J. Chem.

Thermodynamics 42 (2010) 1281–1285

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Separation of aromatic hydrocarbons (toluene or benzene) from aliphatic

hydrocarbon (n-heptane) by extraction with ethylene carbonate
M. Mohsen-Nia a,b,*, F.S. Mohammad Doulabi a
a
Thermodynamic Research Laboratory, University of Kashan, Kashan, Iran
b
Department of Chemical Engineering, Amirkabir University of Technology, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Selectivity factors and partition coefficients of ethylene carbonate and the (ethylene carbonate + sulfo-
Received 23 January 2010 lane) solvent mixture for the separation of benzene or toluene from (benzene or toluene + n-heptane)
Received in revised form 14 April 2010 are obtained from the experimental (liquid + liquid) equilibrium data for ternary mixtures of (ethylene
Accepted 6 May 2010
carbonate + benzene or toluene + n-heptane) at temperatures of (303.15 and 313.15) K and quaternary
Available online 13 May 2010
mixture of (ethylene carbonate + sulfolane + benzene + n-heptane) at 303.15 K. The composition of liquid
phases at equilibrium was determined by gas–liquid chromatography and the results were correlated
Keywords:
with the UNIQUAC and NRTL activity coefficient models. The parameters of the models were evaluated
Separation
Selectivity
and reported. The phase diagrams for the mixtures studied are presented and the correlated tie line
Partition coefficient results have been compared with the experimental results. The comparisons indicate the applicability
Hydrocarbon of the UNIQUAC and NRTL activity coefficients model for (liquid + liquid) equilibrium calculations of
LLE data the mixtures studied.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction
The separation of aromatic hydrocarbons from alkanes by sol-
vent extraction processes has been an area of active research in
various chemical, petrochemical, and oil industries [1–3]. Because
of the known limitations of the direct separation processes such as
distillation for practical extraction of the constituent components
of the non-ideal mixtures, the indirect separation processes such
as solvent extraction may be considered. Many single or mixed sol-
vents have been studied to separate aromatic hydrocarbons from
alkanes [2]. In previous work, we showed that ethylene carbonate
can be used as a suitable solvent in the recovery of aromatics from
alkane mixtures [4].
Simulation and design of extraction processes require an effi-
cient model to describe the involved (liquid + liquid) equilibrium.
Several thermodynamic models have been developed to meet this
requirement by the concept of the local composition. Activity
coefficient models, such as non-random two-liquid models (NRTL)
[5] and the universal quasichemical model (UNIQUAC) [6] have
been applied successfully to correlate LLE data [7]. The accurate
correlation of LLE data by using NRTL and UNIQUAC activity coef-
ficient models depends on experimentally optimized interaction
parameters.
This work reports (liquid + liquid) equilibrium (LLE) data for
the ternary mixtures (ethylene carbonate + benzene or tolu-
ene + n-heptane) at temperatures of (303.15 and 313.15) K and
the quaternary mixture (ethylene carbonate + sulfolane + ben-
zene + n-heptane) at 303.15 are reported.
The experimental and correlated results are compared and
reported. According to these comparisons, the UNIQUAC and NRTL
activity coefficient have been applied successfully to correlate LLE
data of the studied mixtures.
2. Experimental
2.1. Chemicals
All materials ethylene carbonate, sulfolane, benzene, toluene,
and n-heptane were supplied with mole fraction purity 0.99 by
Merck Co. Inc., Germany. The purity of each of the components
was checked by gas chromatography, and the results confirmed
the mole fraction purity was higher than 0.99. All compounds were
used without further purification and were stored in a desiccator
with a drying agent before the use.
2.2. Procedure

* Corresponding author at: Thermodynamic Research Laboratory, University of

The equilibrium apparatus used in the present work was
Kashan, Kashan, Iran. Tel.: +98 3615555333; fax: +98 3615552930. similar to that used in the previous study [3]. The equilibrium
E-mail address: m.mohsennia@kashanu.ac.ir (M. Mohsen-Nia). cell is made of glass with a water jacket to maintain a constant

0021-9614/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2010.05.004
1282 M. Mohsen-Nia, F.S. Mohammad Doulabi / J. Chem. Thermodynamics 42 (2010) 1281–1285

TABLE 1 TABLE 4
Operating condition for the gas chromatography instrument. Binary interaction parameters for the UNIQUAC model.

Column 6% Silar 10C sorb WHP 100–200 mesh i to j Aij/(J  mol1) Aji/(J  mol1)
Detector temperature 548.15 K
{Ethylene carbonate (1) + benzene (2) + n-heptane (3)}
Injector temperature 548.15 K
1 to 2 213.84 1086.48
Oven temperature 298:15 K min1
333:15 K ðisotime ¼ 0:5 minÞ ! 498:15 K 1 to 3 1154.94 132.44
Carrier gas Nitrogen 2 to 3 1104.77 366.00
Flow rate 50 cm3  min1
{Ethylene carbonate (1) + toluene (2) + n-heptane (3)}
1 to 2 112.92 886.71
1 to 3 1154.94 132.44
2 to 3 1046.90 279.48

temperature (±0.1 K). The internal volume of glass cell is

150 cm3. The solutions were made by mass using a Sartorius TABLE 5
Binary interaction parameters for the NRTL model.
analytical balance (model A200S, accurate to 0.0001 g). The
mixtures were prepared inside the cell and were vigorously agi- i to j Aij/(J  mol1) Aji/(J  mol1)
tated with a magnetic stirrer for 1 h and then left to settle for at {Ethylene carbonate (1) + benzene (2) + n-heptane (3)}
least 20 h. The samples of both phases were analyzed by using a 1 to 2 4696.25 3131.43
Perkin–Elmer model 8500 gas chromatography equipped with a 1 to 3 2804.30 7855.30
2 to 3 2142.25 3580.41
flame ionization detector (FID). The operating condition for GLC
instrument is given in table 1. The measured LLE mole fractions, {Ethylene carbonate (1) + toluene (2) + n-heptane (3)}
1 to 2 4384.13 2887.14
x, had an error of less than 0.2% and then the absolute error
1 to 3 2804.31 7855.30
should be less than 0.001. 2 to 3 2502.39 2911.75

TABLE 2
Experimental LLE data for ternary system {ethylene carbonate (1) + toluene or benzene (2) + n-heptane (3)}.

xh1 xh2 xh3 xe1 xe2 xe3 S K

{Ethylene carbonate (1) + benzene (2) + n-heptane (3)} at 303.15 K

0.0917 0.7029 0.2054 0.6302 0.3545 0.0153 6.77 0.50
0.0584 0.6882 0.2534 0.6787 0.3076 0.0137 8.27 0.44
0.0204 0.5881 0.3915 0.7748 0.2161 0.0091 15.80 0.36
0.0124 0.5155 0.4721 0.8340 0.1585 0.0075 19.35 0.30
0.0112 0.4720 0.5168 0.8597 0.1341 0.0062 23.68 0.28
{Ethylene carbonate (1) + benzene (2) + n-heptane (3)}at 313.15 K
0.1111 0.6840 0.2049 0.6136 0.3614 0.0250 4.33 0.52
0.0732 0.6775 0.2493 0.6593 0.3210 0.0197 5.99 0.47
0.0276 0.5709 0.4015 0.7631 0.2247 0.0122 12.95 0.39
0.0207 0.5089 0.4704 0.8235 0.1666 0.0099 15.55 0.31
0.0180 0.4656 0.5164 0.8510 0.1406 0.0084 18.56 0.30
{Ethylene carbonate (1) + toluene (2) + n-heptane (3)} at 303.15 K
0.1592 0.7629 0.0779 0.6087 0.3807 0.0106 3.66 0.49
0.0442 0.8033 0.1525 0.7231 0.2695 0.0074 6.91 0.33
0.0217 0.7608 0.2175 0.7979 0.1966 0.0060 9.36 0.25
0.0275 0.7142 0.2583 0.8259 0.1686 0.0055 11.08 0.23
0.0169 0.6791 0.3040 0.8564 0.1389 0.0047 13.23 0.20
0.0079 0.5880 0.4041 0.8973 0.0987 0.0040 16.95 0.16
{Ethylene carbonate (1) + toluene (2) + n-heptane (3)} at 313.15 K
0.2374 0.7172 0.0454 0.5472 0.4388 0.0140 1.98 0.61
0.1320 0.7603 0.1077 0.6561 0.3336 0.0103 4.59 0.43
0.0545 0.7486 0.1969 0.7622 0.2296 0.0079 7.64 0.31
0.0345 0.7007 0.2648 0.8020 0.1906 0.0073 10.87 0.27
0.0267 0.6595 0.3137 0.8249 0.1672 0.0079 10.07 0.25
0.0158 0.5788 0.4053 0.8624 0.1307 0.0069 13.26 0.22

x is the mole fraction and subscripts indicate the compound and superscripts h and e indicate, respectively, the n-heptane and ethylene carbonate-rich phases. The symbol S
and K represent the selectivity and distribution coefficients, respectively.

TABLE 3
Experimental LLE data for quaternary system {ethylene carbonate (1) + sulfolane (10 ) + benzene (2) + n-heptane (3)}.

xh1 xh10 xh2 xh3 xe1 xe10 xe2 xe3 S K

0
{Ethylene carbonate (1) + sulfolane (1 ) + benzene (2) + n-heptane(3)} at 303.15 K
0.0947 0.0819 0.7922 0.0312 0.3239 0.3396 0.3241 0.0124 1.03 0.41
0.0424 0.0346 0.7778 0.1452 0.3799 0.3646 0.2454 0.0101 4.53 0.31
0.0221 0.0181 0.7001 0.2597 0.4268 0.3945 0.1704 0.0083 7.61 0.24
0.0119 0.0124 0.6929 0.2828 0.4736 0.3838 0.1364 0.0062 8.97 0.16
0.0103 0.0098 0.5941 0.3858 0.4838 0.4100 0.1012 0.0050 13.14 0.17

x is the mole fraction and subscripts indicate the compound and superscripts h and e indicate, respectively, the n-heptane and ethylene carbonate rich-phases. The symbol S
and K represent the selectivity and distribution coefficients, respectively.
 M. Mohsen-Nia, F.S. Mohammad Doulabi / J. Chem. Thermodynamics 42 (2010) 1281–1285 1283

TABLE 6 2
The calculated UNIQUAC structural parameters. 0.0
1.0
Component r q 0.1
0.9
n-Heptane 5.1740 4.3960
Benzene 2.4000 3.1878 0.2
0.8
Toluene 3.9228 2.9680
Ethylene carbonate 1.3532 1.0800 0.3
Sulfolane 4.0356 3.200 0.7

r and q are the volume and surface area parameters, respectively. 0.4
0.6

0.5
0.5

0.6
0.4
TABLE 7
0.7
The root-mean-square deviation (RMSD) values for the studied ternary mixtures. 0.3

Mixtures T = 303.15 K T = 313.15 K 0.8

0.2
NRTL UNIQUAC NRTL UNIQUAC
0.9
RMSD 0.1
(Ethylene carbonate + benzene + 0.0224 0.0258 0.0185 0.0227
1.0
n-heptane) 0.0
(Ethylene carbonate + toluene + 0.156 0.0181 0.0149 0.0162 1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 3
n-heptane)
FIGURE 2. LLE data for {ethylene carbonate (1) + benzene (2) + n-heptane (3)} at
T = 313.15 K: d, experimental tie line data; I, NRTL model; s, UNIQUAC model.

2 2
0.0 0.0
1.0 1.0

0.1 0.1
0.9 0.9

0.2
0.2 0.8
0.8
0.3
0.3 0.7
0.7
0.4
0.4 0.6
0.6
0.5
0.5 0.5
0.5
0.6
0.6 0.4
0.4
0.7
0.7 0.3
0.3
0.8
0.8 0.2
0.2
0.9
0.9 0.1
0.1
1.0
1.0 0.0
0.0
1 1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 3
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 3
FIGURE 3. LLE data for {ethylene carbonate (1) + toluene (2) + n-heptane (3)} at
FIGURE 1. LLE data for {ethylene carbonate (1) + benzene (2) + n-heptane (3)} at
T = 303.15 K: d, experimental tie line data; I, NRTL model; s, UNIQUAC model.
T = 303.15 K: d, experimental tie line data; I, NRTL model; s, UNIQUAC model.

parameters (r and q) are listed in table 6. These parameters depend on molecular

3. Results and discussion
The mole fractions of each component in the two-liquid phases at equilibrium
of the ternary mixtures {ethylene carbonate (1) + benzene or toluene (2) + n-hep-
tane (3)} and the quaternary mixture {ethylene carbonate (1) + sulfolane (10 ) + ben-
zene (2) + n-heptane (3)} are presented in tables 2 and 3. The symbol xei indicates
the mole fraction of constituent i in the ethylene carbonate-rich phase and xhi indi-
cates the mole fraction of constituent i in the n-heptane-rich phase. Also in this ta-
ble, dissolving capacity or the distribution coefficient, K i ¼ xei =xhi and selectivity
factor, S ¼ ðx2 =x3 Þe =ðx2 =x3 Þh are reported. The distribution coefficient refers to the
equilibrium partitioning of the benzene or toluene between two phases. The ability
of ethylene carbonate to separate benzene or toluene from n-heptane is indicated
with the selectivity factor.
As seen from results in tables 2 and 3, the selectivity is not constant over the
whole two-phase region, however, in all cases is greater than one, and this means
that extraction is possible. The calculated UNIQUAC and NRTL parameters are pre-
sented in tables 4 and 5, respectively. The UNIQUAC and NRTL models were used to
correlate the experimental results. As usual in the UNIQUAC model, the lattice coor-
dination number Z was assumed to be equal to 10. The volume and surface area
interactions, molecular size, and molecular external surface areas [7]. The root-
mean-square deviation (RMSD) is a measure of the agreement between the exper-
imental and the calculated values. The RMSD value is defined as follows [8]:
2" #2 31=2
XXX
RMSD ¼ 4 xexp cal
=6M 5
ijk  xijk ð1Þ
i j k
where M is the total number of tie lines, xexp is the experimental mole fraction, xcal
indicates the calculated mole fraction, and the subscripts i, j, and k indicate number
of the tie lines, number of components, and number of the phase, respectively. The
results of RMSD calculations by both models, UNIQUAC and NRTL indicate good
agreement with experimental data as shown in table 7. The phase diagrams for
the ternary mixtures studied are presented in figures 1 to 4. The slopes of tie lines
in the phase diagrams show that benzene or toluene is more soluble in n-heptane
than in ethylene carbonate.
The experimental selectivity at T = (303.15 and 313.15) K for the mixtures of
{ethylene carbonate (1) + benzene (2) + n-heptane (3)} and {ethylene carbonate
(1) + toluene (2) + n-heptane (3)} are reported, respectively, in figures 5 and 6.
Figures 7 and 8 show the experimental distribution coefficient at T = (303.15 and
1284 M. Mohsen-Nia, F.S. Mohammad Doulabi / J. Chem. Thermodynamics 42 (2010) 1281–1285

2 0.55
0.0
1.0

0.1 0.50
0.9

0.2
0.8 0.45

0.3
0.7
0.40

K
0.4
0.6

0.5 0.35
0.5

0.6
0.4 0.30

0.7
0.3
0.25
0.8 0.10 0.15 0.20 0.25 0.30 0.35 0.40
0.2
x2
0.9
0.1
FIGURE 7. Plot of experimental distribution coefficient (K) against mole fraction of
1.0 benzene (x2): {ethylene carbonate (1) + benzene (2) + n-heptane (3)} at tempera-
0.0
tures: s, 313.15 K and d, 303.15 K.
1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 3

FIGURE 4. LLE data for {ethylene carbonate (1) + toluene (2) + n-heptane (3)} at
T = 313.15 K: d, experimental tie line data; I, NRTL model; s, UNIQUAC model. 0.7

25
0.6

20 0.5

0.4
K

15
S

0.3
10

0.2

0.1
0.0 0.1 0.2 0.3 0.4 0.5
0 x2
0.10 0.15 0.20 0.25 0.30 0.35 0.40
x2 FIGURE 8. Plot of experimental distribution coefficient (K) against mole fraction of
toluene (x2): {ethylene carbonate (1) + toluene (2) + n-heptane (3)} at tempera-
FIGURE 5. Plot of experimental selectivity (S) against mole fraction of benzene (x2) tures: s, 313.15 K and d, 303.15 K.
for {ethylene carbonate (1) + benzene (2) + n-heptane (3)} at temperatures: s,
313.15 K and d, 303.15 K.

25
16

14 20

12

15
10
S

8
10

4 5

2
0
0.1 0.2 0.3 0.4 0.1 0.2 0.3 0.4
x2 x2

FIGURE 6. Plot of experimental selectivity (S) against mole fraction of toluene (x2): FIGURE 9. Plot of experimental selectivity (S) against mole fraction of aromatic
{ethylene carbonate (1) + toluene (2) + n-heptane (3)} at temperatures: s, 313.15 K hydrocarbon (x2) at T = 303.15 K: s, {ethylene carbonate (1) + toluene (2) + n-
and d, 303.15 K. heptane (3)} and d, {ethylene carbonate (1) + benzene (2) + n-heptane (3)}.
 M. Mohsen-Nia, F.S. Mohammad Doulabi / J. Chem. Thermodynamics 42 (2010) 1281–1285 1285

0.6

0.5

0.5

0.4

0.4
K

K
0.3
0.3

0.2
0.2

0.1 0.1
0.1 0.2 0.3 0.4 0.1 0.2 0.3 0.4
x2 x2

FIGURE 10. Plot of experimental distribution coefficient (K) against mole fraction of FIGURE 12. Plot of experimental distribution coefficient (K) against mole fraction of
aromatic hydrocarbon (x2) at T = 303.15 K: s, {ethylene carbonate (1) + toluene benzene (x2) at T = 303.15 K: d, {ethylene carbonate (1) + sulfolane (10 ) + benzene
(2) + n-heptane (3)} and d, {ethylene carbonate (1) + benzene (2) + n-heptane (3)}. (2) + n-heptane (3)} and s, {ethylene carbonate (1) + benzene (2) + n-heptane (3)}.

20
4. Conclusions

The LLE data of the ternary mixtures of (ethylene carbon-

15 ate + benzene + n-heptane) and (ethylene carbonate + toluene +
n-heptane) at T = (303.15 and 313.15) K and the quaternary
mixture (ethylene carbonate + sulfolane + benzene + n-heptane) at T =
303.15 K and ambient pressure are reported. The calculated selec-
10 tivity factors and distribution coefficients indicate that ethylene
S

carbonate can be considered as a potential solvent for extraction

of toluene and benzene from (toluene or benzene + n-heptane).
5
The effect of temperature on the extraction process as shown in
table 2 indicates that at lower temperature, S is higher but K is low-
er, therefore in the practical process an optimum temperature
would be considered for extraction of toluene or benzene from (tol-
0 uene or benzene + n-heptane). The UNIQUAC and NRTL activity
0.1 0.2 0.3 0.4 coefficient models satisfactorily correlated the LLE experimental re-
x2
sults of the systems studied are presented. The calculated overall
FIGURE 11. Plot of experimental selectivity (S) against mole fraction of benzene root-mean-square deviations (RMSD) for equilibrium phase mole
(x2) at T = 303.15 K: d, {ethylene carbonate (1) + sulfolane (10 ) + benzene (2) + n- fractions are less than 0.0149 and 0.0162 for NRTL and UNIQUAC
heptane (3)} and s, {ethylene carbonate (1) + benzene (2) + n-heptane (3)}. models, respectively.

313.15) K for the mixtures of {ethylene carbonate (1) + benzene (2) + n-heptane (3)}
and {ethylene carbonate (1) + toluene (2) + n-heptane (3)}, respectively. According
to these figures, at lower temperature the selectivity is higher. However, for an effi-
cient extraction an optimum temperature may be found by considering the exper-
imental values of distribution coefficients as well as the safety and economic
factors.
The comparisons of the experimental selectivity and distribution coefficient for
{ethylene carbonate (1) + benzene (2) + n-heptane (3)} and {ethylene carbonate
(1) + toluene (2) + n-heptane (3)} at T = 303.15 K are shown in figures 9 and 10,
respectively. According to these figures, the extraction efficiency of ethylene car-
bonate for the extraction of benzene from (benzene + n-heptane) is greater than
that for the extraction of toluene from (toluene + n-heptane). Figures 11 and 12,
respectively, show the experimental selectivity and distribution coefficient for (eth-
ylene carbonate + benzene + n-heptane) and (ethylene carbonate + sulfolane + ben-
zene + n-heptane) at T = 303.15 K. These comparisons indicate that the selectivity
and distribution coefficient of ethylene carbonate is higher than that for the (ethyl-
ene carbonate + sulfolane) solvent mixture for the extraction of benzene from (ben-
zene + n-heptane).
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JCT 10-25