Chemical Engineering & Processing: Process Intensification 126 (2018) 81–89

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Chemical Engineering & Processing: Process Intensification

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

Separation of benzene and cyclohexane by extractive distillation intensified T

with ionic liquid
⁎
Wenxue Li, Bo Xu, Zhigang Lei, Chengna Dai
State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Energy Environmental Catalysis, Beijing University of Chemical Technology, Box 266,
Beijing, 100029, China

A R T I C L E I N F O A B S T R A C T

Keywords: The separation of benzene and cyclohexane by extractive distillation was intensified with the addition of ionic
Benzene liquid (IL) as entrainer. The IL [EMIM][BF4] was chosen in terms of selectivity and solvent capacity. Vapor-liquid
Cyclohexane equilibrium (VLE) experiments using pure N-methyl-2-pyrrolidinone (NMP), the NMP and IL mixture, pure
Ionic liquid (IL) sulfolane, and the sulfolane and IL mixture, were conducted. The VLE results indicated that NMP is more suitable
Extractive distillation
than sulfolane, due to the poor miscibility of sulfolane and key components in a whole concentration range.
Process intensification
Moreover, the addition of IL into NMP can slightly improve the relative volatility of cyclohexane to benzene with
UNIFAC-Lei model
the NMP and IL mixed entrainers, but the concentration of volatile NMP in vapor phase decreases obviously with
the addition of IL. Based on the experimental VLE data, the UNIFAC-Lei model was applied, and the corre-
sponding interaction parameters were obtained. The extractive distillation process was designed and optimized
with the equilibrium stage model, in which the UNIFAC-Lei model parameters were implemented. The simulated
results indicated that the extractive distillation process was intensified by the addition of IL in saving energy and
entrainer usage. Moreover, no extra equipment expense is needed compared with benchmark solvent.

1. Introduction
Cyclohexane is not only an important raw material for nylon fibers
and resins, but also the feedstock for the production of cyclohexanone,
cyclohexanol, caprolactam, etc. [1]. The production of cyclohexane
from the hydrogenation of benzene accounts for 80–85% of the total
production worldwide. It is necessary and important to remove un-
reacted benzene from the product stream for pure cyclohexane. Un-
fortunately, the separation of benzene and cyclohexane has been one of
the most challenging tasks in petrochemical industry owing to their
close boiling points (only 0.6 K) and the formation of azeotropic mix-
ture [2,3]. Presently, the most commonly used methods to separate
azeotropic mixture are liquid–liquid extraction, azeotropic distillation,
membrane pervaporation, and extractive distillation [4–6]. Among
these methods, extractive distillation is the most widely applied in in-
dustry because of the good separation performance, the good flexibility
in operation, the high energy efficiency and so on.
In extractive distillation, a third component called entrainer is
added to break the azeotropic point and increase the relative volatilities
of the system [7]. Obviously, the selection of an appropriate entrainer is
a key step to ensure an effective and economical extractive distillation
process. It was reported that two of the most common and suitable
solvents for separating benzene and cyclohexane are sulfolane [8] and
N-methylformamide (NMP) [9]. Most current efforts are made to fur-
ther improve the traditional solvents due to their inevitable short-
comings such as ubiquitous volatility, great toxicity and large usage in
industry [10]. Wang et al. [11] intensified the extractive distillation
using the dimethyl formamide and KAc. However, adding solid in-
organic salts into the entrainer in extractive distillation may lead to
corrosion to equipment in the production. Moreover, the dissolution
and regeneration of the solid inorganic salts are fatal issues in industrial
operation. Richard [7] studied the performances of three kinds of mixed
conventional solvents used for the separation of benzene and cyclo-
hexane, while the great volatilization loss of traditional organic sol-
vents is still a big unsolved problem. In recent years, more and more
attention has been focused on the application of ionic liquids (ILs) in
extractive distillation, owing to their negligible vapor pressure, high
chemical and thermal stability, and high selectivity for aromatic and
non-aromatic components [12]. It is the non-volatile feature that con-
tributes to reducing the content of organic solvent in product stream
and enhancing the recovery of these solvents [13]. In view of large
expense when using pure IL as entrainer, a physical mixture of con-
ventional solvent and an IL were proposed as entrainers in this work to
utilize the advantages of both traditional solvents (good capacity for

⁎
Corresponding author.
E-mail address: daicn@mail.buct.edu.cn (C. Dai).

https://doi.org/10.1016/j.cep.2018.02.016
Received 20 December 2017; Received in revised form 12 February 2018; Accepted 15 February 2018
Available online 21 February 2018
0255-2701/ © 2018 Elsevier B.V. All rights reserved.
W. Li et al. Chemical Engineering & Processing: Process Intensification 126 (2018) 81–89

nonpolar compounds) and IL (high selectivity for nonpolar compounds) systems containing the same groups [20,21]. For our system, [EMIM]
to intensify the separation of benzene and cyclohexane. Besides, the [BF4] was composed of one CH3 group, one CH2 group, and one [MIM]
addition of IL doesn’t change the primary chemical process or need [BF4] group. Benzene was divided into 6 ACH groups, and cyclohexane
extra equipment investment. was decomposed into 6 CH2, while sulfolane and NMP molecules were
The main contents of the work are as follows: (1) a promising IL for treated as whole groups separately.
the system is screened in terms of selectivity and solvent capacity using The activity coefficient of component i in liquid phase (γi) can be
the COSMOthermX package (version C30_1301) based on the COSMO- calculated as follows:
RS model; (2) vapor-liquid equilibrium (VLE) data concerning the se-
paration of benzene and cyclohexane were measured using single tra- ln γi = ln γiC + ln γiR (1)
ditional solvent (NMP or sulfolane) and mixed entrainers (NMP + IL or
sulfolane + IL) at atmospheric pressure (101.3 kPa), and the optimum where ln γCi represents the combinatorial contribution, which reflects
entrainer was chosen; (3) the popular UNIFAC-Lei model, due to its the influence of the size and shape of groups on activity coefficient, and
simple formulation (only two parameters Ri and Qi for each group, and it is a function of group parameters Rk and Qk for group k; and ln γ iR
two interaction parameters αmn and αnm between different groups) and represents the residual contribution owing to energetic interaction be-
being direct incorporation into simulation programs such as Aspen Plus tween different functional groups, and it contains the group binary
and ProII to establish equilibrium stage (EQ) and nonequilibrium stage interaction parameters αmn and αnm. For the systems concerned in this
(NEQ) models, was extended to the systems investigated in this work, work, the interaction parameters can be obtained in previous publica-
and the corresponding group interaction parameters were obtained; tions except for αmn and αnm between the groups sulfolane and [MIM]
and (4) the rigorous EQ stage mathematical model was established [BF4]. The unknown parameters were obtained by correlating the ex-
based on an actual industrial process to evaluate the effectiveness of perimental phase equilibrium data using the following minimized
extractive distillation process by process simulation software (Aspen average relative deviation as objective function (OF):
Plus V7.2), in which the UNIFAC-Lei model parameters were im-
N γij,cal − γij,exp ⎫
plemented. ⎧1
OF = min
⎨N
∑ γij,exp ⎬
⎩ j=1 ⎭ (2)
2. Experimental section
where γij,exp and γij,cal are the activity coefficients of component i in the
2.1. Materials
liquid phase obtained by experiment and calculation from UNIFAC-Lei
model for data point j, respectively; and N is the number of experi-
Benzene, cyclohexane, NMP, sulfolane, and IL [EMIM][BF4] were
mental data points. It should be noted that during the correlation the
used in this work. Benzene with a purity over 99.5 wt% was supplied by
activity coefficients of both benzene and cyclohexane were used.
Tianjin Guangfu Fine Chemical Research Institute. Cyclohexane with a
Description on the fitting procedure can be found in our previous
purity over 99.8 wt% was supplied by Tianjin Qilianxin Chemical Ltd.
publication [17].
NMP with a purity over 99 wt% was supplied by Beijing J&K Scientific
As a result, the new obtained group interaction parameters between
Ltd. Sulfolane with a purity over 98 wt% was supplied by Tianjin
sulfolane and the IL groups, along with the other group interaction
Guangfu Fine Chemical Research Institute. All above mentioned mate-
parameters involved in this work, are listed in Table 1. The current
rials were used directly without any pretreatment. The IL [EMIM][BF4]
UNIFAC-Lei model parameter matrix for ILs is illustrated in Fig. 1.
with a purity above 99.5 wt% was purchased from Shanghai Chengjie
Chemical Co. Before the experiment, a vacuum rotary evaporator was
used to remove trace water and volatile impurities at 333.2 K for12 h to
3.2. Process simulation
ensure the water content of IL less than 400 ppm after drying.
The extractive distillation process for the separation of benzene and
2.2. Apparatus and procedure
cyclohexane was simulated using the RadFrac model in Aspen Plus
software (version 7.2), in which the UNIFAC-Lei model parameters
The VLE data for the ternary systems of benzene + cyclo-
were input. In the process simulation, benzene, cyclohexane, NMP and
hexane + pure entrainer (sulfolane or NMP) and the quaternary sys-
sulfolane were treated as conventional components by default, the
tems of benzene + cyclohexane + sulfolane/NMP + IL were measured
properties of which can be obtained from the Aspen Plus database di-
at atmospheric pressure using a circulation VLE still, more details of
rectly. While the IL was added as a new component, the physical
which can be obtained in our previous publications [14–16]. In this
properties of which were estimated by group contribution methods or
work, the compositions of benzene, cyclohexane, sulfolane and NMP in
obtained from publications [26–29].
vapor phase were determined by a gas chromatograph (GC 4000A)
equipped with a flame ionization detector (FID) and a HJ-WAX capil-
lary column (60 m × 0.32 mm × 0.25 μm). The calibration area nor- Table 1
malization method was applied to handle peak area data by SC1100 Group binary interaction parameters (amn and anm) among benzene, cyclohexane, NMP,
sulfolane and IL in the UNIFAC-Lei Model.
workstation.
m n αmn αnm
3. Computational details
ACH CH2 −11.12 61.13
3.1. Extension of the UNIFAC-Lei model ACH NMP 30.04 −23.88
ACH sulfolane 222.6 −40.12
ACH [MIM][BF4] 1494.39 85.64
The UNIFAC-Lei model, a universal functional-group activity coef- CH2 sulfolane 469.9 52.9
ficients model, was adopted to predict the thermodynamic equilibrium CH2 NMP 220.3 13.89
behavior of the systems containing benzene, cyclohexane, sulfolane, CH2 [MIM][BF4] 1108.51 588.74
sulfolane [MIM][BF4] 3000.98a 1800.83a
NMP and IL. The IL was divided into several contributive groups ac-
NMP [MIM][BF4] −626.2 −234.66
cording to the method proposed by Lei et al. [17–19]. In the method,
the skeleton of cation and anion of ILs is regarded as a whole functional a
Group binary interaction parameters obtained in this work; others are from refer-
group, which makes it easy to extend the obtained parameters to other ences [12,17].

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W. Li et al. Chemical Engineering & Processing: Process Intensification 126 (2018) 81–89

30
29
28
27
26
25
24
23
22
21
20
19
18
17
16
15
14
13
12
11
10
9
8
7
6
5
4
3
2
1

73 [R1R2R3R4P][(C 8 H17 ) 2 PO 2 ]
[MIM][CH 3 OC2 C2 H4 SO4 ]

[MPY][C 2 H5 OC2 H4 SO4 ]

[R1R2R3R4P][MeSO 4 ]
[N-C3OHPY][Tf 2 N]

[(OCH2)2IM][Tf 2 N]

[R1R2R3R4S][Tf 2 N]
[MIM][MDEGSO 4 ]

[OCH2MIM][Tf 2 N]

[R1R2R3R4P][FAP]
[R1R2R3R4][Tf 2 N]

[R1R2R3R4P][BF 4 ]
[N-C3OHPY][FAP]

[R1R2R3R4P][TS]

[R1R2R3R4P][Cl]
[MIM][DMPO 4 ]

[R1R2R3R4][TS]
[MIM][DEPO 4 ]
[MIM][MeSO 3 ]
[MIM][MeSO 4 ]

[MIM][OcSO 4 ]

[MPYR][Tf 2 N]
[MIM][EtSO 4 ]

[MPIP][Tf 2 N]

[MPYR][SCN]
[MIM][Tf 2 N]

[MPY][Tf 2 N]

[MPYR][TfO]

[Quin][Tf2N]
[MIM][NO 3 ]

[MIM][SbF6 ]
[MIM][BOB]

[MIM][TCB]
[MIM][TFO]

[MIM][SCN]

[MIM][TFA]
[MIM][TOS]

[MPY][BF 4 ]
[MPIP][SCN]

[MPY][SCN]
[MPY][TOS]
[MPY][TfO]
[MIM][BF4 ]

[MIM][PF 6 ]
[MIM][Cl]
Thiophene
sulfolane
CH3 OH

CH2 CO
ACCH2

CCOO
ACOH

HCOO
CH2 O

DMF
NMP
CHF2
CHF3
ACH

CHO

CHF

C2 H4
C=C

H2 O

N2 O
CH2

CO2

CH4

CO2

H2 S
OH

CF2

SO2
O2

H2
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72

74
75
1
2
3
4
5
6
7
8
9

0
Fig. 1. Current UNIFAC-Lei model parameter matrix for ILs. (■) Previously published parameters [21–25]; ( ) previously published parameters by our group [12]; ( ) new parameters
(this work); (□) no parameters available.

4. Results and discussion selectivity) and organic solvent (high capacity). Among the ILs, [EMIM]
[BF4] might be the most potential entrainer from the comprehensive
4.1. Screening of ILs for the separation of benzene and cyclohexane consideration of selectivity and solvent capacity together. Besides,
taking account of other advantages such as relative low price and lower
The selectivity reflects the differences of the interactions between viscosity in practice, [EMIM][BF4] was selected as the additive to sul-
the solutes and solvents, which is the essential of extractive distillation folane or NMP for the intensification of benzene and cyclohexane se-
separation. However, several solvents (especially ILs) would lead to paration by extractive distillation.
partial immiscibility of two binary mixtures with the solutes, which is
undesirable for extractive distillation separation. Thus, a suitable and
appropriate entrainer should have both high selectivity and high sol- 4.2. Extractive distillation with NMP entrainer and the intensification with
∞
vent capacity. In this work, the selectivity at infinite dilution (S12 ) and IL
solvent capacity (SP) are used for the screening of ILs, which are de-
fined as 4.2.1. Relative volatility using single NMP and NMP + IL mixed entrainers
To verify the reliability of experimental apparatus, the binary VLE
γ1∞
∞
S12 = data for benzene and cyclohexane system were measured and assessed
γ2∞ (3) for thermodynamic consistency using Herington area test. The results
indicate that the experimental data satisfy the thermodynamic con-
where γ1∞ and γ2∞ refer to the activity coefficients of components to be
sistency test. The detailed binary VLE data are listed in Table S1, and
separated at infinite dilution state.
the details on thermodynamic consistency test are given in
N γi, cal − γi, exp
1 1
SP = Supplementary data. The ARDs (ARD = N ∑ ,
γi∞ (4) 1
γi, exp
i = cyclohexane or benzene) of activity coefficients between experi-
where i refers to cyclohexane (1) or benzene (2). mental data and UNIFAC-Lei model predicted values were 4.42% and
In this work, the COSMO-RS model (COSMOTherm X software, 5.44% for the ternary and quaternary systems, respectively, confirming
version C30_1301) was used to calculate the activity coefficients at that the thermodynamic behavior can be accurately predicted by the
infinite dilution at 298.15 K for the pre-selection of ILs. The calculated UNIFAC-Lei model for ILs.
selectivity of cyclohexane to benzene and solvent capacity of benzene The experimental isobaric vapor-liquid equilibrium data of the
using different entrainers involving 48 types of ILs as well as traditional ternary mixtures of cyclohexane (1) + benzene (2) + NMP (3) and the
organic solvents (sulfolane and NMP), along the experimental data quaternary mixtures of cyclohexane (1) + benzene (2) + NMP (3)
collecting from literature [30–39], are illustrated in Fig. 2. It can be + [EMIM][BF4] (4) with the mole fractions of entrainers ranging from
seen that the tendency for calculated results by COSMO-RS model and 20% to 40%, in which the mass fractions of IL were 10% or 20%, were
experimental data is similar. The selectivity of cyclohexane to benzene measured. The detailed experimental data and UNIFAC-Lei model
and solvent capacity of benzene with several ILs as entrainer are much predicted values, along with the expanded uncertainties with 0.95 level
higher than those with sulfolane or NMP as entrainer. Moreover, the of confidence of experimental temperature T, and mole fractions of
selectivity and solvent capacity with ILs and organic solvents as en- component i in liquid and gas phases xi and yi, are given in Tables S3
trainers exhibit a contradictory trend. That is, the use of an entrainer and S4 in Supplementary data. The relative volatility (α12) of cyclo-
can’t ensure both high selectivity and high solvent capacity simulta- hexane (1) to benzene (2) was calculated by
neously. Thus, in this work the mixture of IL and organic solvent were
proposed to combine the respective advantages of both IL (high

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W. Li et al. Chemical Engineering & Processing: Process Intensification 126 (2018) 81–89

Fig. 2. Selectivity of cyclohexane to benzene (a), solvent capacity of benzene (b), and solvent capacity of cyclohexane (c) at infinite dilution for ILs at T = 298.15 K. (△) Predicted results
by the COSMO-RS model; dashed line, sulfolane; solid line, NMP. (▲) Experimental data obtained from Refs [23–32].

y1 / x1 entrainers, the relative volatility doesn’t exhibit an obvious change.

α12 =
y2 / x2 (5)

The x1′- y1′ (on an entrainer-free basis) and x1′-α12 profiles in a full
concentration range with pure NMP as entrainer and intensified by the
addition of IL were shown in Figs. 3 and 4, along with the values pre-
dicted by UNIFAC-Lei model. It can be seen that the addition of [EMIM]
[BF4] into NMP can slightly intensify the separation of benzene and
cyclohexane. With the further increase of IL content in the mixed
4.2.2. Volatile loss of NMP in vapor phase
The volatile loss of NMP in the vapor phase at 101.3 kPa was pre-
sented in Fig. 5. As seen, after adding IL into entrainers the con-
centration of volatile solvent NMP in vapor phase (y3) is much lower
than that with pure NMP as entrainer. This can be explained from the
following two aspects: (1) the interaction between NMP and IL makes

84
W. Li et al.
Fig. 3. Isobaric VLE data for the cyclohexane (1) + benzene (2) system at 101.3 kPa
using the mixed entrainers (NMP (3) + [EMIM]+[BF4]−(4)). (a) xentrainer = 20%; (b)
xentrainer = 30%; (c) xentrainer = 40%. Lines, predicted results by the UNIFAC-Lei model;
scattered points, experimental data. (□) wIL = 0; ( ) wIL = 10%; ( ) wIL = 20%.
less NMP volatilize into vapor phase; (2) less NMP was used in mixed
entrainer compared with using pure NMP as entrainer. Therefore, the
addition of IL into NMP can help to further improve the purity of cy-
clohexane product obtained at the top of extractive distillation column,
which is a significant criterion when evaluating the process of ex-
tractive distillation. In addition, the decrease of NMP in vapor phase
can also intensify the solvent recovery process and save the energy
consumption required.
4.3. Relative volatility using single sulfolane and mixed entrainers
The vapor liquid equilibrium experimental data of the ternary
system of benzene (1) + cyclohexane (2) + sulfolane (3) and the qua-
ternary system of benzene (1) + cyclohexane (2) + sulfolane
(3) + [EMIM][BF4] (4) at 101.32 kPa were measured in the same
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Chemical Engineering & Processing: Process Intensification 126 (2018) 81–89
Fig. 4. Relative volatility of cyclohexane (1) to benzene (2) using the mixed entrainers
(NMP + [EMIM]+[BF4]−). (a) xentrainer = 20%; (b) xentrainer = 30%; (c) xentrainer = 40%.
Lines, predicted results by the UNIFAC-Lei model; scattered points, experimental data.
(□) wIL = 0; ( ) wIL = 10%; ( ) wIL = 20%.
method as mentioned above. The detailed experimental data and
UNIFAC-Lei model predicted values, as well as the experimental un-
certainties, are listed in Tables S5 and S6 in Supplementary data.
The x1′- y1′ profiles and relative volatility profiles ( x1′-α12) were illu-
strated in Figs. 6 and 7. As seen, the results predicted by UNIFAC-Lei
model were in agreement with experimental data, and the ARDs of
activity coefficients for the ternary system and quaternary system were
8.41% and 7.80%, respectively. This confirmed the reliability of the
new obtained interaction parameters between IL and sulfolane. Thus,
the new obtained parameters can be input into commercial simulation
softwares (e.g., Aspen Plus and Pro II) to simulate and design extractive
distillation and other separation processes containing the same func-
tional groups. Meanwhile, it showed that the addition of IL doesn’t
obviously intensify the separation of benzene and cyclohexane by ex-
tractive distillation with sulfolane as entrainer, and the three lines
displayed in x1′- y1′ and x1′-α12 profiles almost overlap. Moreover, it is
noted that with the increase of cyclohexane in liquid phase there is a
sharp decrease in case of x1′ over 0.4, which may be attributed to the
partial immiscibility of sulfolane with cyclohexane.
W. Li et al.
Fig. 5. NMP content in vapor phase for the cyclohexane (1) + benzene (2) + mixed
entrainers (NMP (3) + [EMIM]+[BF4]− (4)) system at 101.3 kPa. (a) xentrainer = 20%; (b)
xentrainer = 30%; (c) xentrainer = 40%. Lines, predicted results by the UNIFAC-Lei model;
scattered points, experimental data. (□) wIL = 0; ( ) wIL = 10%; ( ) wIL = 20%.
4.4. Comparison among four types of entrainers
We went a further step to make a comparison among the four types
of entrainers (i.e., pure NMP, NMP + IL, pure sulfolane, and
sulfolane + IL) for the separation of benzene and cyclohexane by ex-
tractive distillation. It can be seen from Fig. 7 that pure sulfolane en-
trainer exhibits high separation performance when cyclohexane content
is small; however, the relative volatility of cyclohexane to benzene
decreases sharply due to the limited solvent capacity of cyclohexane in
sulfolane, leading to the partial immiscibility. In case of sulfolane + IL
mixed entrainer, the selectivity and solvent capacity don’t improve
obviously. When using pure NMP as entrainer, the relative volatility
can be affected by benzene concentration to some extent, but the partial
immiscibility phenomenon doesn’t appear. Considering the separation
performance within the whole composition range, it is more efficient to
get purer product using NMP as entrainer than using sulfolane. Fur-
thermore, the energy consumption to recycle NMP was smaller than
sulfolane owing to the lower boiling point of NMP. Therefore, the
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Chemical Engineering & Processing: Process Intensification 126 (2018) 81–89
Fig. 6. Isobaric VLE data for the cyclohexane (1) + benzene (2) system at 101.3 kPa
using the mixed entrainers (sulfolane (3) + [EMIM]+[BF4]− (4)). (a) xentrainer = 20%; (b)
xentrainer = 30%; (c) xentrainer = 40%. Lines, predicted results by the UNIFAC-Lei model;
scattered points, experimental data. (□) wIL = 0; ( ) wIL = 10%; ( ) wIL = 20%.
mixed entrainers containing NMP are more appropriate to separate
benzene and cyclohexane by extractive distillation. When using IL to
intensify the extractive distillation with NMP, the volatile loss of NMP
in vapor phase can obviously decrease. Thus, the mixture of NMP and IL
were proposed as the entrainer for the extractive distillation process
design and simulation.
4.5. Design and optimization of the extractive distillation process
The extractive distillation process with the mixture of NMP and
[EMIM][BF4] (90 wt% NMP + 10 wt% IL) as entrainers was simulated
and compared with the benchmark entrainer NMP. The flow sheet of
extractive distillation processes with pure and mixed entrainers is the
same, consisting of one extractive distillation column (EDC) and one
solvent recovery column (SRC), as shown in Fig. 8. The feed (benzene
and cyclohexane mixture) is introduced into EDC from the middle
stage, while the entrainer is input from the stage near the top of EDC.
Then, the cyclohexane product is obtained at the top of EDC, and the
bottom stream containing benzene and entrainer is introduced into SRC
to obtain the benzene product at the top and entrainer at the bottom
W. Li et al. Chemical Engineering & Processing: Process Intensification 126 (2018) 81–89

Fig. 8. Extractive distillation process for the separation of benzene and cyclohexane.

Table 2
Optimized operating conditions for the separation of benzene and cyclohexane using pure
entrainer and using the mixed entrainers of NMP + IL.

Contents Entrainers

NMP NMP + [EMIM]+[BF4]−

EDC Pressure (atm) 1 1

Total stages 29 29
Feed stage 19 19
Entrainer feed stage 5 5
Temperature of entrainer ( °C) 75 75
Molar reflux ratio 1 0.9
Solvent ratio 1.8 1.6
Distillate rate (kmol h−1) 50 50
SRC Pressure (atm) 0.1 0.1
Total stages 10 10
Feed stage 5 5
Distillate rate (kmol h−1) 50 50

mixed entrainers and that using pure NMP is given in Table 3. It can be
seen that the total heat duties of reboilers and condensers using mixed
entrainer decrease by 5.42% and 6.57% compared with those using
Fig. 7. Relative volatility of cyclohexane (1) to benzene (2) using the mixed entrainers pure NMP, respectively. It means that the addition of IL can decrease
(sulfolane + [EMIM]+[BF4]−). (a) xentrainer = 20%; (b) xentrainer = 30%; (c)
energy consumption and save the amount of entrainer to intensify the
xentrainer = 40%. Lines, predicted results by the UNIFAC-Lei model; scattered points, ex-
perimental data. (□) wIL = 0; ( ) wIL = 10%; ( ) wIL = 20%.
whole separation process. Noting that the addition of IL is very small,
and it is a one-time investment. Thus, the price issue of IL is not taken
into consideration during the evaluation of the new process.
which is recycled back to the entrainer stream of EDC after cooling. In
the process, a small fresh entrainer stream is added into the solvent
5. Conclusions
stream to make up unavoidable losses. Based on an actual industrial
process, the operation conditions including feed composition, feed flow
In this work, the separation of benzene and cyclohexane by ex-
rate and total stage number were determined. The feed with the flow
tractive distillation with NMP as entrainer was intensified by the ad-
rate of 100 kmol h−1 is an equimolar mixture of benzene and cyclo-
dition of IL. [EMIM][BF4] was chosen as the suitable additive for the
hexane, the composition of which is close to azeotrope.
separation of benzene and cyclohexane when considering selectivity
The objectives of designing the extractive distillation process are
and solvent capacity together. In addition, the cost and viscosity of
that: 1) the mole fraction of cyclohexane at the top of EDC over 99.9%,
[EMIM][BF4] are acceptable. Then, the VLE data of benzene and cy-
and 2) the mole fraction of benzene at the top of SRC more than 99.9%.
clohexane with four types of entrainers (i.e., pure NMP, NMP + IL, pure
A sensitivity analysis was carried out to obtain the optimized operation
sulfolane, and sulfolane + IL) were measured at 101.3 kPa. On this
condition for the separation process concerning the following operating
basis, the UNIFAC-Lei model was extended to the concerned systems,
parameters: the molar ratio of solvent (entrainer) to feed of EDC, the
and the corresponding interaction parameters were obtained. The re-
reflux ratios of EDC and SRC, the feed stage and the entrainer feed
sults indicated that NMP is more suitable than sulfolane as entrainer for
stage, the temperature of entrainer, and the operating pressure of SRC.
the separation of benzene and cyclohexane, because of poor miscibility
The details of the optimized operating conditions are listed in Table 2. It
of sulfolane with the components to be separated in a full concentration
can be seen that the amount of entrainer decreases from 180 kmol h−1
range.
for pure NMP to 160 kmol h−1 for NMP + IL mixture.
The experimental and UNIFAC-Lei model predicted VLE data
The comparison of the simulated results for the process using the
showed that the addition of IL can slightly improve the relative

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W. Li et al. Chemical Engineering & Processing: Process Intensification 126 (2018) 81–89

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