Chemical Engineering Science 115 (2014) 186194

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Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Reprint of: Simulation based ionic liquid screening

for benzenecyclohexane extractive separation$
Zhaoxian Lyu a, Teng Zhou b, Lifang Chen a, Yinmei Ye a, Kai Sundmacher b,c, Zhiwen Qi a,n
a

Max Planck Partner Group at the State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
Max Planck Institute for Dynamics of Complex Technical Systems, 39106 Magdeburg, Germany
c
Process Systems Engineering, Otto-von-Guericke University, 39106 Magdeburg, Germany
b

H I G H L I G H T S

[C4mim][AlCl4] is selected as proper solvent to separate benzene and cyclohexane.

COSMO-RS is applied to screen solvent from combinations of 12 cations and 22 anions.
Interaction between ionic liquids and benzene is investigated by DFT calculation.
Continuous extraction processes are simulated using [C4mim][AlCl4] and sulfolane as solvent.

art ic l e i nf o

a b s t r a c t

Article history:
Received 8 June 2013
Received in revised form
4 April 2014
Accepted 5 April 2014
Available online 28 May 2014

In order to screen ionic liquids (IL) as suitable solvents for the separation of benzene and cyclohexane,
the extraction efciency of ILs (12 cations and 22 anions) was estimated based on COSMO-RS predictions
of innite dilution activity coefcients of benzene and cyclohexane in different ILs..[C4mim][AlCl4] was
found to be the most promising solvent. To provide deep insight on how the IL structure inuences the
extraction efciency, molecular interactions between IL ions and benzene were determined from DFT
calculations. Moreover, liquidliquid equilibrium data of the ternary system benzenecyclohexane
[C4mim][AlCl4] were experimentally determined and used to t parameters of the NRTL activity
coefcient model. Based on the NRTL model the continuous extraction process was simulated and
compared with a reference process using sulfolane as solvent. For the extraction process using [C4mim]
[AlCl4], high cyclohexane product purity (99.65 wt%) and high benzene recovery efciency (98.03%) can
be reached with at much lower energy consumption and higher product yield compared to conventional
extraction solvents. In conclusion, the ionic liquid [C4mim][AlCl4] is a promising solvent for the
extractive separation of benzene and cyclohexane.
& 2014 Elsevier Ltd. All rights reserved.

Keywords:
Ionic liquid [C4mim][AlCl4]
Benzenecyclohexane separation
COSMO-RS
Quantum chemical calculation
Process simulation

1. Introduction
As an important industrial chemical, cyclohexane can be produced
by catalytic hydrogenation of benzene. Due to the limitation of the
reaction equilibrium, non-converted benzene is entrained into the
cyclohexane product and must be removed. Since benzene and
cyclohexane have very close boiling points and can even form an
azeotrope, it is difcult to separate this mixture. In industry, the

DOI of original article: http://dx.doi.org/10.1016/j.ces.2014.04.011

A publisher's error resulted in this article appearing in the wrong issue. The
article is reprinted here for the reader's convenience and for the continuity of the
special issue. For citation purposes, please use the original publication details;
Chem. Eng. Sci, 113, pp. 45-53.
n
Corresponding author.
E-mail address: zwqi@ecust.edu.cn (Z. Qi).

http://dx.doi.org/10.1016/j.ces.2014.05.032
0009-2509/& 2014 Elsevier Ltd. All rights reserved.

separation is commonly achieved by liquidliquid extraction using

organic compounds, such as sulfolane, as the solvent. In current
processes, the organic solvent is normally withdrawn from the top
of the regenerator as vapor stream and returned to the bottom of the
extractor as liquid stream. The vaporization of solvent results in high
regeneration cost (Schneider, 2004). In addition, the volatility of
organic solvents can lead to serious environmental problems.
Ionic liquids (ILs) are innovative solvents entirely composed of ions.
Their negligible vapor pressure makes the regeneration much easier,
namely by evaporation or pervaporation of the other mixture components (Seddon, 1997; Huddleston et al., 1998). Due to much lower
energy consumption and investment costs, extraction processes with
ILs as solvents are economically feasible (Meindersma and de Haan,
2008). Moreover, the large number of possible cation and anion
combinations makes it possible to tailor a highly efcient ionic liquid
solvent for a specic separation task (Huddleston et al., 2001). Over

Z. Lyu et al. / Chemical Engineering Science 115 (2014) 186194

the past decade, ILs have been widely studied as solvents for aromatic/
aliphatic liquidliquid separations (Arce et al., 2007a, 2007b, 2008a,
2008b, 2009, 2010; Ferreira et al., 2012; Meindersma and De Haan,
2012; Zhang et al., 2007). According to Meindersma et al. (2010), more
than 120 ILs have been identied as possible candidates aromatic/
aliphatic separation since the rst application reported by John et al.
(1982). It was found that ILs composed of anions with delocalized
electron (e.g., [RSO4]  and [AlCl4]  ) show much better extraction
efciency than other ILs. In several experimental studies, the separation of benzene and cyclohexane was chosen as a benchmark case
(Wang et al., 2008a, 2008b; Gonzlez et al., 2010a, 2010b; Zhou et al.,
2012a, 2012b).
Due to the huge number of cations and anions, it is necessary to
apply reliable theoretical methods to guide the screening of ILs for
separation processes. So far, various predictive methods have been
developed for modeling the thermodynamic properties of ILcontaining systems, e.g., the Perturbed-Chain Statistical Associating
Fluid Theory (PC-SAFT) (Paduszynski and Domanska, 2012; Domanska
et al., 2012) and the Conductor-like Screening Model for Real Solvents
(COSMO-RS) model (Klamt and Eckert, 2000). As a quantum chemistry
based predictive method, the COSMO-RS model has been proven to be
a powerful tool for fast IL solvent screening, including the separation of
aliphatic and aromatic hydrocarbon mixtures (Anantharaj and
Banerjee, 2010, 2011a; Banerjee and Khanna, 2006; Burghoff et al.,
2008; Gutier rez et al., 2010, 2012). Importantly, the available COSMO
database covers a large number of common cations and anions, which
makes it very efcient for screening of ILs as solvents (Klamt and
Eckert, 2000; Diedenhofen et al., 2003).
In order to explain why a selected IL has a pronounced extraction
efciency, it is necessary to determine the specic molecular interactions between the solute molecules and IL ion pairs (Rezabal and
Schfer, 2013). Quantum chemical calculations are the best approach
for studying the cationanion interactions, and interactions between
ILs and solute molecules (Dong et al., 2006, 2012; Dong and Zhang,
2012; Nockemann et al., 2006; Cabao et al., 2011; L et al., 2012). On
the basis of the well-founded HohenbergKohn theorem, density
functional theory (DFT) provides a sound method for obtaining
information of energetics, structures, and properties of atoms and
molecules at high enough accuracy and at much lower computational
costs than traditional ab initio wave function techniques (Geerlings et
al., 2003).
Due to their higher molecular weight, most of the reported ILs
cannot provide a high mass-based extraction efciency, which may
obstruct their applications (Meindersma et al., 2010). Therefore, a
potential IL identied with the help of COSMO-RS might not be
qualied for industrial application. Hence, the extraction performance
of ILs as solvents needs to be further evaluated through extraction
process simulations. For simulating a continuous extraction process,
ternary liquidliquid equilibrium (LLE) data need to be determined
and correlated with a thermodynamic activity coefcient model, such
as the NRTL model (Renon and Prausnitz, 1968).
The objective of this work is to screen ILs as potential solvents to
extract benzene from mixtures with cyclohexane based on simulations
on different scales, i.e., COSMO-RS predictions, DFT calculations, and
process simulations. First of all, innite dilution extraction efciencies
of ILs composed of 12 cations and 22 anions were calculated by using
the COSMO-RS model. The interaction energy and the natural bond
orbital (NBO) were analyzed by quantum chemical calculations to
investigate the suitability of selected ILs from the molecule point of
view. For further conrming the extraction performance of the
selected IL and exploring its potential for industrial application,
process simulations were carried out using Aspen Plus 12.1. Since
the molar content of the unreacted benzene in mixtures with
cyclohexane in practice is lower that 20%, special attention was paid
to the removal of the reactant at low-concentrations of benzene (Zhou
et al., 2012b).

187

2. Ionic liquid screening

2.1. COSMO-RS model
COSMO-RS is a quantum chemistry based statistical thermodynamics model for the prediction of thermodynamic properties
of uids (Klamt and Eckert, 2000). There are generally two steps in
the COSMO-RS prediction procedure, namely (1) the quantum
chemical COSMO computation for the molecular species involved,
and (2) the COSMO-RS statistical thermodynamic treatment. A
standard COSMO-RS prediction only requires the screening charge
density (SCD) information of the interested compounds. The SCD
distribution of a compound is normally obtained from quantum
chemical calculation using the DFT approximation. The SCD needs
to be calculated only once and afterwards it can be stored in a
COSMO le. Nowadays, the available COSMO database already
contains COSMO les of a huge number of common solvents and IL
cations and anions. This makes the COSMO approach very fast and
efcient when predicting thermodynamic properties, e.g., activity
coefcients, of various systems (Klamt and Eckert, 2000, 2004).
In this work, innite dilution activity coefcients of benzene and
cyclohexane in ionic liquids, composed of 12 common cations and 22
common anions, were calculated by using the COSMOthermX software package (COSMOlogic GmbH & Co. KG, Version C3.0, Release
13.01) based on the COSMO-RS method. Among the 12 cations, four
main types of cations with different side chain length were selected
to evaluate the impact of cation classes and side chain lengths on
solvent extraction efciency. For the 22 anions, F-containing and Clcontaining anions, sulfate- and phosphate-anions with different alkyl
substituents were chosen to investigate the inuence of delocalized
electron of anions on the extraction efciency. The detailed information about the considered 12 cations and 22 anions is provided in
Tables S1 and S2, respectively.
Among the studied cations and anions, [AlCl4]  is not in the
current COSMO database. Therefore, the COSMO le of [AlCl4] 
was determined from quantum chemical calculation at the BPTZVP level by Gaussian 03W (Frisch et al., 2004). COSMO les of
other ions, benzene, and cyclohexane were taken directly from the
latest COSMO database (version: BP_TZVP_C21_0111). An IL can be
treated as either a single compound or a mixture of ions. In this
work, cations and anions are treated as individual species with
equal molar fractions (Diedenhofen and Klamt, 2010).

2.2. Extraction efciency at innite dilution

The activity coefcient of a solute i in a solvent S is calculated
from the difference between the chemical potentials of the solute
in the solvent iS and in the pure solute ii

iS  ii

iS exp

!
1

RT
1

The solute distribution coefcient at innite dilution i , which

indicates the extraction capacity of the solvent, can be expressed
in terms of the innite dilution activity coefcient of the solute in
the solvent

1
i

1
i

ILphase
2

where the subscript i represents benzene or cyclohexane. The

extraction selectivity is dened as the ratio of the composition of
benzene in the extract phase to that of benzene in the rafnate
phase. The separation selectivity at innite dilution S1
23 is dened

188

Z. Lyu et al. / Chemical Engineering Science 115 (2014) 186194

as Lei et al. (2007)

1
3

1
2

4.0

ILphase
3

1
In Eq. (3), 1
2 and 3 stand for the innite dilution activity
coefcients of benzene and cyclohexane in the IL solvent, respectively. They can be predicted by the COSMO-RS method. The
performance index (PI p ) is dened as the product of the solute
distribution coefcient and the separation selevtivity, which
indicates the overall extraction efciency of a solvent at innite
dilution (Anantharaj and Banerjee, 2010).
1

PI 1 2  S1
23

In order to validate the COSMO-RS predictions, the experimental and calculated innite dilution benzene/cyclohexane selectivities of four ILs ([C2mim][BF4], [C4mim][BF4], [C6mim][BF4],
[C8mim][BF4]) at different temperatures are compared in Table 1.
The predicted selectivity decreases as the temperature increases
and as the length of the cation side chain grows. This tendency is
in full agreement with the experimental ndings. The estimated
root mean square deviation (rmsd) between the experimental and
calculated selectivities is 15.6%. This deviation is comparable with
the predictions (rmsd 11.0%) of Anantharaj and Banerjee (2011a)
where the COSMO-RS model was successfully applied for the
screening of ILs as solvent for the aliphatic/thiophene separation.
After the benchmarking of COSMO-RS predictions, the screening of
ionic liquids was subsequently carried out. As shown in Fig. 1a, for
most of the investigated cations, the benzene distribution coefcients
of ILs with anions Cl  , [AlCl4]  , and [TOS]  are generally higher than
that of ILs with F-containing anions, such as [BF4]  , [CF3SO3]  . This is
because anions containing a Cl atom or an aromatic ring have more
delocalized electrons than F-containing anions. Anions with more
delocalized electrons show weaker interactions with cations, which
promotes the interaction of the IL with benzene.
For [HSO4]  and [H2PO4]  , their benzene distribution coefcients are lower than that of other anions. However, as the alkyl
chain length increases, e.g., from [H2PO4]  to [DBP]  (anion
number: 1821), the distribution coefcient increases substantially. This is because the electron-donating ability of alkyl groups
is stronger than that of the hydrogen atom. Thus the electrons of
anions with alkyl chain are more delocalized, which nally results
in a stronger interaction between ILs and benzene. But, it was
found that anions with highly delocalized electrons can not only
form -complextion with aromatics (Zhang et al., 2007), but also
facilitate aromatics to share the positive charge of the cation
(Meindersma et al., 2010). The major factor dominating the
interaction between IL and benzene was further studied via
quantum chemical calculations as discussed in the next section.
For most of the anions, similar effects of the cation side chain
length on the solvent extraction capacity were found for both
imidazolium and ammonium ILs. Benzene distribution coefcients
gradually increase with the cation side chain length, i.e., [C2mim] o
[C4mim] o[C6mim] o[C8mim] o[C10mim] . This is consistent
Table 1
The comparision of experimental and COSMO-RS predicated benzene/cyclohexane
selectivities of IL solvents at innite dilution condition.
Ionic liquids

[C2mim][BF4]
[C4mim][BF4]
[C6mim][BF4]
[C8mim][BF4]
a

Experimental dataa

[C4mpyro]

[C4mpip]

[P4444]

[N2222]

[C4mim]

3.5

[C6mim]

3.0

[C8mim]

[C10mim]

2.5

[N3333]

[C4py]

2.0

[N4444]

[AlCl4]

[TOS]
[HSO4]

1.5

[H2PO4]

1.0
0.5
0.0
0

10

12

14

16

18

20

22

24

Anions

10
[C2mim]+

[AlCl4]

[C4mpyro]+

[C4mpip]

[P4444]

[N2222]

[C4mim]

[C6mim]

[C8mim]

+
+

[C10mim]

[N3333]

[C4 py]

[N4444]

5
4
3
2
1
0

10

12

14

16

18

20

22

24

Anions
Fig. 1. Benzene distribution coefcient (a) and performance index (b) of ILs composed
of 12 different cations and 22 different anions (Tables S1 and S2) predicted by the
COSMO-RS method at the innite dilution condition (1. [Br]  , 2. [Cl]  , 3. [NO3]  , 4.
[BF4]  , 5. [PF6]  , 6. [AlCl4]  , 7. [CH3COO]  , 8. [ClO4]  , 9. [SCN]  , 10. [CF3COO]  , 11.
[CH3SO3]  , 12. [CF3SO3]  , 13. [TOS]  , 14. [HSO4]  , 15. [CH3SO4]  , 16. [EtSO4]  , 17.
[BuSO4]  , 18. [H2PO4]  , 19. [DMP]  , 20. [DEP]  , 21. [DBP]  , 22. [Tf2N]  ).

with the reported experimental results where [Cnmim][PF6] (n 4, 5,

6) was studied as solvent for the separation of benzene from
cyclohexane (Zhou et al., 2012a) and [Cnmim][NTf2] (n2, 4, 8, 10)
for the separation of benzene from hexane (Arce et al., 2007b).
In order to evaluate the overall extraction efciency of ILs, their
performance index at innite dilution was analyzed. As seen in
Fig. 1b, for all studied cations, ILs containing [AlCl4]  show very
high PI p values. Among them, [C2mim][AlCl4] was found to be the
best solvent candidate; but, it is a solid at room temperature, thus
cannot be applied as solvent in an extraction process. Taking into
account the overall extraction efciency, [C4mim][AlCl4] and
[C4py][AlCl4] were found to be promising solvents. But, as the
relatively high viscosity of [C4py][AlCl4] make it unsuitable for
industrial operation (Meindersma and De Haan, 2012), [C4mim]
[AlCl4] is nally proposed as solvent for the separation of benzene
from cyclohexane via liquidliquid extraction.

Calculated data

303 K

323 K

343 K

303 K

323 K

343 K

22.20
18.80
11.44
6.66

18.39
15.79
10.01
6.19

15.74
13.22
9.05
5.71

20.61
13.86
10.11
7.63

17.51
11.72
8.66
6.63

14.94
10.03
7.50
5.82

From Foco et al. (2006).

[C2mim]

Cl

Benzene distribution coefficient

Performance Index

S1
23

3. Quantum chemical calculations

3.1. Calculation methods
It was found out by COSMO-RS predictions that ILs with
[AlCl4]  have an excellent extraction efciency. It would be very

Z. Lyu et al. / Chemical Engineering Science 115 (2014) 186194

helpful to explain the suitability of [C4mim][AlCl4], if the contributions of specic interactions, such as hydrogen bonding or
-complextion, is analyzed in detail. As suggested, the impact of
CH- and interactions between the IL-cation and benzene on
the extraction efciency cannot be neglected (Anantharaj and
Banerjee, 2011b; L et al., 2012; Zhou et al., 2008). However, there
are still very few theoretical studies about the inuence of anions
on the extraction efciency of ILs for benzene.
In this work, [C4mim][BF4] was taken as reference solvent to
[C4mim][AlCl4] in the investigation of the interactions between ILs
and benzene, due to their similar structure but differently delocalized electrons of anions. All quantum chemical calculations were
performed with the Gaussian 03 software package (Frisch et al.,
2004), where the structures were optimized at the B3LYP/631 G** level. The radii of elements used are the Bondi Van
der Waals radius (Bondi, 1964). By means of optimizing several
initial congurations and comparing their nal energies, the
chosen geometry can be approximately regarded as global minimum. After the geometry optimization, the characteristics of the
stationary points were checked and zero-point energies were
evaluated by frequency analysis at the same DFT level. The
interaction energy was calculated via Eq. (5)

E EAB  EA  EB

rij= 3.20
r= -0.05
= 158.8

rij= 3.05
r= -0.20
= 158.8

IL=

-68.27 kcal/mol
= -2.04 kcal/mol

rij = 2.85
r = +0.18
= 123.1

where EAB is the energy of the AB complex, and in the case of this
work is IL-benzene or the cationanion complex. Furthermore,
second-order perturbation delocalization energies E(2) were
obtained by NBO analysis at the same level. E(2) is associated
with the delocalization of i-j, which was is estimated from Eq. (6)
E2 Eij

ni F ij 2
j  i

189

rij = 2.39
r= -0.28
= 153.8

IL=

-81.46 kal/mol
= -1.49 kal/mol

where ni is the donor orbital occupancy, i and j are the diagonal

elements, and Fij is the off-diagonal NBO Fock matrix element.
3.2. Interaction between ionic liquids and benzene
Fig. 2 shows the most stable congurations of the two studied
ILs with benzene. As seen, anions are located in the middle of the
cation and benzene molecule. Moreover, benzene is closer to the
butyl chain of the cation, and is parallel with the imidazole ring.
The interaction energy between the solvent and benzene
indicates the extraction ability of the solvent to some extent (L
et al., 2012). From Fig. 2, the extraction ability of [C4mim][AlCl4] to
benzene (E  2.04 kcal/mol) is stronger than that of [C4mim]
[BF4] to benzene (E 1.49 kcal/mol). This is in accordance
with benzene distribution coefcients calculated by COSMO-RS
(Fig. 1a). As a possible interpretation, the interaction between
[AlCl4]  and [C4mim] (EIL  68.27 kcal/mol) is weaker than
that between [BF4]  and [C4mim] (EIL  81.46 kcal/mol).
Therefore, it is easier for the benzene molecule to penetrate the
bond network in [C4mim][AlCl4] and interact with the anion or the
cation (Ferreira et al., 2012).
Moreover, for the conguration of [C4mim][AlCl4] and benzene
(Fig. 2a), the distance Cl5H14 is 3.05 and Cl4H13 is 3.20 .
Both distances are less than the sum of van der Waals radii of the
H atoms and the neighboring Cl atoms (the differences r are
0.20 and 0.05 , respectively), which indicates two H-bonds
between the anion and benzene. For [C4mim][BF4] and benzene
(Fig. 2b), the r between F27 and H41 is  0.28 . Normally, the
H-bond is strengthened with the decreasing of r. Therefore, the
H-bond strength between [BF4]  and benzene is stronger than
that between [AlCl4]  and benzene. That is to say, the higher
extraction efciency of [C4mim][AlCl4] may not be directly
explained by the H-bond interactions between benzene and
the anion.

Fig. 2. Optimized spatial congurations of IL-benzene complexes ((a) [C4mim]

[AlCl4], (b) [C4mim][BF4]) (Notes: EIL is the interaction energy between cations and
anions, E is the interaction energy between IL and benzene).

Table 2
NBO analysis and second-order perturbation stabilization energy E(2) (kcal/mol)
between ILs and benzene.
Solvent

Cationbenzene
Donor

Acceptor

Anionbenzene
E(2) Donor

Acceptor

E(2)

[C4mim][BF4]

(C33C34) n (C7H17)
(C35C36) n (C4C5)

0.24 LP (B26) sn (C35H41) 0.14

0.10 LP (F27) sn (C35H41) 1.83
LP (F30) sn (C34H40) 0.14

[C4mim][AlCl4]

(C6C7)
(C8C9)

0.48 LP (Cl4) sn C7H13

0.17 LP (Cl5) sn C8H14

n (C24H34)
n (C21C22)

0.39
0.92

The NBO analysis was performed to further determine other

possible orbital interactions, such as CH- and interactions
between ILs and benzene. The results are listed in Table 2.
Generally, the higher the E(2) is, the stronger the interaction in
the orbits will be (Zhao et al., 2012). As seen, E(2) between
[AlCl4]  and benzene (1.31 kcal/mol) is lower than that between
[BF4]  and benzene (2.11 kcal/mol), which indicates that the interaction between [AlCl4]  and benzene is weaker than that between
[BF4]  and benzene. Moreover, the interaction of (C6C7)-n
(C24H34) and (C8C9)-n (C21C22) indicates the existence of
CH- and interactions between [C4mim] and benzene,

190

Z. Lyu et al. / Chemical Engineering Science 115 (2014) 186194

respectively. Importantly, E(2) between benzene and the cation

[C4mim] in [C4mim][AlCl4] (0.65 kcal/mol) is higher than that
between benzene and the cation in [C4mim][BF4] (0.35 kcal/mol).
It may indicate that the weaker bond between [AlCl4]  and
[C4mim] can facilitate the association of benzene and the cation.
In conclusion, there are not only strong H-bonds between
anion and benzene but also comparable CH- and interactions
between the cation and benzene. Compared to [BF4]  , [AlCl4] 
shows a weaker interaction with [C4mim] . This makes it much
easier for benzene to disrupt the connection between cation and
anion. As a result, the CH- and interactions between
[C4mim] and benzene are promoted, which nally results
in a higher afnity of [C4mim][AlCl4] towards benzene. This may
be the main reason why [C4mim][AlCl4] has the better extraction
efciency.

0.00

0.25

e
an
hex
clo
Cy

0.50

ene

The mass-based LLE data for the ternary system benzene

cyclohexane[C4mim][AlCl4] at 298.15 K and atmospheric pressure are displayed in Table S3 and illustrated in Fig. 3. From the LLE

nz
Be

4.2. Evaluation of solvent extraction performance

0.50

0.25

1.00

0.00
0.25

0.50

0.75

1.00

[C4mim][AlCl4]

4. Liquidliquid equilibrium

In order to preliminarily evaluate the extraction efciency of

the selected solvent [C4mim][AlCl4] in practice, LLE experiments
were conducted. Benzene and cyclohexane were purchased from
Lingfeng Co., Ltd. China, with purity higher than 99.5 wt%. The
ionic liquid [C4mim][AlCl4] was purchased from Chengjie Chemical
Co., Ltd. Shanghai, with a purity higher than 99.0 wt% at a water
content below 0.03 wt%. All chemicals were used directly without
further purication.
The LLE experiments were carried out at isothermal conditions
controlled by the oil bath with temperature uctuations below
70.1 K (Huber Ministat 230, Germany). The compositions of the
liquid mixture were determined by the Sartorius BSA224S-CW
balance with a precision of 7 0.0001 g. A certain amount (3.0 g) of
the liquid mixture was sealed in a bottle and stirred with a
magnetic stirrer for at least 3 h and then settled overnight. Afterwards, the upper and lower phases were carefully separated with
syringes and weighted. Considering the instability of the ionic
liquid [C4mim][AlCl4] in humid air, the whole experiment was
carried out under dry nitrogen atmosphere in a glove box. The
samples of both phases were analyzed by gas chromatograph
(Agilent 7890 GC, USA) equipped with a ame ionization detector
(FID) and a PEG-20M column. The GC was equipped with a precolumn as the ionic liquid cannot be analyzed due to its negligible
vapor pressure. First, the GC relative response factor of benzene to
cyclohexane was obtained by using a standard mixture of pure
components. An area normalization method was then applied to
determine the mass ratio of benzene to cyclohexane in each phase.
With the initial weights of benzene and cyclohexane in the
mixtures and the weight of both phases, the content of benzene
and cyclohexane in each phase can be determined. Finally, the
content of IL in each phase can be obtained by subtracting the sum
of the measured mass fractions of benzene and cyclohexane
from unity.
All the LLE experiments were carried out twice and each
sample was analyzed three times to check the reproducibility
and allow for statistical data analysis. The analysis of the two
liquid phases with the syringe causes a variance of 70.02 g. The
absolute deviation of the compositions was estimated to be less
than 1.5 wt%.

0.75

0.75

0.00

4.1. Experimental

Exp.
NRTL fitting

1.00

Fig. 3. Phase diagram for the experimental and NRTL predicted LLE data (mass
based) of the ternary system {[C4mim][AlCl4] benzene cyclohexane} at 298.15 K.

diagram, it is clear that benzene shows a much higher solubility in

the extract phase than cyclohexane. Moreover, the miscibility gap
is very broad at the low-benzene-content region, which indicates
that [C4mim][AlCl4] is very suitable to separate benzene at low
concentration from cyclohexane.
The solvent usage for the extraction process is determined by the
solute distribution coefcient and the product purity mainly depends
on the solvent selectivity. For the benzene and cyclohexane separation,
a good solvent should exhibit a high distribution coefcient for
benzene and meanwhile a reasonable separation selectivity. The
mass-based benzene distribution coefcient () and solvent selectivity
(S) are expressed by Eqs. (7) and (8), respectively

wE2
wR2

wE2 =wR2
wE3 =wR3

S23

where subscripts 2 and 3 represent benzene and cyclohexane,

respectively; superscripts E and R represent the extraction and
rafnate phases, respectively. To evaluate the overall extraction
efciency of a solvent, the performance index (PI) was calculated by
Eq. (9).
PI 2  S23

As [C4mim][PF6] and [C4mim][BF4] were already reported as

promising IL solvents in the benzenecyclohexane separation (Zhou
et al., 2012b), they were used as reference solvents for comparison
with the here selected [C4mim][AlCl4]. In addition, the organic solvent
sulfolane which is commonly used in industry was also considered.
and PI values of these four solvents are plotted together with the
benzene mass fraction in the rafnate phase (see Fig. 4).
From Fig. 4a, [C4mim][AlCl4] has a much higher benzene
distribution coefcient than the other three solvents. Moreover,
its benzene distribution coefcient increases at decreasing benzene concentration in the rafnate phase. 41.0 when the
benzene concentration is lower than 0.2.
From Fig. 4b, the PI of all four solvents decreases as the benzene
concentration in the rafnate phase increases. [C4mim][AlCl4] shows
the largest PI value over the whole benzene concentration region, and
it is about 47 times higher than the PI value of sulfolane.
Furthermore, the solvent selectivity can be calculated by Eq. (8)
based on the data in Fig. 4a and b. As a result, in the low benzene
concentration region, the selectivity of [C4mim][AlCl4] is above 20
and much higher than that of sulfolane.

Z. Lyu et al. / Chemical Engineering Science 115 (2014) 186194

Benzene distribution coefficient

1.4

where g ij is an energy parameter that characterizes the interaction between species i and j, xi is the mole fraction of component i,
ij is a non-randomness parameter related to the mixture, R is the
gas constant, and T is the absolute temperature.
The regression was carried out using Aspen Plus and the IL was
treated as a non-associating component (Seiler et al., 2004). The
non-randomness parameter ij was set to 0.2 or 0.3 according to
the characteristics of the component in the mixture, as recommended by Renon and Prausnitz (1968). The NRTL model parameters were regressed by least squares minimization of the
differences between the calculated and the experimental mole
fraction of the components in the two liquid phases.
In order to compare the extraction processes with [C4mim]
[AlCl4] and sulfolane as alternative solvents, the LLE experimental
data for both systems were tted (LLE data of the system
sulfolanebenzenecyclohexane were taken from Chen et al.
(2000)). The identied NRTL model parameters for the studied
systems are listed in Table 3. The mass-based rmsd between the
experimental and calculated LLE compositions was evaluated to
provide a measure of the correlation accuracy (Domaska et al.,
2007). The calculated rmsd are 0.0044 and 0.0084, respectively,
indicating high regression quality for both systems.

[C4mim][PF6] (Zhou et al., 2012b)

[C4mim][BF4] (Zhou et al., 2012b)

1.2

[C4mim][AlCl4] (This work)

Sulfolane (Chen et al., 2000)

1.0
0.8
0.6
0.4
0.2
0.0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

wben in the raffinate phase (mass)

30

[C4mim][PF6] (Zhou et al., 2012b)

[C4mim][BF4] (Zhou et al., 2012b)

25

[C4mim][AlCl4] (This work)

5.2. Extraction process analysis

Performance Index

Sulfolane (Chen et al., 2000)

20

15

10
5

0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

wben in the raffinate phase (mass)

Fig. 4. Experimental benzene distribution coefcient (a) and solvent performance
index (b) for the ternary systems {solvent benzene cyclohexane} at 298.15 K.
Error bars represent the standard deviations.

The LLE experiment data presented and discussed above,

conrm that the computationally preselected solvent [C4mim]
[AlCl4] in fact has a high extraction efciency at low benzene
concentration, indicating its great potential for the deep separation of benzene from cyclohexane. These ndings suggest that the
COSMO-RS model is an effective tool for pre-screening of solvents
without the need for extensive experiments.

5. Process simulation and analysis

In order to investigate the solvent extraction efciency under

continuous process operation conditions, rst the experimentally
determined phase equilibrium data were regressed with the NRTL
model. The activity coefcient i for component i is given by the
NRTL model (Renon and Prausnitz, 1968)


j ji xj Gji
xj Gij
x G

ij  m mj m mj
10
ln i
k xk Gki
k xk Gkj
j k xk Gkj

gij
RT

Gij exp  ij ij

Using the NRTL model, a continuous extraction process for

separating benzene from cyclohexane was preliminarily simulated
in Aspen Plus 12.1. The extractor, evaporator, and distillation
column are modeled by the Extract block, Flash block, and RadFrac
block, respectively. The simulated feed contained 14 wt% of benzene and was added to the bottom of the extractor. The extract
phase and the rafnate phase were collected separately and
delivered to the ash or distillation column to remove the solvent.
Recycled solvents were added to the top of the extractor, together
with the fresh solvent. The process owsheet is depicted in Fig. 7.
In order to achieve a high cyclohexane product purity of at least
99.50 wt% and meanwhile to ensure a high benzene recovery ratio
of about 98.0%, the required stage number of the extractor and the
corresponding solvent-to-feed ratio (S/F) for the studied solvents
were calculated and plotted in Fig. 5. As can be seen, the required
solvent amount decreases at increasing number of stages. For the
same separation task, the required amount of [C4mim][AlCl4] is
only about 30% of [C4mim][BF4] (Zhou et al., 2012b) and also of
sulfolane with the same number of stages. For example, when the
number of stages is n 6, the required solvent-to-feed ratio are
S/F1.49, 5.33, and 5.29 for [C4mim][AlCl4], [C4mim][BF4], and
sulfolane, respectively.
For [C4mim][AlCl4] as extracting solvent, the purity of the cyclohexane product and the benzene recovery ratio as functions of the S/F
ratio at different number of stages are given in Fig. 6. Obviously, when
Table 3
NRTL parameters regressed from the experimental LLE data for the ternary system
{[C4mim][AlCl4] or sulfolane (1) benzene (2) cyclohexane (3)} at 298.15 K.

5.1. NRTL model regression

ij

191

11
12

Component

NRTL parameters

ij

(gij/R)/K

rmsd
(gji/R)/K

{[C4mim][AlCl4] (1) benzene (2) cyclohexane (3)}

12
 1613.92
184.48
13
344.13
1127.42
23
1635.88
 1259.25
{sulfolane (1) benzene (2) cyclohexane (3)}a
12
81.45
 79.28
13
636.79
1857.73
23
1063.45
 707.30
a

The LLE data are from Chen et al. (2000).

ij
0.3
0.3
0.3
0.3
0.2
0.3

0.0044

0.0084

192

Z. Lyu et al. / Chemical Engineering Science 115 (2014) 186194

7
1.000

Mass ratio of S/F

Mass purity of cyclohexane product

[C4mim][BF4] (Zhou et al., 2012b)

Sufolane (This work)

3
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4

[C4mim][AlCl4] (This work)

10

12

14

16

18

20

0.995
0.990

NT=4
NT=6
NT=8
NT=10
NT=12

0.985
0.980
0.975
0.970

22

1.0

1.2

Number of stages
Fig. 5. Mass ratio of solvent-to-feed (S/F) plotted with the number of stages for the
separation demands of cyclohexane mass purity 499.50% and benzene recovery
ratio 498%.

1.6

1.8

2.0

2.2

1.00
0.98

Recovery ratio of benzene

S/F or the number of stage increases, both the cyclohexane product

purity (Fig. 6a) and the benzene recovery ratio (Fig. 6b) are enhanced.
But this improvement is very limited when S/F or the number of stages
reaches a high value. For example, taking S/F1.2, when the number
of stages increases from 4 to 6, there are signicant improvements of
the cyclohexane product purity (from 98.92 wt% to 99.47 wt%) and the
benzene recovery ratio (from 93.79% to 97.00%), while with the stage
number changing from 6 to 8, the improvement of the cyclohexane
product purity (from 99.47 wt% to 99.63 wt%) and benzene recovery
ratio (from 97.00% to 97.88%) is almost negligible. Based on the above
analysis, the number of stages and the solvent-to-feed ratio for
[C4mim][AlCl4] were nally chosen to be n6 and S/F1.49,
respectively.
With the obtained operation parameters, the extraction process
using [C4mim][AlCl4] as solvent was simulated. The main unit
congurations with the stream ow rate and component mass
fraction information as well as the energy consumptions are given
in Fig. 7a. The total mass ow rate of the cyclohexane/benzene
feed was set to 8310.0 kg/h (100 kmol/h). The nally achieved
mass purity of the cyclohexane product was 99.65 wt% and the
recovery ratio of benzene was 98.03%.
Before returning to the top of the extractor, the recycled IL
stream from Flash B is used to preheat the extract phase stream to
its bubble point in order to reduce the total energy consumption.
The calculated energy of the heat exchanger is 161.0 kW. After
such heat exchange, the total energy consumption is mainly
caused by the regeneration of solvent and condensation of the
ashed vapor. From Fig. 7a, the total energy consumption for
solvent regeneration is 1686.2 kW, and for cooling of the recycled
IL and the ashed vapor it is  1629.0 kW.
The extraction process was also simulated with sulfolane as
the solvent under the same feed and extractor conditions as in
the case of [C4mim][AlCl4]. The sulfolane usage is determined by
the separation requirements, as dened in the [C4mim][AlCl4]
process. Similarly, the extract phase stream is preheated by the
recycled solvent stream, and the exchanged energy is 723.4 kW.
Instead of ash units, a distillation column is used for the
solvent regeneration, as shown in Fig. 7b. The energy required
for heating in the reboiler is 5572.6 kW and for cooling in the
condenser it is  5479.1 kW. These energy consumptions are
about 3.3 and 3.4 times of those in the [C4mim][AlCl4] process,
respectively. The much higher energy consumption of the
sulfolane process is mainly attributed to its larger amount of
recycled solvent (43,998.5 kg/h), compared to 12,400.0 kg/h in
the [C4mim][AlCl4] process. Moreover, the cyclohexane recovery

1.4

Mass ratio of S/F

0.96
NT=4
NT=6
NT=8
NT=10
NT=12

0.94
0.92
0.90
0.88
0.86
0.84
0.82
1.0

1.2

1.4

1.6

1.8

2.0

2.2

Mass ratio of S/F

Fig. 6. Mass purity of cyclohexane product (a) and recovery ratio of benzene
(b) plotted with the mass ratio of solvent-to-feed (S/F) at different number of stages
for the solvent [C4mim][AlCl4].

in the sulfolane process (87.70%) is less than that in the [C4mim]

[AlCl4] process (90.10%), due to the lower extraction selectivity
of sulfolane.
In summary, compared to conventional organic solvents, the
ionic liquid [C4mim][AlCl4] is demonstrated to be a suitable
alternative solvent for the separation of benzene and cyclohexane.
This solvent leads to much low energy consumption and a high
product yield. Considering the stability problem of [C4mim][AlCl4]
in the presence of water, an inert gas could be used to purge
humid air out of the process during the start-up phase of an
industrial extraction process.

6. Conclusions
For the screening of ILs as solvents for separating the mixture of
benzene and cyclohexane, the benzene distribution coefcient and
solvent performance index at innite dilution were calculated by
using the COSMO-RS model for 264 IL solvents (12 cations and 22
anions). As a result, [C4mim][AlCl4] was identied as the best
solvent candidate. The molecular interactions between IL ions and
benzene were analyzed by DFT calculations. The results reveal
that, compared to [BF4]  , [AlCl4]  shows a weaker interaction
with [C4mim] , which contributes to the reinforcement of CH-
and interactions between [C4mim] and benzene. This leads
to the relatively higher capacity of [C4mim][AlCl4] as extraction
solvent. Based on own experimental LLE data, NRTL parameters

Z. Lyu et al. / Chemical Engineering Science 115 (2014) 186194

193

Recycled ionic liquid

Cyclohexane
-844.7 KW product 6461.7 kg/hr

6749.9 kg/hr
w1=0.0426
w2=0.0034
w3=0.9539

0.0 kg/hr
w1=1.0000
w2=0.0000
w3=0.0000

P=0.01 atm
T=356.15 K
845.0 KW

NT=6
P=1 atm
T=298.3K

Solvent

Residual liquid
-350.4 KW

14010.1kg/hr
w1=0.8645
w2=0.0850
w3=0.0505

Feed
8310.0 kg/hr
w1=0.0000
w2=0.1400
w3=0.8600

w1=0.0000
w2=0.0035
w3=0.9965

P=0.01 atm
T=523.15 K
841.2 KW

1848.3 kg/hr
w1=0.0000
w2=0.6171
w3=0.3829

12161.8 kg/hr
w1=0.9959
w2=0.0041
w3=4 PPM

161.0 KW

-433.9 KW

288.2 kg/hr
w1=0.9988
w2=0.0010
w3=0.0002

Recycled ionic liquid

Cyclohexane
product 6291.5 kg/hr
w1=760 PPM
w2=0.0030
w3=0.9962
4.8 kg/hr
w1=1.0000
w2=0.0000
w3=0.0000

Solvent

T=349.3 K
-651.7 KW

NT=6
P=1 atm
T=300.0 K

R=1.5

46018.5 kg/hr
w1=0.9560
w2=0.0249
w3=0.0191

Feed

2020.0 kg/hr
w1=7 PPM
w2=0.5650
w3=0.4350

NT=5
P=1 atm
T=558.6 K
5572.6 KW

8310.0 kg/hr
w1=0.0000
w2=0.1400
w3=0.8600

723.4 KW

Recycled solvent

43998.5 kg/hr
w1=1.0000
w2=70 PPM
w3=16 PPB

-4827.4 KW
Fig. 7. Extraction processes for the separation of benzene and cyclohexane using [C4mim][AlCl4] (a) and sulfolane (b) as the solvent. wmass fraction, 1solvent,
2benzene, 3cyclohexane.

were regressed and the extraction process with [C4mim][AlCl4] as

the solvent was simulated. The optimal number of stages and
solvent-to-feed mass ratio are n 6 and S/F1.49, respectively. For
these values, a high cyclohexane product purity of 99.65 wt% and a
high benzene recovery ratio of 98.03% can be achieved. Moreover,
compared to conventional extraction processes where sulfolane is
used as the solvent, the proposed extraction process exhibits much
lower energy consumption and a higher product yield. This shows
that [C4mim][AlCl4] is a very attractive solvent for the separation
of benzenecyclohexane mixtures.

2012AA061601, Fundamental Research Funds for the Central

Universities of China, and 111 Project (B08021).

Appendix A. Supporting information

Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/110.1016/j.ces.2014.05.032.

References
Acknowledgements
The authors gratefully acknowledge the support from the Max
Planck Society in the framework of the Max Planck Partner Group
program, the Specialized Research Fund for the Doctoral Program
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