions for multicomponent mixtures

T(K) Pexp. AP%


(bar)
t-mPR/k,, a PSRK LCVM

%CO, Turek Synthetic Oil


93.38 99.53 _b 3.5 3.0
94.98 322.0 98.80 3.6 3.3
96.66 97.29 3.2 3.0

87.30 127.07 2.3 0.4


90.31 338.7 125.28 2.5 1.2
95.21 120.59 3.8 3.8

Mix/T (OF) Yarborough Mixtures


3/200 366.5 226.15 12.2 10.4 9.1
5/200 366.5 189.54 0.1 3.9
6/150 338.7 229.60 11.6 9.1 8.5
6/200 366.5 219.25 6.4 7.5 5.1
6/250 394.3 199.26 3.4 2.0
7/200 366.5 234.08 11.5 10.0 5.0
8C/200 366.5 216.50 5.1 1.5 6.9
BE~IOO 310.9 218.01 11.0 7.3 10.7
8E/l50 338.7 217.87 8.2 8.3 9.9
20/100 310.9 273.58 31.8 13.1 21.3
20A/lOO 310.9 331.09 21.4 15.8 20.9
23/250 394.3 263.38 18.7 14.2 10.4

a Results from Anastasiades et al. (1994).


b Results not available.

mixture components, comparing the performance of the LCVM model with that of PSRK. In
order to make this figure easier to study, the curves for some components are not included.
Typical prediction results for VPL obtained from isothermal flash are shown in Fig. 9 for
synthetic oils. The same is shown for synthetic gas condensates in Fig. 10 for a near-critical
system and in Fig. 11 for a far-critical one.

3.2. Discussion

The UNIFAC interaction parameters estimated in the previous section, together with those
presented in the original paper (Boukouvalas et al., 1994), allow the prediction of a large
number of multicomponent systems, involving gaseous components. We present next our
observations on the performance of the LCVM model and compare our model with other
methods when possible.
(1) The assumption that gas/gas interaction parameters can be set equal to zero for the MHV2
model (Dahl et al., 1991) affects, as expected, the results of the multicomponent systems; e.g. the
200 N. Spiliotis er al. /Fluid Phase Equilibria 101 (1994) 187-210

q oooo BLbble Exp. Pts


nn~dn Dew cxp Pts
~ LCVM
_ _ PSRK

0.0 0.2 0.3 0.6 08 1.0


CO2 mde fraction
Fig. 6. Prediction of the saturation pressure curve for a synthetic oil (Table S(b)) at 338.7 K from Turek et al. (1980).

ooooo N,
OOOOL co2
nnnnn Cl
00000 c,
***** c,
***** “C,
***** nCs
9009Q :1&
00000 IC,
BOBQB lC*
ceeee nC,c
. . . . . nc,,

Fig. 7. Pressure dependence of K values for a synthetic oil containing 20% CO, (Table 8(b)) at 322 K from Turek
et al. (1980). Prediction with the LCVM model.
N. Spiliofis et al. / Fluid Phase Equilibria 101 (1994) 187-210 201

Table 11
Absolute average error in 1nK values (Eq. (3)) for multicomponent mixtures

T(K) P range NDP A In K


(bar)
PSRK LCVM

%COz Turek Synthetic Oil


20.00 35.5-107.1 6 0.2109 0.1624
69.52 322.0 34.8-111.6 6 0.1318 0.0995
89.65 50.1-103.7 7 0.3384 0.2672

79.96 41.6-130.6 I 0.1635 0.1179


338.7
95.39 69.0-117.4 5 0.1430 0.1312

Mix/T (“F) Yarborough Mixtures


3/200 366.5 80.0-208.6 5 0.0876 0.0653
4/200 366.5 15.7-200.2 8 0.0990 0.0769
5/200 366.5 43.2-167.5 5 0.0659 0.0626
6/150 338.7 106.9-209.5 4 0.0953 0.0943
6,‘200 366.5 37.3-208.2 6 0.0973 0.0764
6/250 394.3 37.6-174.0 5 0.0735 0.0528
7/200 366.5 37.5-210.2 6 0.1167 0.0801
8C/200 366.5 38.1-209.3 6 0.1142 0.0811
8E/lOO 310.9 16.2-209.6 7 0.1623 0.1593
8E/150 338.7 17.9-208.8 7 0.1279 0.1091
20/100 310.9 37.0-310.0 9 0.1341 0.151I
2OAjlOO 310.9 36.3-255.0 7 0.1185 0.1584
23/250 394.3 37.2-248.8 7 0.1876 0.1552

obtained errors in K values for the Turek and Yarborough mixtures are typically three to four
times larger than those with the LCVM and PSRK models shown in Table 11. For this reason,
results from MHV2 have not been included in the figures that follow and the tables pertaining
to multicomponent systems.
(2) The results for bubble-point pressure prediction of the synthetic oil systems (Table 9; Figs.
5 and 6) indicate that LCVM yields satisfactory results, similar to those of PSRK, and those
obtained with the t-mPR EoS with conventional mixing rules and interaction parameters (k,)
obtained by regressing the corresponding binary data.
(3) Equally good results are obtained in the prediction of the dew-point pressures, shown in
Table 10 with LCVM and PSRK models. They are not very satisfactory, however, for the five
near-critical Yarborough mixtures, but better than those obtained with the t-mPR/k, approach.
Notice, however, that owing to numerical difficulties the critical region could not be predicted
in all cases (Figs. 5 and 6).
(4) Table 11 and Figs. 7 and 8 indicate that LCVM gives satisfactory prediction of K values,
which are similar, and occasionally better, than those of PSRK. The large errors in K values for
nC14, as shown in Fig. 7, can be attributed to the uncertainties in the experimental data arising
from the extremely low vapor phase mole fractions involved.
202 .N. Spiliobs et al. /Fluid Phase Equilibria101 (1994) 187-510

DO000 c,
3uooo c,
naaan 1-S

00000 MC,
****a nC,o

/
*

a_//..i
7.7
__ LCVM
_ _ PSRK

Fig. 8. Comparison of various models in predicting the pressure dependence of K values for selected components of
a synthetic gas condensate (Mixture 8E/150. Table 8(a)), from Yarborough (1972).

0 50 100 150 200 253


P (bar)

Fig. 9. Prediction of VPL curve for a synrhetic oil (Mixture 4/200, Table 8(a)), from Yarborough (1972).
IV. Spiliotir et al. 1 Fluid Phase Equilibria 101 (1994) 187-210 203

18
- 00300 Exp. Pts
- LCVM
_ _ PSHK /-

.-
3
u

0 50 100 150 200 25c


P (bar)
Fig. 10. Prediction of VPL curve for a near-critical synthetic gas condensate (Mixture 6/150, Table X(a)), from
Yarborough (1972).

9
_ 00~00 Exp. Pts
~ LCVM
8: _ _ FSRK /-
tbmPR / k;, / \

,,,,,,,,,,,,,,,,,,,,,,,,,,141,‘)1
0 50 1oc 150 200 2 0
P (barj
Fig. 11. Prediction of VPL curve for a far-critical synthetic gas condensate (Mixture 6/200, Table 8(a)), from
Yarborough (1972).
(5) Prediction results for the VPL obtained from isothermal flash indicate that LCVM,
t-mPR/k,, and PSRK, perform similarily, as shown in Figs. 9- 11. Notice, however, that PSRK
often overpredicts higher maximum VPL than LCVM or conventional mixing rules do. The
results are very satisfactory for the case of oils and the low-pressure part of gas condensates, but
not for the high-pressure one, where the errors in the predicted dew-point pressure lead to
substantial error in the VPL, especially for the near-critical mixtures.

4. Conclusions

The original UNIFAC interaction parameter table used with the LCVM model has been
enhanced to include gas/gas, gas/CHz, gas/ACH and gas/ACCHz parameters for the gases CO?,
CH4, C2H6, NT and H$.
Very satisfactory correlation and prediction results are obtained for both symmetric and
asymmetric systems, and for very high pressures reaching over 2000 bar in the case of prediction
for the N&zC,~ system.
Application to the prediction of the VLE behavior of synthetic gas condensate and oil
mixtures shows that the LCVM model gives satisfactory results for bubble- and dew-point
pressures, VPL and phase compositions, outperforming other EoS/GE models; less satisfactory
results are obtained, however, for VPL near high pressure dew-points. Finally, the results are
comparable with those obtained with conventional mixing rules using k, parameters determined
by regressing the corresponding binary data. The LCVM model, thus, provides satisfactory
prediction of multicomponent mixtures without the need for the tedious search of binary data.

Acknowledgments

We would like to thank Professor S. Stamataki for useful discussions and for providing us
with some data, as well as Mr. K. Anastasiades for making his results available to us prior to
publication.

Nomenclature

EoS attractive term (cohesion) parameter


Ii mixing rule constant
A,, B, coefficients defined in Eq. (2)
b EoS covolume parameter
Cl, c2, c; pure compound parameters as defined in Eq.(AS)
GE excess Gibbs free energy
k binary interaction parameter in quadratic mixing rule for parameter a
K equilibrium ratio
binary interaction parameter in quadratic mixing rule for parameter b
P pressure
IV. Spiliotis et al. /Fluid Phase Equilibria 101 (1994) 187-210 205

Q structural group or molecular surface area


R gas constant
R’ structural group or molecular volume
t volume translation
T temperature, K
V molar volume
X mole fraction for both phases

Greek symbols

c1 EoS parameter, CI= a/bRT


Y activity coefficient
i parameter of LCVM model as defined in Eq.( 1)
‘y, interaction energy parameter in UNIFAC
w acentric factor

Subscripts

C critical value
cal calculated value
exp experimental value
i component i
M Michelsen mixing rule
reduced property
; Vidal mixing rule

Table symbols

* near-critical system
_ vapor phase composition not available
=
- calculation failure
> 30 APO/ogreater than 30 (do not apply)
AlnK error in K defined in Eq.(3)
AP% average absolute error % in bubble- or dew-point pressure
AY average absolute error in vapor phase composition
NDP total Number of Data Points per system

Appendix A: The LCVM model

The equation of state

The EoS used is the translated and modified Peng-Robinson (t-mPR) EoS (Magoulas and
Tassios, 1990):
206 A’. Spiliofis et al. /Fluid Phase Equilibria 101 (1994) 187-210

RT a
(A1)
P=w-b-(V+f)(V+f+b)+b(V+t-b)

The pure component parameter a is:

a = 0.45724Yf(7.) I (A3

For nonpolar compounds (gases and alkanes), f(T,) is related to the acentric factor w :

f(TJ = [ 1 t ??I(1 - &)I* (A 3)

m = 0.384401 + 1.52276~ - 0.213808~~ + 0.034616~0~- 0.001976w4 (A4)


Compared with the PR EoS using a single expression of m = f(w), similar to Eq. (A4), Eq.
(Al) provides similar overall vapor pressure (P”) predictions, but better ones at low P” levels.
Additionally, it gives very good predictions of saturated liquid densities, especially for com-
pounds with large o values, through the introduction of the translation.
For other (polar, aromatic, etc.) compounds, we have used the Mathias and Copeman
expression (1983).
If T, < 1.0:

f(T,) =[l +c1(1 -fi) +cJl -\K)z+cj(l -&)‘I’ (A5)


If T, > 1.0:

fu3=[1+c*(l-,:T;)12 (A61
where cl, c2, c3 are compound specific constants given in Table 2.
The pure component parameter b is given by:

b = 0.0778F (‘47)
c

The translation t does not affect VLE calculations and its influence on the volumetric
prediction of the synthetic oil and gas mixtures was insignificant due to the small amount of
components with large o values present in them (nClo and n&J. The expression for t is given
by Magoulas and Tassios (1990).
The T,, PC and w values suggested by Magoulas and Tassios (1990) were used for all
n-alkanes. For other compounds, these values are presented in Tables 1 and 2.

The mixing rules

The mixing rule for the EoS parameter a( =a/bRT), is given by:

(‘48)

with i = 0.36. Av = - 0.623 and AM = - 0.52,


N. Spiliotis et al. / Fluid Phase Equilibria 101 (1994) 187-210 207

For parameter b, the conventional linear mixing rule is used:

b = xx,b, (A9)

The GE model

Original UNIFAC (Fredenslund et al., 1975) is used (in Eq.(A8)), as it is a widely applicable
GE model, which is being updated and extended regularly. The interaction parameters used in
this work, were taken from a recent revision (Hansen et al., 1991) and from Boukouvalas et al.
(1994).

The expression for the fugacity coejicients gioen by the LCVM model

The fugacity coefficient of component i in mixture, for the PR EoS, is given by:

1
P(V-b) cCj ,ln
_ln RT __
2s
with:

(All)
where yi refers to the activity coefficient coming from the GE model.

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