J. Chem. Eng.

Data 2001, 46, 169-171 169

Liquid-Liquid Equilibria of Quaternary and Quinary Systems

Including Sulfolane at 298.15 K
Jian Chen,* Jianguo Mi, Weiyang Fei, and Zongcheng Li
Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

Liquid-liquid equilibria (LLE) were measured at 298.15 K for three quaternary systemsshexane +
heptane + toluene + sulfolane, heptane + octane + m-xylene + sulfolane, and heptane + benzene +
toluene + sulfolanesand for two quinary systemsshexane + heptane + toluene + m-xylene + sulfolane
and heptane + octane + benzene + m-xylene + sulfolane. The equilibrium data of these systems are
compared with those predicted using the nonrandom two-liquid (NRTL) model with parameters fitted
from ternary LLE data. The predicted data are in good agreement with experimental ones.

Introduction Table 1. LLE Data of Quaternary Systems Including

Sulfolane at 298.15 K
Because sulfolane has been widely used as a solvent in
hydrocarbon-rich phase sulfolane-rich phase
the recovery of high-purity aromatics, such as benzene,
toluene, and xylenes, from refinery process streams, many x1 x2 x3 x1 x2 x3
investigators have studied the liquid-liquid phase equi- Hexane (1) + Heptane (2) + Toluene (3) + Sulfolane (4)
libria for ternary systems containing sulfolane and aro- 0.699 0.139 0.151 0.012 0.004 0.068
matic hydrocarbons (De Fré and Verhoeye, 1976; Hassan 0.236 0.515 0.241 0.005 0.013 0.106
et al., 1988; Cassell et al., 1989a,b; Masohan et al., 1990; 0.407 0.240 0.336 0.013 0.008 0.155
0.201 0.250 0.514 0.014 0.017 0.271
Mondragón-Garduño et al., 1991; Letcher et al., 1996; Lee 0.177 0.151 0.603 0.024 0.024 0.381
and Kim, 1995, 1998; Kao and Lin, 1999a,b). Almost all of
the literature data concern ternary systems. In most of the Heptane (1) + Octane (2) + m-Xylene (3) + Sulfolane (4)
0.442 0.380 0.168 0.007 0.003 0.058
above literature, the well-known nonrandom two-liquid 0.305 0.363 0.313 0.007 0.004 0.087
(NRTL, Renon and Prausnitz, 1968) and UNIQUAC 0.331 0.197 0.433 0.012 0.005 0.136
(Abrams and Prausnitz, 1975) models were used for the 0.136 0.251 0.579 0.006 0.008 0.191
correlation and prediction of liquid-liquid equilibria (LLE). 0.158 0.052 0.688 0.018 0.005 0.316
In a previous paper (Chen et al., 2000a), LLE data for Heptane (1) + Benzene (2) + Toluene (3) + Sulfolane (4)
ternary systems including cyclohexane, 1-heptane, benzene, 0.671 0.163 0.147 0.014 0.106 0.068
toluene, and sulfolane had been shown. Further, values for 0.635 0.231 0.114 0.018 0.165 0.057
0.505 0.188 0.285 0.023 0.132 0.150
the quaternary systems cyclohexane + 1-heptene + ben- 0.412 0.390 0.154 0.038 0.310 0.097
zene + sulfolane and cyclohexane + 1-heptene + toluene 0.294 0.197 0.431 0.045 0.155 0.277
+ sulfolane were shown and compared with the values
predicted using the NRTL equation with parameters Table 2. LLE Data of Quinary Systems Including
regressed from the ternary systems. Sulfolane at 298.15 K
In this paper, quaternary and quinary LLE data includ- hydrocarbon-rich phase sulfolane-rich phase
ing sulfolane were measured and compared with values x1 x2 x3 x4 x1 x2 x3 x4
predicted using the NRTL equation with parameters
Hexane (1) + Heptane (2) + Toluene (3) +
regressed from ternary systems. The results show that m-Xylene (4) + Sulfolane (5)
quaternary and quinary LLE can be predicted using the 0.227 0.492 0.132 0.138 0.004 0.009 0.051 0.034
NRTL equation with parameters from ternary systems. 0.407 0.166 0.198 0.210 0.012 0.006 0.091 0.067
0.204 0.314 0.283 0.176 0.008 0.012 0.125 0.058
Experimental Section 0.280 0.150 0.171 0.364 0.015 0.008 0.076 0.131
0.162 0.139 0.472 0.136 0.019 0.018 0.236 0.065
Materials. Sulfolane, imported by China Medicine Co., Heptane (1) + Octane (2) + Benzene (3) +
was purified by distillation. The fraction distilling between m-Xylene (4) + Sulfolane (5)
383 K and 393 K at 0.67 kPa was collected for use. The 0.276 0.475 0.162 0.084 0.004 0.004 0.094 0.019
purified sulfolane was transparent without smell and color. 0.451 0.240 0.174 0.126 0.008 0.003 0.099 0.032
0.232 0.355 0.247 0.150 0.007 0.009 0.163 0.041
Other chemicals were produced by Beijing Chemical Co.
0.272 0.191 0.202 0.302 0.011 0.006 0.130 0.094
and were purified also by distillation. All of the chemicals 0.156 0.148 0.498 0.119 0.030 0.023 0.406 0.067
used were analyzed by gas chromatography to be at least
99.5 mass %. 2000a). For clarity, this procedure is not presented here
Procedures. The measurement procedure is almost the again.
same as that described in the previous paper (Chen et al.,
Results and Discussion
* Corresponding author. Fax: 86-10-62770304. E-mail: cj-dce@ Experimental Data. The experimental tie-line data for
mail.tsinghua.edu.cn. three quaternary systemsshexane + heptane + toluene
10.1021/je0001983 CCC: $20.00 © 2001 American Chemical Society
Published on Web 12/12/2000
170 Journal of Chemical and Engineering Data, Vol. 46, No. 1, 2001

Table 3. NRTL Parameters, (gij - gjj)/R in Kelvin, Regressed from Ternary Systems at 298.15 K: 1, Hexane; 2, Heptane;
3, Octane; 4, Benzene; 5, Toluene; 6, m-Xylene; 7, Sulfolane
j)1 j)2 j)3 j)4 j)5 j)6 j)7
i)1 0.0000 0.0000 0.0000 0.1523 × 101 0.3470 × 103 0.1155 × 103 0.2045 × 104
i)2 0.0000 0.0000 0.0000 -0.1813 × 102 0.3598 × 103 0.1398 × 103 0.1960 × 104
i)3 0.0000 0.0000 0.0000 -0.1635 × 103 0.1155 × 103 -0.3318 × 103 0.2235 × 104
i)4 0.9089 × 102 0.9893 × 102 0.2837 × 103 0.0000 0.0000 0.0000 0.4032 × 103
i)5 -0.2676 × 103 -0.2798 × 103 -0.8422 × 102 0.0000 0.0000 0.0000 0.5623 × 103
i)6 -0.9856 × 102 -0.5849 × 102 0.3645 × 103 0.0000 0.0000 0.0000 0.4137 × 103
i)7 0.8706 × 103 0.1018 × 104 0.1231 × 104 -0.1038 × 103 -0.5359 × 102 0.1451 × 103 0.0000

Table 4. Predicted Results for the Quaternary System Hexane (1) + Heptane (2) + Toluene (3) + Sulfolane (4) (RMSD )
0.0048)
hydrocarbon-rich phase sulfolane-rich phase
x1exp x1cal x2 exp x2cal x3 exp x3cal x4exp x4 cal x1exp x1cal x2exp x2cal x3exp x3cal x4exp x4cal
0.699 0.701 0.139 0.142 0.151 0.155 0.010 0.002 0.012 0.013 0.004 0.002 0.068 0.064 0.916 0.921
0.236 0.235 0.515 0.517 0.241 0.244 0.008 0.004 0.005 0.006 0.013 0.009 0.106 0.103 0.875 0.882
0.407 0.408 0.240 0.243 0.336 0.339 0.017 0.009 0.013 0.015 0.008 0.007 0.155 0.153 0.823 0.825
0.201 0.199 0.250 0.249 0.514 0.516 0.036 0.036 0.014 0.017 0.017 0.018 0.271 0.269 0.698 0.697
0.177 0.167 0.151 0.148 0.603 0.606 0.068 0.079 0.024 0.028 0.024 0.022 0.381 0.368 0.572 0.583

Table 5. Prediction RMSDs for LLE of Three Quaternary

+ sulfolane, heptane + octane + m-xylene + sulfolane, and and Quinary Systems
heptane + benzene + toluene + sulfolaneswere measured,
and the results are shown in Table 1. system RMSD
The experimental tie-line data for two quinary systemss Quaternary Systems
hexane + heptane + toluene + m-xylene + sulfolane and hexane + heptane + toluene + sulfolane 0.0048
heptane + octane + benzene + m-xylene + sulfolanesare heptane + octane + m-xylene + sulfolane 0.0069
heptane + benzene + toluene + sulfolane 0.0059
shown in Table 2.
Data Correlation and Prediction. The NRTL ther- Quinary Systems
hexane + heptane + toluene + m-xylene + sulfolane 0.0086
modynamic model was used to express LLE as in the heptane + octane + benzene + m-xylene + sulfolane 0.0098
previous paper (Chen et al., 2000a). First the calculation
of equilibrium data from NRTL with parameters was
from ternary LLE systems can be used to predict LLE of
carried out with the minimization of Gibbs energy as the
quaternary and quinary systems. But for the calculation
objective function, and the equality of activity for each
of other properties such as vapor-liquid equilibria, pa-
component in two phases was carefully confirmed. Then
rameters between two aliphatic hydrocarbons or between
the parameters in NRTL were regressed with the minimi-
two aromatic hydrocarbons should be used for better
zation of all root-mean absolute deviations of mole fractions
results.
for all components:
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 Journal of Chemical and Engineering Data, Vol. 46, No. 1, 2001 171

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