Benzene and cyclohexane separation using 1-butyl-3-methylimidazolium thiocyanate

Girma Gonfa, Marhaina Ismail, and Mohamad Azmi Bustam

Citation: AIP Conference Proceedings 1877, 020005 (2017); doi: 10.1063/1.4999855

View online: https://doi.org/10.1063/1.4999855
View Table of Contents: http://aip.scitation.org/toc/apc/1877/1
Published by the American Institute of Physics

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Preface: 4th International Conference on the Advancement of Materials and Nanotechnology

AIP Conference Proceedings 1877, 010001 (2017); 10.1063/1.4999850
 Benzene and Cyclohexane Separation Using 1-Butyl-3-
Methylimidazolium Thiocyanate

Girma Gonfa1,b) , Marhaina Ismail2 and Mohamad Azmi Bustam 1,2, a)

1
Research Centre for Carbon Dioxide Capture, RCCO2C, Universiti Teknologi PETRONAS, 32610 Bandar Seri
Iskandar, Perak, MALAYSIA
2
Chemical Engineering Department, Universiti Teknologi PETRONAS, 32610 Bandar Seri Iskandar, Perak,
MALAYSIA

Corresponding author: a)azmibustam@utp.edu.my, b)kiyaagonfaa@gmail.com

Abstract. Cyclohexane is mainly produced by catalytic hydrogenation of benzene. Removal of unreacted benzene from
the product stream is very important in this process. However, due to their close boiling points and azeotrope formation,
it is very difficult to separate cyclohexane and benzene by conventional distillation. Currently, special separation
processes such as processes extractive distillation is commercially used for this separation. However, this extractive
distillation suffers from process complexity and higher energy consumption due to their low extractive selectivity of
molecular entrainers used. The aim of the present work is to investigate the applicability of ionic liquids as entrainer in
extractive distillation of benzene and cyclohexane mixture. In this study, we investigated 1-butyl-3-methylimidazolium
thiocyanate ([BMIM][SCN]) ionic liquid for separation of benzene and cyclohexane by measuring the Vapor Liquid
Equilibrium data of the two components in the presence of the ionic liquid. As green and potential environmentally
friendly solvents, ionic liquids have attracted increasing attention as alternative conventional entrainers in extractive
distillation. Isothermal Vapor Liquid Equilibrium for the benzene + cyclohexane + [BMIM][SCN] ternary system was
obtained at 353.15 K using a Head Space Gas Chromatography. The addition of [BMIM][SCN] breaks the benzene-
cyclohexane azeotrope and increased the relative volatility cyclohexane to benzene in the mixture. The effect of
[BMIM][SCN] on the relative volatility cyclohexane to benzene was studied at various benzene and cyclohexane
compositions and solvent to feed ratios. The performance of [BMIM][SCN] was compared with typical conventional
solvents, dimethylformamide (DMF) and dimethylsulfoxide (DMSO). The results show that the relative volatility of
cyclohexane to benzene in the presence of [BMIM][SCN] is higher compared that of DMSO and DMF.

Keywords: Cyclohexane, catalytic hydrogenation, [BMIM][SCN]

INTRODUCTION
Cyclohexane is used as varnish and paint remover, as organic solvent for cellulose ethers, polyethylene, rubber,
fats and essential oils [1]. However, the primary use of cyclohexane is to produce intermediate precursors for
production of feedstock for Nylon 6 and Nylon 6,6 [1, 2]. Since, cyclohexane sparsely present in crude oil, it is
mainly produced by hydrogenation of benzene in the presence of hydrogen and catalyst under exothermic condition
[1, 3]. The highly exothermic reaction makes reaction yield control very difficult, and the process requires a
multistage design that includes cyclohexane separation and recycling, staged benzene feed injection and inner
reactor cooling to remove the excess heat generated. However, separation of benzene and cyclohexane mixture is
known as one of the most difficult process in the petrochemical industry because of their close boiling points and
formation of an azeotropic mixture. Benzene and cyclohexane form azeotropic mixture at 45 volume % cyclohexane
whose constant boiling point is 77.5 °C [4]. Moreover, the boiling point of benzene and cyclohexane is very close in
all other composition ranges. Consequently, it is not possible to separate benzene and cyclohexane by using

4th International Conference on the Advancement of Materials and Nanotechnology (ICAMN IV 2016)
AIP Conf. Proc. 1877, 020005-1–020005-5; doi: 10.1063/1.4999855
Published by AIP Publishing. 978-0-7354-1557-7/$30.00

020005-1
conventional distillation process. Special separation processes such as extractive distillation and azeotropic
distillation are the main technologies presently used for separation of cyclohexane and benzene [1]. In extractive
distillation, higher boiling point and relatively stable solvents; sometimes called entrainers, are used to change the
phase equilibrium of the system in such a way that the relative volatility of the interest component is increased. Up
to date, two kinds of entrainers, liquid solvents and mixture of solid salt and liquid solvents, have been used. Solid
salts such as potassium thiocyanate [5], potassium acetate [6] and ammonium thiocyanate [7] are reported for this
process. However, the application of solid salts in extractive distillation is limited because of their difficulties in
industrial operation and limited dissolution [8]. The most common liquid solvents reported for separation of benzene
and cyclohexane are sulfolane [9], dimethylformamide (DMF) [10-12], N-methylpyrrolidone (NMP) [11, 13], N-
formylmorpholine (NFM) [14] and dimethylsulfoxide (DMSO) [12]. In extractive distillation with these
conventional liquid entrainers, the solvent to feed ratio is high and leads to high energy consumption. In addition,
the purification of the products and recycling of solvents incurs additional cost of the separation process.
Recently, ionic liquids (ILs) have attracted attention for replacement of these conventional entrainers in
separation aromatic and aliphatic hydrocarbons. ILs can overcome most of the problems associated with the use of
solid salts (dissolution, reuse, and transport) and liquid solvent (low performance, thermal degradability and
volatility). This means, extractive distillation using ILs offers advantages of liquid solvent (easy operation) and solid
salt (high separation ability). In our previous works we reported that cyano-based ILs are good potential candidates
for separation of benzene and cyclohexane [15-17]. In this work, we measured the vapour-liquid equilibrium of the
ternary system (benzene + cyclohexane + [BMIM][SCN]) was measured by using headspace gas chromatography.
The performance of [BMIM][SCN] was evaluated by comparing with that of DMSO and DMF at various solvent to
feed ratios.

MATERIALS AND METHODS

The isothermal vapour-liquid equilibrium (VLE) of ternary system (cyclohexane (1) + benzene (2) + solvent (3)
were measured by using headspace gas chromatography (HSGC). Here solvent refers to [BMIM][SCN], DMSO or
DMF. The apparatus consists of a headspace autosampler (HS-sampler) and a gas chromatograph (GC).The detail
descriptions of the equipment can be found in the previous work [15]. Samples (12 cm 3) of ternary mixtures with
known composition were transferred in 20 vials. Then, the vials were closed tightly with cap and septum and
themostatted at 353.15 K in headspace sampler until equilibrium condition was attained. After phase equilibrium
was reached, sample from the vapour phase (headspace) was taken by headspace autosampler and analyzed by gas
chromatography. Only two peaks were obtained for both ternary and quaternary systems because the vapour
pressures of the solvents are negligible. The gas chromatography was calibrated with known composition of binary
mixtures. Samples of benzene-cyclohexane binary mixture were prepared and injected directly into the gas
chromatograph. The calibration curve of the average area percentage against the mole percentage was used to
determine the vapour phase composition of the ternary and quaternary systems.

RESULTS AND DISCUSSION

The isothermal VLE data and relative volatility (α12) of cyclohexane (1) + benzene (2) + solvent (3) at 353 K are
shown in Table 1. The compositions of benzene and cyclohexane reported are based on solvent free basis. The plots
of isothermal VLE data are shown in Fig. 1. The relative volatility α12 is defined as follows:

y1 x1
D 12 (1)
y 2 x2
where, x and y the mole fractions in the liquid and the vapour phase. The subscripts 1 and 2 are for cyclohexane and
benzene, respectively. For an easy separation by extractive distillation the α12 values should be far away from unity.
For benzene (1) + cyclohexane (2) binary systems the α12 values are near to unity for all composition ranges.
However, the azeotrope is broken and the relative volatility the cyclohexane to benzene are improved in the
presence of both benchmarking solvents (DMSO and DMF) and [BMIM][SCN] (Fig.1). In the presence of
[BMIM][SCN], cyclohexane becomes relatively more volatile than Bz as ILs have tendency to retain Bz in the
liquid phase. Moreover, the effect [BMIM][SCN] on the phase relative volatility of cyclohexane to benzene is
higher than that of DMSO and DMF. This implies [BMIM][SCN] can be considered as one of the potential ionic

020005-2
liquids for this separation process. The separation of benzene and cyclohexane is not only depend on the type of
solvent used, but also on the amount of solvents used per unit feed. The effect of solvent to feed ratio on the relative
volatilities of cyclohexane to benzene in the presence of DMF, DMSO and [BMIM][SCN] were presented in Table
2. The effect of solvent quantity on the relative volatility is quantified by the ratio of the liquid-phase mass of
solvent (Ws) to the mass of the feed (Wf) as shown in Equation (2) [18].

Ws
Rsf (2)
Wf
where, Rsf is the solvent to feed ratio, Ws and Wf are the mass of solvent ([BMIM][SCN], DMSO or DMF) and the
mass of the feed (azeotropic mixture of benzene and cyclohexane), respectively.

TABLE 1. VLE data and relative volatility (α12) for the system cyclohexane (1) + benzene (2) in the presence of 80 mol%
solvent at 353.15 K
[BMIM][SCN] DMF DMSO
x1 y1 α12 x1 y1 α12 x1 y1 α12
0.111 0.0226 5.406 0.051 0.042 1.226 0.057 0.049 1.173
0.208 0.0469 5.341 0.106 0.056 1.999 0.097 0.066 1.520
0.323 0.0743 5.948 0.202 0.109 2.069 0.189 0.117 1.759
0.457 0.1244 5.924 0.305 0.170 2.143 0.303 0.182 1.954
0.567 0.2006 5.218 0.398 0.235 2.152 0.409 0.247 2.110
0.673 0.2880 5.087 0.501 0.303 2.310 0.509 0.329 2.114
0.736 0.3859 4.436 0.598 0.402 2.213 0.603 0.409 2.195
0.851 0.5462 4.745 0.705 0.524 2.171 0.695 0.513 2.163
0.941 0.7878 4.297 0.799 0.651 2.131 0.797 0.647 2.142
0.894 0.801 2.095 0.901 0.817 2.040
0.954 0.915 1.927 0.949 0.912 1.795

0 2 4 6 8 10
1.0

0.8

0.6
y1

0.4

0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0
x1

FIGURE 1. VLE of benzene (1) + cyclohexane (2) + 80 mole % solvent (3) at 353.15 K. ♦, [BMIM][SCN]; ○, DMF; ×, DMSO.

020005-3
 Figure 2 shows the effect of solvent-to feed ratio on the relative volatility of cyclohexane to benzene. For the
purpose of comparison, the relative volatility was measured at different solvent-to feed ratio both conventional
solvents (DMSO and DMF) and [BMIM][SCN]. For DMSO and DMF the α12 increase rapidly with increasing Rsf at
low solvent to feed rations and α12 appears to have no obvious change when Rsf reaches a certain value. This trend is
consistent with previously reported results for conventional solvents [18].The Rsf at which the α12 does not show
significant change is usually considered as the suitable solvent to feed ratio for economic design and design of the
separation process. For [BMIM][SCN], the relative volatility versus Rsf shows the same trend with that DMSO and
DMF solvents except differences in relative volatility values at a given Rsf. That means, [BMIM][SCN] provides
higher α12 for a given solvent to feed ratio or for the same relative volatility the solvent to feed ratio for
[BMIM][SCN] is lower compared to DMSO and DMF.

TABLE 2. Relative volatility of cyclohexane to benzene at different solvent to feed ratio at 353.15 K
[BMIM][SCN] DMSO DMF
Rsf α12 Rsf α12 Rsf α12
1.175 1.545 1.006 1.316 1.106 1.416
2.978 2.504 2.643 2.354 2.354 2.287
4.257 3.223 4.329 2.938 3.929 2.998
5.189 3.576 5.564 3.111 5.535 3.213
6.596 3.962 6.678 3.187 6.876 3.317
8.564 4.099 8.235 3.213 8.967 3.351
11.090 4.137 11.256 3.2240 11.256 3.356
4.5

4.0

3.5

3.0
D12

2.5

2.0

1.5

1.0
0 2 4 6 8 10 12
Rsf

FIGURE 2. Effect of Rsf on α12 at 353.15 K. ■, [BMIM][SCN]; ○; DMF and ×; DMSO

CONCLUSIONS
Isothermal vapour-liquid equilibrium (VLE) data for benzene-cyclohexane system in the presence conventional
solvents (DMSO and DMF) and [BMIM][SCN] ionic liquid were measured using head space Gas chromatography.
The effect of the conventional solvents and [BMIM][SCN] on the relative volatility of cyclohexane to benzene were
investigated. All solvents (DMSO and DMF and [BMIM][SCN]) can break the benzene-cyclohexane azeotrope and
increases the relative volatility of cyclohexane to benzene. The effects of solvent to feed ratio were also examined
by measuring the VLE at different solvent to feed ratios. The results show that the effect of [BMIM][SCN] on
relative volatility of cyclohexane to benzene is higher than that of DMSO and DMF. This could help to reduce the
size of the extractive distillation column used for benzene and cyclohexane separation.

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 ACKNOWLEDGMENTS
This work is supported by a fundamental research grant scheme (ERGS-0153AB-110) of Ministry of Higher
Education of Malaysia and Universiti Teknologi PETRONAS.

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