Fluid Phase Equilibria 220 (2004) 189–198

Interaction parameters for multi-component aromatic

extraction with sulfolane
S.A. Ahmad, R.S. Tanwar, R.K. Gupta, A. Khanna∗
Department of Chemical Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India

Received 11 May 2002; accepted 4 February 2004

Available online 4 June 2004

Abstract

Aromatic extraction is an important operation in petrochemical processing. Design of an aromatic extractor requires the knowledge of
multi-component liquid–liquid equilibrium (LLE) data. Such experimental LLE data are usually not available and therefore can be predicted
using various activity coefficient models. These models require proper binary interaction parameters, which are not yet available for all
aromatic extraction systems. Furthermore, the parameters available for most of the ternary systems are specific to that system only and cannot
be used for other ternary or multi-component systems. An attempt has been made to obtain these parameters that are globally applicable. For
this purpose, the parameter estimation procedure has been modified to estimate the parameters simultaneously for different systems involving
common pairs. UINQUAC and UNIFAC models have been used for parameter estimation. The regressed parameters are shown to be applicable
for the ternary as well as for the multi-component systems. It is observed that UNIQUAC parameters provide a better fit for ternary LLE data,
whereas, as one moves towards the higher component systems (quaternary and quinary) the UNIFAC parameters, which are a measure of the
group contributions, predict the LLE better. Effect of temperature on UNIQUAC binary interaction parameters has been studied and a linear
dependence has been observed.
© 2003 Published by Elsevier B.V.

Keywords: Multi-component; Maximum likelihood; Liquid–liquid equilibria; Binary interaction parameters; IVEM

1. Introduction represent LLE for highly non-ideal liquid mixtures usually

Aromatics such as benzene, toluene, and xylene are con-
sidered essential in the chemical industry because they are
the source of many organic chemicals. These aromatics are
present in the naphtha feed. High purity aromatics are dif-
ficult to be separated using ordinary distillation operation,
since they form several binary azeotropes with aliphatics.
Extraction is therefore a better choice to separate the aromat-
ics from the naphtha feed, as they are preferentially soluble
in a variety of solvents.
To predict the separation, it is necessary to know the LLE
data for a particular system. Various thermodynamic mod-
els such as UNIQUAC, UNIFAC and NRTL can be used to
predict the LLE. These models use the activity coefficients,
which require proper binary interaction parameters that can
∗ Corresponding author. Tel.: +91-512-2597117;
fax: +91-512-2590104.
E-mail address: akhanna@iitk.ac.in (A. Khanna).
encountered in aromatic extraction. These parameters are
yet not entirely available for the multi-component systems
encountered in aromatic extraction. These are generally es-
timated using experimental LLE data. In case no experimen-
tal liquid–liquid equilibrium data for the systems of interest
are available, the infinite dilution activity coefficients can be
used for parameter estimation but at the cost of accuracy [1].
A least square minimization or a maximum likelihood ap-
proach can be used for the estimation of binary interaction
parameters. It has been observed that the binary interaction
parameters for the same pairs are found to be different for
different ternary systems [2]. For example, the binary inter-
action parameters between the pair hexane–benzene in the
system hexane–benzene–sulfolane are different from those
in hexane–benzene–triethylene glycol system [3]. Interac-
tion parameters are therefore specific for the system from
which they have been estimated and hence cannot be used to
predict LLE for the other systems or for the multi-component
extraction. It has also been reported that the different sets of

0378-3812/$ – see front matter © 2003 Published by Elsevier B.V.

doi:10.1016/j.fluid.2004.02.008
190 S.A. Ahmad et al. / Fluid Phase Equilibria 220 (2004) 189–198

initial guesses result in different estimates of the parameters
due to existence of several local minima [4].
To overcome these problems, the parameter estimation
approach is modified in which the binary interaction pa-
rameters for different ternary systems involving common
pairs are estimated simultaneously using a modified objec-
tive function. A brief description of the method used for the
parameter estimation is given in the next section. Results of
parameter estimation and multi-component LLE prediction
are presented and discussed in the later section. The effect
of temperature on UNIQUAC binary interaction parameters
is also presented and discussed in the same section. The
conclusions drawn are reported in the final section.
In the maximum likelihood approach a priori estimate of
variances is made based on the experimental errors, but this
method is internally inconsistent. This is because the apri-
ori estimate of variance-covariance matrix is not, in general,
equal to the final values obtained from the residuals at the
conclusion of the regression procedure [4]. To avoid this
inconsistency in maximum likelihood approach, an Inside
variance estimation method (IVEM) recently implemented
by Vasquez et al. [4] has been adopted in which the ob-
jective function of Eq. (1) is used, but V k is re-estimated
at each iteration of the optimization procedure. At the end,
the residuals are consistent with V k guaranteeing the most
likely values for the parameter vector θ.

2.1. Choice of initial guess

2. Estimation of interaction parameter
Two approaches are widely used for parameter estima-
tion [4]. Least square minimization approach and maxi-
mum likelihood approach. The least square minimization
approach requires less computational effort but it does not
take into account the possible random errors in the exper-
iments. The maximum likelihood approach maximizes the
likelihood function and also takes into account the possible
random errors in the experiments [4]. This is therefore the
preferred method. The objective function that is to be mini-
mized takes the following form

n
 F(θ) =
mn m 
F(θ) = −ln L = ln 2π + ln vii
2 2
i=1
m
1  T −1
+ ek V k ek
2 represent the coexisting phases.
k=1
where L is the likelihood function, m is the number of ex-
perimental data or tie lines, n is the number of measured
variables, ek is the vector of errors for kth experimental data,
V k is the variance-covariance matrix for kth experimental
data, and νii is the variance of ith measured variable. This
method has been discussed in detail by Esposito et al. [5].
The Objective function defined by Eq. (1) is highly non-
linear and non convex in nature. Different initial guesses may
lead to different minima. A proper choice of initial guess is,
therefore, important in parameter estimation. Any one of the
following strategies may be used to obtain the initial guess.
1. By running “property estimation” program of Aspen Plus
simulator using UNIF–LL method to estimate UNIQUAC
binary interaction parameters.
2. By minimizing the activity difference objective function
n
m 

I I II II
[aik (xik , θ) − aik (xik , θ)]2 (2)
k=1 i=1
using any initial guess. In Eq. (2) aik represents the ac-
tivity of the component i for the kth tie line and I and II
(1)
The objective function defined by Eq. (2) does not yield
a good agreement between experimental and predicted
LLE. However it has a very good convergence property
and therefore is better suited for initial guess for mini-
mization of any other objective function [6].
3. By using reported values in the literatures. Both system
specific or common parameters can be used.

Table 1
Ternary systems at different temperatures used for parameter estimation
S. no. System name Temperature (◦ C) Reference

1 Hexane–benzene–sulfolane 25, 50, 75, 100 [7,8]

2 Hexane–toluene–sulfolane 25 [7]
3 Hexane–xylene–sulfolane 25 [7]
4 Heptane–benzene–sulfolane 25 [9]
5 Heptane–toluene–sulfolane 25, 50, 75, 100 [8–11]
6 Heptane–xylene–sulfolane 17, 25, 50 [10,11]
7 Octane–benzene–sulfolane 25, 35, 45, 70.2, 99.2, 129.2 [7,12,13]
8 Octane–toluene–sulfolane 25, 35, 45, 70.2, 99.2, 129.2 [7,12,13]
9 Octane–xylene–sulfolane 25, 30, 35, 45, 70.2, 99.2, 129.2 [7,12,13]
10 Pentane–benzene–sulfolane 17, 25, 50 [14]
11 Pentane–toluene–sulfolane 17, 25, 50 [14]
12 Cyclohexane–benzene–sulfolane 25, 50, 75, 100 [8]
13 Cyclohexane–toluene–sulfolane 25 [10]
 S.A. Ahmad et al. / Fluid Phase Equilibria 220 (2004) 189–198 191

Table 2
Quaternary and quinary systems used for validation
S. no. System name Temperature (◦ C) Reference

1 Hexane–benzene–xylene–sulfolane 25 [7]
2 Hexane–octane–benzene–sulfolane 25 [7]
3 Octane–toluene–xylene–sulfolane 25 [7]
4 Hexane–heptane–toluene–sulfolane 25 [15]
5 Heptane–octane–xylene–sulfolane 25 [15]
6 Heptane–benzene–toluene–sulfolane 25 [15]
7 Hexane–octane–benzene–toluene–sulfolane 25 [7]
8 Hexane–heptane–toluene–xylene–sulfolane 25 [15]
9 Heptane–octane–benzene–xylene–sulfolane 25 [15]

The predicted LLE using binary interaction parameters
obtained by minimization of the objective function of Eq. (1)
are compared with the experimental ones using either the
value of the objective function at optimality or the value of
root mean square deviation (RMSD) which for c component
system is defined as
 1/2
m  c 2 j j
 (xik − x̂ik )2
RMSD = 100   (3)
2mc
k=1 i=1 j=1
j j
where xik and x̂ik are the experimental and predicted mole
fraction of the component i in the phase j for the tie line k
respectively.
3. Results and discussions
The naphtha feed from which the aromatics are extracted
contains large number of components belonging to different
families (paraffin, iso-parrafin, olefin, naphthene, and aro-
matics). It is very difficult to model the aromatic extraction
system exactly because of the presence of components cov-
ering a large range of molecular weights and also due to
different compositions of aromatic and non-aromatic com-
pounds in the naphtha feed obtained from different sources.
Therefore, the feed is generally assumed to be composed of
only key components. The number of such key components
is also tentative and depends largely on the availability of ex-
perimental data. Therefore for simplicity, the feed has been
modeled as having only one aromatic and one non-aromatic
key component. More components can be added based on
the availability of experimental LLE data. Binary interac-
tion parameters for different ternary systems are estimated
separately, they are specific for a particular system. To over-
come this specificity, parameters for different ternary sys-
tems involving common pairs are estimated simultaneously.
The parameters obtained from simultaneous estimation have
been used for the prediction of multi-component LLE and
they are compared with experimental data. The systems con-
sidered in this work for parameter estimation are listed in
Table 1 and those for validation in Table 2. The correspond-
ing temperatures and source of experimental LLE data are
also shown in these tables.
3.1. Separate estimation of parameters
Varhegyi and Eon [16] have shown that the binary in-
teraction parameters for a particular ternary system must
be evaluated from the same ternary data. This significantly
reduces the RMSD. Consequently this approach has been

Table 3
Specific UNIQUAC binary interaction parameters at 298.15 K for hexane–benzene–sulfolane for different initial guesses [7]
Binary pair i–j Initial guess, aij Regressed parameters, aij Objective function, −ln L RMSD RMSD DECHEMA [17]
Initial guess 1
Hexane–benzene −116.105 −117.626 −154.822 0.6045 n.a.
Hexane–sulfolane 561.401 609.336
Benzene–hexane 157.958 156.310
Benzene–sulfolane 21.908 19.931
Sulfolane–hexane 67.843 69.250
Sulfolane–benzene 59.084 60.264
Initial guess 2
Hexane–benzene −288.367 −263.377 −143.962 0.7753 n.a.
Hexane–sulfolane 501.863 459.073
Benzene–hexane −25.304 −29.183
Benzene–sulfolane 54.486 60.821
Sulfolane–hexane 99.005 80.761
Sulfolane–benzene −239.095 −260.902
n.a.: not available.
192 S.A. Ahmad et al. / Fluid Phase Equilibria 220 (2004) 189–198

Table 4
Specific UNIQUAC binary interaction parameters for at 298.15 K Hexane–toluene–sulfolane for different initial guesses [7]
Binary pair i–j Initial guess, aij Regressed parameters, aij Objective function, −ln L RMSD RMSD DECHEMA [17]

Initial guess 1
Hexane–toluene 167.205 139.977 −161.705 0.6851 n.a.
Hexane–sulfolane 561.401 658.218
Toluene–hexane −137.162 −105.237
Toluene–sulfolane 47.058 60.637
Sulfolane–hexane 67.843 66.196
Sulfolane–toluene 79.687 69.181
Initial guess 2
Hexane–toluene −53.247 −53.808 −98.785 0.8528 n.a.
Hexane–sulfolane 392.861 366.612
Toluene–hexane −312.903 −296.944
Toluene–sulfolane 246.093 255.279
Sulfolane–hexane 132.275 121.639
Sulfolane–Toluene −194.270 −221.172
n.a.: not available.

implemented in DECHEMA Chemistry Data Series [2]
for the ternary systems reported. Similar approach has
been adopted to confirm the specificity of the regressed
parameters. Two systems, hexane–benzene–sulfolane and
hexane–toluene–sulfolane at 298.15 K have been consid-
ered. UNIQUAC binary interaction parameters for these
systems have been estimated using two sets of initial
guesses. Initial guess 1 is obtained by running the param-
eter estimation program of Aspen Plus simulator using
UNIF–LL method and initial guess 2 is obtained by min-
imizing the activity difference objective function defined
by Eq. (2). The binary interaction parameters thus ob-
tained are shown in Tables 3 and 4 respectively with the
common pair parameters underlined. The corresponding
values of objective function and RMSD are also shown. It
can be seen that the binary interaction parameter for the
common pair hexane–sulfolane are different for both the
systems. For the first set of initial guesses, the value of in-
teraction parameter of hexane–sulfolane pair in the system
hexane–benzene–sulfolane is 609.336 whereas that in the
system hexane–toluene–sulfolane is 658.218. The same is
true for the reverse pair sulfolane–hexane. Similar results
are obtained with the second set of initial guesses. It is also
evident that the different sets of initial guesses result in
different estimates of the binary interaction parameters. A
proper choice of initial guess is therefore important. An ac-
ceptable choice would be that which gives the better RMSD
and/or the objective function value. The parameters reported
in this work are those which exhibit less RMSD values.
Further the parameters estimated from different sets of
LLE data for the same systems are found to be different.
For example, UNIQUAC binary interaction parameters re-
gressed from LLE data reported by Chen et al. [7] are
different from those regressed from LLE data reported by
DeFré and Verhoeye [8]. The regressed parameters for these
two data sets along with the corresponding objective func-
tion and RMSD values are shown in Table 5. To avoid this
discrepancy such data sets are taken simultaneously in the
regression procedure. Also both the objective function and
RMSD values indicate that DeFré’s data [8] is slightly bet-

Table 5
Specific UNIQUAC binary interaction parameters at 298.15 K for Hexane–benzene–sulfolane
Binary pair i–j Initial guess, aij Regressed parameters, aij Objective function, −ln L RMSD RMSD DECHEMA [17]
Data Set 1 [7]
Hexane–benzene −116.105 −117.626 −154.822 0.6045 n.a.
Hexane–sulfolane 561.401 609.336
Benzene–hexane 157.958 156.310
Benzene–sulfolane 21.908 19.931
Sulfolane–hexane 67.843 69.250
Sulfolane–benzene 59.084 60.264
Data Set 2 [8]
Hexane–benzene −116.105 −114.532 −184.434 0.5090 0.52
Hexane–sulfolane 561.401 606.890
Benzene–hexane 157.958 151.923
Benzene–sulfolane 21.908 21.759
Sulfolane–hexane 67.843 70.830
Sulfolane–benzene 59.084 59.254
n.a.: not available.
 S.A. Ahmad et al. / Fluid Phase Equilibria 220 (2004) 189–198 193

Table 6
Simultaneous UNIQUAC binary interaction parameters at 298.15 K for Hexane–benzene/toluene/xylene–sulfolane
Binary pair i–j No. of data Initial guess, aij Regressed parameters, aij Objective function, −ln L RMSD RMSD
sets [Ref.] DECHEMA [17]
Hexane–benzene −116.105 −126.003 −329.271 0.6167 5.15
Hexane–sulfolane 561.401 681.179
Benzene–hexane 2 157.958 165.755
Benzene–sulfolane [7,8] 21.908 21.598
Sulfolane–hexane 67.843 65.573
Sulfolane–benzene 59.084 59.180
Hexane–toluene 167.205 180.432 −157.126 0.9302 n.a.
Hexane–sulfolane 561.401 681.179
Toluene–hexane 1 −137.162 −128.705
Toluene–sulfolane [7] 47.058 50.487
Sulfolane–hexane 67.843 65.573
Sulfolane–toluene 79.687 79.309
Hexane–xylene 272.415 262.852 −138.991 0.9120 n.a.
Hexane–sulfolane 561.401 681.179
Xylene–hexane 1 −212.109 −199.216
Xylene–sulfolane [7] 98.425 97.216
Sulfolane–hexane 67.843 65.573
Sulfolane–xylene 65.007 48.879
Overall objective function value = −625.388
Overall RMSD = 0.8321
n.a.: not available.

ter than Chen’s data [7]. Also for DeFré’s data [8] RMSD
value is compared with those reported in DECHEMA
[17] for the specific UNIQUAC parameters. The RMSD
value obtained in this work is better than those reported
in DECHEMA, which confirms the authenticity of the es-
timated parameters using IVEM. Chen’s data [7] have not
been processed for UNIQUAC parameters and hence their
RMSD values could not be compared with those of present
work.
3.2. Simultaneous estimation of parameters involving
common pair
lined. The number of data sets available for each system
with their sources is indicated. The objective function val-
ues and the corresponding RMSD values are also shown.
The RMSD values calculated from using the available com-
mon UNIQUAC parameters reported in DECHEMA [17]
for these systems are also given in the table.
Table 7
Simultaneous UNIQUAC binary interaction parameters at 298.15 K for
systems in Table 1
Binary pair i–j Binary interaction parameters (K)
aij aji

In simultaneous estimation of parameters the objective Pentane–benzene −124.530 154.243

function is calculated for each ternary system keeping the Pentane–toluene 140.138 −105.381
Pentane–sulfolane 849.121 82.770
parameters between the common pair same in all the sys- Hexane–benzene −126.003 165.755
tems. The modified objective function is taken as the sum Hexane–Toluene 180.432 −128.705
of objective functions of individual system. Hexane–xylene 262.852 −199.216
Using the above scheme the UNIQUAC binary interaction Hexane–sulfolane 681.179 65.573
parameters have been estimated simultaneously taking the Heptane–benzene −125.230 166.246
Heptane–toluene 181.432 −129.505
systems that involve only one common pair. Table 6 shows Heptane–xylene 264.201 −200.150
the results of simultaneous parameter estimation for the sys- Heptane–sulfolane 683.994 65.776
tem hexane–benzene–sulfolane, hexane–toluene–sulfolane, Octane–benzene −120.367 165.083
and hexane–xylene–sulfolane, at 298.15 K. The common Octane–toluene 181.706 −126.341
pair involved in this system is hexane–sulfolane whose Octane–xylene 257.508 −198.570
Octane–sulfolane 747.083 67.323
parameters are kept same in all the three systems. Ini- CycloHexane–benzene −131.926 176.370
tial guesses of the parameters have been obtained from Cyclohexane–toluene 161.663 −152.302
running the property estimation program of Aspen Plus CycloHexane–sulfolane 554.680 67.652
simulator, as the results with these initial guesses exhibit Benzene–sulfolane 21.598 59.180
better RMSD values. The parameters for the common pair Toluene–sulfolane 50.487 79.309
Xylene–sulfolane 97.845 48.879
hexane–sulfolane and sulfolane–hexane are shown under-
194 S.A. Ahmad et al. / Fluid Phase Equilibria 220 (2004) 189–198

Table 8 are presented in Table 8. The fixed parameters are shown in

UNIFAC group interaction parameters at 298.15 K for sulfolane with other italics and the estimated parameters are shown bold faced.
main groups
The RMSD values obtained using the UNIQUAC binary
i–j Binary group interaction parameters, aij interaction parameters in Table 7 and UNIFAC binary group
CH3 CH2 ACHa ACCH3 a Sulfolane interaction parameters given in Table 8 are shown in Table 9.
The calculated RMSD values using available common UNI-
CH3 0 0 −114.80 −115.70 665.45
CH2 0 0 −114.80 −115.70 665.45
QUAC parameters reported in DECHEMA [17] are also
ACHa 156.50 156.50 0 167.00 36.30 given for comparison. It is to be noted that the RMSD values
ACCH3 a 104.40 104.40 −146.80 0 236.58 obtained using UNIQUAC parameters are better than those
Sulfolane 52.39 52.39 54.33 9.93 0 obtained using UNIFAC parameters for all the ternary sys-
a AC stands for aromatic carbon. tems studied. Additionally the RMSD values for simultane-
ous parameter estimation are at least five times better than
those calculated from using common parameters reported in
Similar approach has been adopted to estimate the UNI- DECHEMA [17].
QUAC binary interaction parameters for the other ternary
systems (System 4 to 13 in Table 1) at 298.15 K by changing 3.3. Validation of simultaneous estimation of parameters
only the nonaromatic component. The binary parameters re-
ported in Table 6 have been supplied as initial guesses. While The UNIQUAC and UNIFAC parameters estimated in the
estimating the parameters for these systems, the parame- previous section and reported in Tables 7 and 8 have been
ters of the aromatic-solvent pairs that is benzene–sulfolane, tested for their validity for the multi-component systems
toluene–sulfolane, and xylene–sulfolane have been kept listed in Table 2. Table 10 shows the experimental and pre-
fixed at those obtained from earlier regression and as shown dicted equilibrium composition for the quaternary system
in Table 6. The comprehensive results of such parameter hexane–benzene–xylene–sulfolane at 298.15 K using the ex-
estimations are given in Table 7. The parameters that are perimental LLE data reported by Chen et al. [7]. Interaction
kept fixed at previously obtained values are shown in italics. parameters between the components of same homologous
UNIFAC group interaction parameters have also been series (e.g. benzene–xylene) are taken as zero as suggested
estimated in our previous work [18] with the same ap- by Salem et al. [20]. Prediction of Chen et al. [7] using
proach taking the three systems hexane–benzene–sulfolane, their NRTL parameters are also shown. The corresponding
hexane–toluene–sulfolane, and hexane–xylene–sulfolane, at RMSD values are also given in the table. The UNIFAC pa-
298.15 K simultaneously. Sulfolane is considered as a single rameters show a better agreement between the experimental
group and its interaction parameter with the groups CH3 , and predicted compositions than those for UNIQUAC and
CH2 , ACH and ACCH3 have been estimated. Mutual inter- NRTL parameters as evident from their respective RMSD
action parameters between the groups CH3 , CH2 , ACH and values.
ACCH3 are directly taken from those given by Magnussen LLE for the other multi-component systems listed in
et al. [19] and are kept fixed because these are universally ac- Table 2 have been predicted similarly. The RMSD values
cepted parameters tested by several investigators. The results using UNIQUAC and UNIFAC parameters as well as those

Table 9
Comparative RMSD values for the ternary systems
S. no. System name UNIFAC UNIQUAC
This work This work DECHEMA [17]
Estimation
1 Hexane–benzene–sulfolane 0.6249 0.6167 5.15
2 Hexane–toluene–sulfolane 0.4852 0.9302 n.a.
3 Hexane–xylene–sulfolane 0.9236 0.9120 n.a.
Prediction
4 Heptane–benzene–sulfolane 0.7233 0.5378 3.85
5 Heptane–toluene–sulfolane 0.7810 0.5799 2.18
6 Heptane–xylene–sulfolane 0.9166 0.5749 n.a.
7 Octane–benzene–sulfolane 1.0542 0.9062 n.a.
8 Octane–toluene–sulfolane 0.8164 0.5339 n.a.
9 Octane–xylene–sulfolane 1.1409 1.0370 n.a.
10 Pentane–benzene–sulfolane 0.8100 0.7193 n.a.
11 Pentane–toluene–sulfolane 0.9515 0.6985 n.a.
12 Cyclohexane–benzene–sulfolane 0.8494 0.6955 2.91
13 Cyclohexane–toluene–sulfolane 0.8338 0.7716 8.60
n.a.: not available.
 S.A. Ahmad et al. / Fluid Phase Equilibria 220 (2004) 189–198 195

Table 10
Comparison of experimental and predicted LLE using estimated binary interaction parameters for the system hexane (1), benzene (2), xylene (3), Sulfolane
(4) at 298.15 K
Tie line Raffinate phase Extract Phase
x1 x2 x3 x4 x1 x2 x3 x4

1 Experimental 0.857 0.076 0.051 0.017 0.016 0.052 0.010 0.921

UNIQUAC 0.863 0.081 0.054 0.002 0.016 0.047 0.008 0.929
UNIFAC [18] 0.869 0.079 0.049 0.002 0.020 0.049 0.012 0.919
NRTL [7] 0.876 0.074 0.049 0.001 0.014 0.054 0.013 0.919
2 Experimental 0.709 0.135 0.143 0.013 0.021 0.094 0.043 0.841
UNIQUAC 0.702 0.142 0.148 0.009 0.020 0.086 0.036 0.858
UNIFAC [18] 0.709 0.138 0.145 0.008 0.023 0.091 0.041 0.845
NRTL [7] 0.719 0.132 0.143 0.006 0.019 0.098 0.044 0.739
3 Experimental 0.575 0.266 0.134 0.025 0.028 0.199 0.046 0.727
UNIQUAC 0.577 0.261 0.140 0.022 0.026 0.190 0.046 0.938
UNIFAC [18] 0.577 0.271 0.133 0.019 0.031 0.195 0.047 0.726
NRTL [7] 0.587 0.263 0.133 0.017 0.030 0.203 0.049 0.718
4 Experimental 0.450 0.156 0.356 0.038 0.026 0.107 0.135 0.732
UNIQUAC 0.446 0.155 0.356 0.032 0.026 0.108 0.136 0.730
UNIFAC [18] 0.448 0.154 0.358 0.040 0.028 0.109 0.133 0.729
NRTL [7] 0.457 0.150 0.357 0.036 0.027 0.114 0.138 0.721
5 Experimental 0.316 0.497 0.098 0.088 0.083 0.432 0.062 0.423
UNIQUAC 0.323 0.492 0.105 0.079 0.077 0.436 0.056 0.431
UNIFAC [18] 0.322 0.495 0.098 0.085 0.077 0.434 0.062 0.427
NRTL [7] 0.316 0.494 0.098 0.091 0.082 0.435 0.061 0.422
RMSD using UNIQUAC parameters = 0.6633 [This work]
RMSD using UNIFAC parameters = 0.4156 Ref. [18]
RMSD using NRTL parameters = 0.6900 Ref. [7]

reported by Chen et al. [7,15] are given in Table 11. It is
seen that RMSD values for UNIFAC parameters are better
in most of the cases. Further, it is even better for the quinary
systems than those for quaternary systems. Thus it can be
said that UNIFAC parameters are more suitable for predic-
tion of multi-component LLE as the number of components
increase.
3.4. Effect of temperature on UNIQUAC binary interaction
parameters
Temperature dependence of UNIQUAC binary interac-
tion parameters have been investigated for the systems,
given in Table 1 for which LLE data are available at more
than one temperature. The results are shown in Tables
12–16. To establish the temperature effect the binary inter-
action parameters for the aromatic–sulfolane pairs (such as
benzene–sulfolane, etc.) which are involved in all the sys-
tems are plotted against the temperature and are shown in
Fig. 1. A best-fit straight line is also drawn along with the
estimated points. For other pairs the goodness of linear fit
can also be gauged from the coefficient of correlation which
lies in the range 0.6–0.98. The values of the coefficient
of correlation, r, for the different pairs are also reported
in the respective tables. This establishes a linear depen-
dence of binary interaction parameters on temperature,

Table 11
Root mean square deviation (RMSD) between experimental and predicted LLE for quaternary and quinary systems at 298.15 K
S. no. System name UNIQUAC (this work) UNIFAC [18] NRTL [7,15]
1 Hexane–benzene–xylene–sulfolane 0.6633 0.4156 0.6900
2 Hexane–octane–benzene–sulfolane 0.8806 1.0566 0.9900
3 Octane–toluene–xylene–sulfolane 0.8332 0.6200 0.6600
4 Hexane–heptane–toluene–sulfolane 0.5933 0.4566 0.4800
5 Heptane–octane–xylene–sulfolane 0.5506 0.5644 0.6900
6 Heptane–benzene–toluene–sulfolane 0.9412 0.3541 0.5900
7 Hexane–octane–benzene–toluene–sulfolane 0.6416 0.3700 0.4200
8 Hexane–heptane–toluene–xylene–sulfolane 0.8091 0.6302 0.8600
9 Heptane–octane–benzene–xylene–sulfolane 0.9933 0.5211 0.9800
196 S.A. Ahmad et al. / Fluid Phase Equilibria 220 (2004) 189–198

Table 12
UNIQUAC binary interaction parameters at different temperature for Hexane–benzene–sulfolane
Binary pair i–j Temperature (K) r
298.15 323.15 348.15 373.15
Hexane–benzene −126.003 −128.299 −139.180 −143.562 0.9705
Hexane–sulfolane 681.179 570.130 565.053 447.108 0.9551
Benzene–hexane 165.755 164.399 147.655 162.628 0.6015
Benzene–sulfolane 21.598 22.580 23.626 24.275 0.8137
Sulfolane–hexane 65.573 65.560 64.276 64.843 0.7167
Sulfolane–benzene 59.180 65.100 67.873 68.527 0.9435
RMSD 0.6167 0.3602 0.8158 0.3325

Table 13
UNIQUAC binary interaction parameters at different temperatures for Pentane–benzene/toluene–sulfolane
Binary pair i–j Temperature (K) r
290.15 298.15 323.15
Pentane–benzene −125.791 −124.530 −127.329 0.7642
Pentane–sulfolane 852.671 849.121 838.204 1.0000
Benzene–pentane 157.850 154.243 154.910 0.6029
Benzene–sulfolane 21.844 21.598 22.580 0.8137
Sulfolane–pentane 80.249 82.770 81.722 0.6255
Sulfolane–benzene 60.048 59.180 65.10 0.9435
Pentane–toluene 150.199 140.138 147.187 0.6069
Toluene–pentane −104.923 −105.381 −105.349 0.6448
Toluene–sulfolane 45.811 50.487 52.018 0.6384
Sulfolane–toluene 77.576 79.309 83.389 0.8327
RMSD 0.7358 0.7090 0.6042

Table 14
UNIQUAC binary interaction parameters at different temperatures for heptane–toluene/xylene–sulfolane
Binary pair i–j Temperature (K) r
290.15 298.15 323.15 348.15 373.15
Heptane–toluene – 181.432 178.809 173.809 177.601 0.6719
Heptane–sulfolane 734.982 683.994 677.464 681.344 701.836 0.6266
Toluene–heptane – −129.505 −130.562 −135.701 −135.836 0.9329
Toluene–sulfolane 45.811 50.487 52.018 52.076 52.456 0.6384
Sulfolane–heptane 63.961 65.776 65.260 64.483 64.122 0.6474
Sulfolane–toluene 77.576 79.309 83.389 84.880 85.295 0.8327
Heptane–xylene 272.322 264.201 273.643 – – 0.6065
Xylene–heptane −177.500 −200.150 −194.354 – – 0.6875
Xylene–sulfolane 99.815 97.845 96.625 – – 0.7819
Sulfolane–xylene 46.059 48.879 51.467 – – 0.9072
RMSD 0.8562 0.5799 0.7813 0.8472 0.8191

Table 15
UNIQUAC binary interaction parameters at different temperatures for Octane–benzene/toluene/xylene–sulfolane
Binary pair i–j Temperature (K) r
298.15 308.15 318.15 343.35 372.35 402.35
Octane–benzene −120.367 −131.472 −144.329 −145.753 −149.229 −160.722 0.9094
Octane-Sulfolane 747.083 777.310 747.070 742.058 701.039 646.127 0.9275
Benzene–octane 165.114 165.491 163.086 161.158 158.327 150.997 0.9713
Benzene–sulfolane 21.598 23.161 23.511 23.802 24.828 23.847 0.8137
Sulfolane–octane 67.323 77.160 77.518 79.949 79.961 79.813 0.6777
Sulfolane–benzene 59.180 62.660 64.613 67.210 66.985 72.028 0.9435
Octane–toluene 181.706 182.684 156.195 154.468 155.577 154.141 0.7352
Toluene–octane −126.341 −130.990 −141.442 −136.695 −139.776 −141.355 0.7214
Toluene–sulfolane 50.487 49.116 49.416 51.418 51.069 51.157 0.6384
Sulfolane–toluene 79.309 82.012 84.005 84.701 85.115 85.426 0.8327
Octane–xylene 257.508 279.014 269.609 239.457 225.751 206.011 0.9320
Xylene–octane −198.570 −171.034 −156.062 −164.696 −168.305 −188.333 0.6421
Xylene–sulfolane 97.845 97.501 95.823 98.816 101.192 106.052 0.7819
Sulfolane–xylene 48.879 49.631 47.944 50.780 52.006 55.393 0.9072
RMSD 0.9062 0.6655 0.9430 0.7553 0.9383 0.6190
 S.A. Ahmad et al. / Fluid Phase Equilibria 220 (2004) 189–198 197

Table 16
UNIQUAC binary interaction parameters at different temperature for CycloHexane–Benzene–sulfolane
Binary Pair i–j Temperature (K) r

298.15 323.15 348.15 373.15

CycloHexane–benzene −131.926 −143.454 −150.836 −168.332 0.9863
CycloHexane–sulfolane 554.680 456.733 405.443 390.101 0.9469
Benzene–cyclohexane 176.370 185.511 198.411 201.515 0.9773
Benzene–sulfolane 21.598 22.580 23.626 24.275 0.8137
Sulfolane–cyclohexane 67.632 72.469 73.098 70.081 0.6133
Sulfolane–benzene 59.180 65.100 67.873 68.527 0.9435
RMSD 0.6955 0.8680 0.9291 0.6376

Table 17
Coefficients of the linear temperature dependent UNIQUAC binary interaction parameters
I j aij0 aij1 aji0 aji1
Pentane Benzene −107.2440 −0.0624 174.7540 −0.0615
Pentane Toluene 146.8190 −0.0021 −102.5710 −0.0095
Pentane Sulfolane 982.1280 −0.4388 74.4837 0.0239
Hexane Benzene −49.0543 −0.2547 158.7020 −0.0990
Hexane Sulfolane 1519.4000 −2.8345 69.9034 −0.0129
Heptane Toluene 200.5190 −0.0661 −100.7270 −0.0966
Heptane Xylene 233.8820 0.1212 −89.6206 −0.3324
Heptane Sulfolane 770.0360 −0.2219 67.4096 −0.0018
Octane Benzene −33.7946 −0.3184 205.6910 −0.1307
Octane Toluene −251.4260 −0.2551 −98.7479 −0.1105
Octane Xylene 464.4700 −0.6382 −169.3070 −0.0165
Octane Sulfolane 1061.4800 −1.0674 49.1646 0.0820
Cyclohexane Benzene 7.9271 −0.4686 72.0021 0.3393
Cyclohexane Sulfolane 1185.9800 −2.1830 60.2334 0.0320
Benzene Sulfolane 15.6213 −0.0230 31.0430 0.1022
Toluene Sulfolane 38.9405 0.0345 62.3736 0.0621
Xylene Sulfolane 70.3958 0.0660 28.1608 0.0665

hence systems at all available temperatures have been taken simul-

taneously, leading to the estimation of a total of sixty-eight
aij = aij0 + aij1 T (4) coefficients (four coefficients aij0 , aij1 , aij0 , aji0 , and aij1 corre-
sponding to each seventeen i-j pairs). Initial guess for these
where T is in Kelvin.
coefficients are obtained by fitting a straight line through the
The coefficients of the Eq. (4), aij0 and aij1 , have been esti-
points by linear regression. The estimated parameter values
mated using simultaneous parameter estimation scheme. All
are given in Table 17. The overall RMSD value for each sys-
tem is given in Table 18. The RMSD values are in the range
140 of 0.6–0.95, which can be considered satisfactory. Addition-
Benzene-Sulfolane Sulfolane-Benzene
Toluene-Sulfolane Sulfolane-Toluene ally, the parameters obtained are applicable over a wider
120
range of temperatures and systems.
Interaction parameters, K

Xylene-Sulfolane Sulfolane-Xylene

100

Table 18
80
Overall RMSD values for the ternary systems for estimation of coefficients
in temperature dependent equation
60
S. no. System name RMSD
40
1 Pentane–benzene–sulfolane 0.7698
2 Pentane–toluene–sulfolane 0.7756
20
3 Hexane–benzene–sulfolane 0.7463
4 Heptane–toluene–sulfolane 0.8717
0
280 300 320 340 360 380 400 420 5 Heptane–xylene–sulfolane 0.9188
6 CycloHexane–benzene–sulfolane 0.7980
Temperature, K 7 Octane-benzene–sulfolane 0.8324
8 Octane–toluene–sulfolane 0.7503
Fig. 1. UNIQUAC binary interaction parameters for aromatic–sulfolane
9 Octane-xylene-Sulfolane 0.6761
pairs.
198 S.A. Ahmad et al. / Fluid Phase Equilibria 220 (2004) 189–198
4. Conclusions
An Inside variance estimation method based on maxi-
mum likelihood function has been used to estimate the bi-
nary interaction parameters using ternary systems. Results
of separate estimation show that the binary interaction pa-
rameters for the same pair are different for different systems.
To overcome this problem, the objective function has been
modified to estimate the binary interaction parameters us-
ing three systems with common pairs simultaneously. The
parameters thus obtained have been found applicable for
the other ternary systems. Results of simultaneous param-
eter estimation have been used successfully to predict the
multi-component (quaternary and quinary) LLE. The pre-
dicted LLE have been found in good agreement with the
reported experimental LLE. Both UNIQUAC and UNIFAC
models have been used. The UNIQUAC model gives better
prediction for ternary systems whereas UNIFAC is found
to be more suitable for multi-component systems. Temper-
ature dependence of UNIQUAC binary interaction parame-
ters has been investigated and a linear dependence has been
observed. Coefficients in the linear model have been ob-
tained by linear regression, which are further modified using
simultaneous estimation scheme taking all the data sets for
all systems at different temperature simultaneously.
List of symbols
a activity, binary interaction parameters
c total number of components
e vector of errors
L likelihood function
m number of tie lines or experimental data
n number of measured variables
r coefficient of correlation for linear regression
reported in Tables 12–16
V variance-covariance matrix
x experimental mole fraction
x̂ predicted mole fraction
Greek letters
θ vector of parameters
ν variance
Subscripts
i component, measured variable
j component
k tie line
Superscripts
j phase
I, II coexisting liquid phases
Acknowledgements
Financial support from BPCL project entitled “extraction
of aromatics from petroleum naphtha” is gratefully acknowl-
edged.
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