Review

pubs.acs.org/jced

Comparison of Ionic Liquids to Conventional Organic Solvents for

Extraction of Aromatics from Aliphatics
Roberto I. Canales† and Joan F. Brennecke*
Department of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame, Indiana 46556, United States

ABSTRACT: Commonly used solvents for separation of aromatics from

aliphatics using liquid−liquid extraction are reviewed in terms of their
physical properties and separation performance. The experimental liquid−
liquid measurements for conventional solvents are contrasted with the phase
behavior when using an ionic liquid as the extracting component. For
comparison purposes, ternary systems of heptane + toluene + extraction
solvent are used as representative mixtures, where sulfolane is the main
organic extraction solvent discussed. Since ionic liquid properties are
drastically changed by changing the anion, comparisons are performed for 1-
ethyl-3-methylimidazolium based ionic liquids using different anions. Ionic
liquids containing cyano-substituted and bis(trifluoromethylsulfonyl)imide
anions provide good selectivities and distribution ratios. On the basis of the
phase behavior and capacities, as well as their relatively low viscosities, they
appear to be competitive alternatives to organic solvents.

■ INTRODUCTION
The main source of aromatics in industry, for example,
benzene, toluene, xylenes, and ethylbenzene, are catalytic
reforming and steam cracking processes. During catalytic
reforming, low-octane heavy naphtha from paraffinic or
naphthenic oil is processed at 723−823 K and 1.7−7.0 MPa
to obtain a high-octane reformate gasoline by isomerizing
aliphatics, ring-formation from these alkanes, and finally
dehydrogenating the cyclic aliphatics to form aromatics. A
typical reformate gasoline stream can have an aromatic content
ranging from 20 to 65 wt %,1,2 in which the main fraction of
aromatics in this product is composed of xylenes and a smaller
amount of toluene.3 In the steam cracking process any of a
diverse range of oil streams, from light hydrocarbons to heavy
naphtha, are fed to the reactor with the objective of producing
olefins, such as ethylene, propylene, and other higher olefins.
This process is highly endothermic, so near ambient pressure
and temperatures over 950 K are required, depending on the
feed.4 The product from the steam cracking is called pyrolysis
gasoline, which is rich in benzene, and contains between 50 and
over 90 wt % of aromatics.1,3
Aromatics from reformate and pyrolysis gasolines are
generally not separated by simple distillation because the
boiling points of the components in the mixture span a very
narrow range and a variety of azeotropes exist. Different
processes are used to perform the separation of the aromatics,
depending on their concentration in the effluent. When the
concentration of aromatics is high, i.e. over 90 wt %, it is
economically viable for the aromatics to be separated through
azeotropic distillation by adding a strong polar compound.
Streams with a medium aromatic concentration, that is, from 65
to 90 wt %, can be processed by extractive distillation using, for
example, N-methylpyrrolidone, phenols, glycols, etc. Streams
with lower concentrations of aromatics, that is, from 20 to 65
wt %, are separated by liquid−liquid extraction, which is
reviewed in this work.1 For aromatic concentrations below 20
wt %, other techniques have to be pursued to economically
remove the aromatics.5 The recovery of the aromatics from the
extraction solvents used in the various processes is done by
direct distillation or stripping with a secondary solvent,
followed by further distillation.1,3
The main solvents reported in the literature for aliphatic−
aromatic liquid−liquid extraction, which have also been used in
industrial separations,1 are sulfolane6−41 and glycols,35,37,42−59
but many compounds have been tested for application in
aliphatic−aromatic separations, including dimethyl sulfox-
ide,30,39 ethylene and propylene carbonate,30,57,60−64 N-
methylpyrrolidone,65−68 N-formylmorpholine,27,56,69−74 and
dimethylformamide,64 among others. The ternary aliphatic +
aromatic + solvent systems, with compositional analysis,
distribution factors, and selectivities, are detailed in each
study, which is useful for performance comparisons among
different compound combinations. Moreover, multicomponent
systems with more than three constituents have been published.
Those publications focus on the addition of a modifier to the
extraction solvent or the use of two typical sol-
vents29,30,38,56,64,68,75 for the extraction of mixed aromatics
from a single or multiple aliphatics.8,12,13,76−81
Ionic liquids have been introduced as an alternative to
conventional solvents for liquid−liquid separations due to their
very low vapor pressure, wide liquid range, and high density
compared with common aliphatics and aromatics, such as
Received: January 26, 2016
Accepted: April 4, 2016
Published: April 15, 2016

© 2016 American Chemical Society 1685 DOI: 10.1021/acs.jced.6b00077

J. Chem. Eng. Data 2016, 61, 1685−1699
Journal of Chemical & Engineering Data Review

Table 1. Properties of Common Solvents Used in Aliphatic−Aromatic Liquid−Liquid Extraction at 298.15 K and 0.1013 MPa
solvents MW (g·mol−1) Tb (K) Tm (K) ρ (g·cm−3) μ (mPa·s) Pvap (Pa) σ (mN·m−1) ref
c
ethylene glycol 62.07 470.65 260.15 1.10 16.06 13 48.60 188−190
dimethylformamide 73.09 426.25 212.75 0.94 0.90 370 35.83 172, 191
dimethyl sulfoxide 78.13 462.25 291.75 1.10 2.00 60 41.70 172, 192
ethylene carbonate 88.06 519.15 309.48 1.32b 1.85b 1.3 50.60 188, 193−195
N-methylpyrrolidone 99.13 475.05 248.75 1.03 1.67 50 40.25 172, 191
propylene carbonate 102.09 514.75 224.35 1.20 2.47 6 34.60 188, 194−196
diethylene glycol 106.12 518.65 262.85 1.11 30.2 17c 27.93 188, 197
N-formylmorpholine 115.13 513.15 296.15 1.15 7.67 198, 199
sulfolane 120.17 560.45 301.55 1.26a 10.35a 9.1a 47.95a 172, 200
toluene 92.14 383.75 178.15 0.86 0.56 3787c 27.76 188, 191
heptane 100.20 371.53 182.60 0.68 0.39 6066c 19.63 188,191
a
At 303.15 K. bAt 313.15 K. cEstimated with a correlation.201

heptane and toluene. One of the challenges is trying to find an
ionic liquid with low viscosity, high selectivity, high capacity,
and low toxicity, in order to improve the existing methods
practiced in industry for aliphatic/aromatic separation.
Liquid−liquid phase equilibrium, capacity, and selectivity
have been reported for several combinations of aliphatics and
aromatics using ionic liquids as the extraction solvent. Among
the ionic liquids studied, the cations used are mostly
imidazolium41,82−128 and pyridinium.41,93,116,128−149 A few
studies use pyrrolidinium,150 ammonium,95,131,151 morpholi-
nium,152 and other cations,86,153 while the most investigated
ionic liquid anion is bis(trifluoromethylsulfonyl)imide
([Tf2N]−). In addition, aromatic extractions have been
performed with ionic liquid mixtures in an attempt to improve
both selectivity and capacity.154−159 In some cases, infinite
dilution activity coefficients of aromatic and aliphatic
compounds in ionic liquids have been used as a first pass
evaluation of the suitability of a particular ionic liquid for
aliphatic−aromatic separation.160,161 Here we focus on liquid−
liquid equilibrium studies of ternary mixtures of heptane +
toluene + imidazolium-based ionic liquids, paying particular
attention to those containing the 1-ethy-3-methylimidazolium
([emim]+) cation.
The method usually proposed for recovery of the aromatic
from the ionic liquid extraction solvent is simple distillation or
stripping, taking advantage of the thermal stability and low
volatility of the ionic liquid.162 Jongmans et al.163 simulated the
ethylbenzene/styrene extractive distillation process using 4-
methyl-N-butylpyridinium tetrafluoroborate ([4-mebupy]-
[BF4]), proposing several regeneration techniques: simple
evaporation, two stage evaporation with the second unit at
very low pressure, nitrogen stripping, distillation, and super-
critical CO2 extraction. The most promising recovery technique
according to this author is the low pressure regeneration.
Scurto et al.,164,165 Aki et al.,166 Mellein and Brennecke,167
Canales and Brennecke168 and Canales et al.169 have studied
the salting-out effect of sub- and supercritical CO2 on mixtures
of ionic liquids with different organic solvents and water. The
addition of CO2 results in a liquid−liquid phase split, where the
organic-rich or aqueous-rich phase can be quite pure. This
technique is another promising method for recovering the
aromatic and regenerating the ionic liquid for reuse if one can
find an ionic liquid that releases the aromatic at moderate
pressures and low CO2 compositions in the liquid phase. Lower
pressures and use of less CO2 makes the liquid−liquid phase
split process more attractive than supercritical CO2 extraction.
1686
The objective of this brief review is to show the performance
of ionic liquids in liquid−liquid separation of aromatic from
aliphatics compared with common organic solvents. We will
focus on physical and transport properties (e.g., density and
viscosity) and the performance of the solvents in terms of
selectivity and distribution ratio.
■ LIQUID−LIQUID SEPARATION OF AROMATICS
FROM ALIPHATICS USING COMMON SOLVENTS
Liquid−liquid separation is the most popular process in
industry to extract aromatics from aliphatics. Selection of a
suitable solvent is the crucial first step in performing successful
liquid−liquid extractions. The best solvents have good
selectivity and capacity, high thermal stability, good availability,
low cost, high surface tension and low to moderate viscosity.170
More environmentally friendly solvents, which have a smaller
impact on human health and the environment, is another
feature to consider. These compounds, frequently called
“green” solvents, must have a very low toxicity, persistence,
and volatility.171
Table 1 presents some properties, such as boiling temper-
ature at 0.1013 MPa, melting point, density, viscosity, vapor
pressure and surface tension at 298.15 K of the typical solvents
used for liquid−liquid extraction of aromatics from aliphatics.
These properties are compared with the representative aliphatic
and aromatic used in this work: heptane and toluene. The main
characteristics observed for the conventional extraction solvents
are their relatively low vapor pressure, low viscosity, and high
surface tension. The low vapor pressure is an important factor
for avoiding significant loss of the solvent, which would require
replacement and add cost. Low viscosity is essential to decrease
mass transfer problems in the mixing and separation of the
liquid phases. A high surface tension is necessary for avoiding
the presence of emulsions.170
All of the solvents have higher density than either heptane or
toluene. This is virtually a requirement for selective extraction
of the aromatic, since the aromatics are more dense than the
aliphatics. If the solvent is to have good capacity and selectivity
for the aromatic compound, the extract will inevitably be the
more dense of the two liquid phases, facilitating their
gravimetric separation. The aliphatics, with a small portion of
solvent and aromatics, will be the raffinate, which is the low
density upper phase in the liquid−liquid equilibrium. All the
solvents show a liquid range of approximately 200 K and some
of them melt close to the room temperature, such as sulfolane,
dimethyl sulfoxide, ethylene carbonate, and N-formylmorpho-
line. The boiling point of the solvent is also important because
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it has to be significantly higher than that of the aromatic if the
aromatic is to be recovered by simple distillation. It is also
noted that the molecular weight of the extraction solvents are
comparatively close to the values for heptane and toluene. The
molecular structures of the different solvents shown in Table 1
are presented in Figure 1.
Figure 1. Molecular structure of some typical solvents used in
aromatic/aliphatic liquid−liquid extraction.
Sulfolane is the most studied separation solvent in the
literature and is widely used in industry in extractive distillation
and liquid−liquid aromatic extraction.1 In Figure 2, a
comparison of the literature data for liquid−liquid equilibrium
of the heptane + toluene + sulfolane system at 298.15 K is
presented in mole and mass fraction bases, showing high
consistency in the tie lines and coexistence curves among
results from different researchers. Therefore, sulfolane is a good
choice as a “base-case” solvent with which to compare
experimental measurements of aliphatic + aromatic + solvent
liquid−liquid equilibrium. However, note that sulfolane is more
highly toxic than some other extraction solvents.172 It is not
surprising that the mole and weight fraction diagrams are
similar since the molecular weights of the three components are
similar.
There is usually some temperature effect on liquid−liquid
equilibrium, with larger miscibility gaps generally observed at
lower temperatures. However, the pressure effect on the phase
behavior is negligible close to atmospheric conditions.170 Figure
3 presents a comparison of the tie lines in the system heptane +
toluene + sulfolane at three different temperatures: 298.15 K,
313.15 K, and 323.15 K. In this mixture, the immiscible area is
slightly larger at the lower temperature, as expected, but the tie
lines follow the same slope and the compositions in both
phases are not considerably different. Thus, there is not a
strong temperature effect for this mixture over the relatively
small temperature range shown in Figure 3.
Figure 4 shows a comparison of the immiscibility gaps when
different solvents are used for separating toluene from heptane
at 313.15 K, where the largest immiscible region is with
ethylene carbonate and the smallest is with N-methylpyrroli-
1687
Review
Figure 2. Comparison of ternary liquid−liquid equilibrium data for the
heptane + toluene + sulfolane system at 298.15 K13,14,26,34,36 in (a)
mole fraction and (b) mass fraction.
done. All the solvents appear to have a plait point, so high
toluene concentration mixtures cannot be separated. Compar-
ison of the ternary liquid−liquid phase equilibrium diagrams is
useful in determining the compositions of the initial heptane +
toluene mixtures that can be separated with a particular solvent.
However, the best analysis is provided by calculating the
capacity and selectivity of the solvent at different compositions
of the two phases.
The capacity of the solvent to dissolve heptane or toluene is
defined as the distribution ratio (or distribution factor) Di. It
can be defined in mole fraction (Dx,i in eq 1) or mass fraction
(Dw,i in eq 2) basis where xαi or β is the mole fraction of
compound i in the α or β phase and wαi or β is the mass fraction
of compound i in the α or β phase, calling α as the lower extract
phase and β as the upper raffinate phase,
xiα
Dx , i =
xiβ (1)
wiα
Dw , i =
wiβ (2)
A solvent with good capacity for separating the aromatic has to
show a lower distribution ratio for the aliphatic than the
aromatic. A high distribution ratio of the aromatic is required to
decrease the solvent usage in the liquid−liquid extraction. The
selectivity (S in eq 3) is calculated as the distribution ratio of
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Figure 3. Temperature effect on the liquid−liquid equilibrium for

heptane + toluene + sulfolane mixtures36 in (a) mole fraction and (b)
mass fraction: (black square) 298.15 K, (red circle) 313.15 K, and
(blue triangle) 323.15 K.
Figure 4. Liquid−liquid equilibrium of the heptane + toluene +
solvent system at 313.15 K in (a) mole fraction and (b) mass fraction:
(black square) sulfolane,36,41 (red circle) ethylene carbonate,30 (blue
triangle) N-formylmorpholine,56,69 (green diamond) N-methylpyrro-
lidone,68 (cross) ethylene glycol59

the aromatic divided by the distribution ratio of the aliphatic in

mole or mass fraction. As shown in Figure 2, there is good agreement among
literature data for the heptane + toluene + sulfolane system at
Daromatic xα β
/xaromatic α
waromatic β
/waromatic 298.15 K. In Figure 6, the selectivity and distribution ratio are
S= = aromatic =
Daliphatic α
xaliphatic β
/xaliphatic α
waliphatic β
/waliphatic shown as a function of xβtoluene (and wβtoluene for mass distribution
(3)
ratio) for the same data shown in Figure 2 at 298.15 K. Despite
As a consequence, a good liquid−liquid separation solvent or a the apparent agreement in the liquid−liquid equilibrium data,
mixture of extracting solvents has to have a high distribution there are significant differences in the selectivities at low
ratio for the aromatic, and a low distribution ratio for the toluene concentrations. This is because the selectivity is very
aliphatic that results in a high selectivity for the target sensitive to small variations in the mole fractions of the two
compound, in order to obtain low amounts of aromatic in liquid phases at low toluene concentrations. For example, the
the aliphatic-rich phase. data of Tripathi et al.36 gives a selectivity of 44.9 at xβtoluene =
Selectivity is highly dependent on composition, so it also 0.0898 but for Chen et al.13 S = 28.6 at xβtoluene = 0.083. These
depends on the temperature. Figure 5 shows the selectivity and large variations in selectivity are decreased when xαtoluene > 0.2,
distribution ratio for the heptane + toluene + sulfolane system where the compositions of the two liquid phases are closer to
at different temperatures obtained from the work of Tripathi et the plait point. All of the reports show increasing distribution
al.,36 where selectivity decreases and the distribution ratio tends ratio with increasing toluene composition, but as seen with the
to increase by enhancing the concentration of toluene in the selectivity, there is more disparity at low toluene compositions.
upper phase (xβtoluene). The most significant temperature effect To evaluate data from different research groups, experimental
on selectivity is observed at the lowest xβtoluene, where the compositions and selectivities should be analyzed for
selectivity is about 45 at 298.15 K but closer to 30 at 323.15 K. thermodynamic consistency, as is done with the Gibbs−
There is no clear temperature effect on the distribution ratio in Duhem equation for vapor−liquid equilibrium. Consistency of
the heptane + toluene + sulfolane system. Distribution ratio liquid−liquid equilibrium data is commonly checked by
values decrease slightly when based on mass fraction because applying the correlations proposed by Hand173 and Othmer
the molecular weight of sulfolane is bit higher than the and Tobias,174 but it has been demonstrated that these “tests”
molecular weights of toluene and heptane. are not sensitive enough to weight fraction and selectivity
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Figure 5. (a) Selectivity, (b) distribution ratio in mole fraction basis
and (c) distribution ratio in mass fraction basis versus composition of
toluene in the upper raffinate phase for the heptane + toluene +
sulfolane36 system at (black square) 298.15 K, (red circle) 313.15 K,
and (blue triangle) 323.15 K.
variations and do not have a strong theoretical basis.175
Unfortunately, to our knowledge, there are no procedures to
check thermodynamic consistency of liquid−liquid equilibrium
data based on a robust theoretical technique.
■
LIQUID−LIQUID SEPARATION OF AROMATIC
FROM ALIPHATICS USING IONIC LIQUIDS
Ionic liquids are usually immiscible with aliphatics, with very
small mutual solubilities. On the other hand, the solubility of
aromatics in many ionic liquids is quite high, but generally they
are not completely miscible. This behavior allows the ionic
liquid to separate aromatic/aliphatic mixture at any feed
composition but a selectivity and capacity analysis is necessary
1689
Review
Figure 6. (a) Selectivity, (b) distribution factor in mole fraction basis
and (c) distribution factor in mass fraction basis versus composition of
toluene in the upper raffinate phase for the heptane + toluene +
sulfolane system at 298.15 K. (black square) Tripathi et al.;36 (red
circle) Lin et al.; (blue triangle) Chen et al.;13 (green diamond) De Fré
and Verhoeye;14 (cross) Rawat and Gulati.34
to evaluate the economic feasibility of using ionic liquids for
aliphatic−aromatic separations. Typical cations and anions used
for aliphatic/aromatic liquid−liquid separation are shown in
Tables 2 and 3, respectively.
Ionic liquids using the 1-ethyl-3-methylimidazolium
([emim]+) cation are commonly studied since the short alkyl
chains result in good selectivity and distribution ratios (as
discussed below). Table 4 presents densities, viscosities, and
surface tensions of several [emim]+ based ionic liquids with
different anions, in comparison to sulfolane, heptane, and
toluene. The density and surface tension of ionic liquids are
very similar to common liquid−liquid extraction solvents. The
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Table 2. Ionic Liquid Cations Used for Liquid−Liquid Table 3. Ionic Liquid Anions Used for Liquid−Liquid
Extraction of Aromatics from Aliphatics Extraction of Aromatics from Aliphatics

a
A, B, C, D, n = number of carbons in the alkyl chain; X, Y = initial of
alkyl chain.

main difference is the higher viscosities of the ionic liquids,

ranging from 15 to 320 mPa·s. On the basis of viscosity, the
most competitive ionic liquid alternatives are ones with the
[emim]+ cation and anions containing cyano groups, such as
[DCA]−, [TCM]−, and [SCN]−, as well as [Tf2N]−, all of
which have viscosities similar to sulfolane. The vapor pressures
of the ionic liquids are generally very small compared to organic
solvents and this represents an advantage for the reduction of
the gas emissions to the atmosphere and the reduction of the
regeneration cost of the solvent. The molecular weights of ionic
liquids are usually much higher than those of common
extraction solvents.
A typical ternary diagram for heptane + toluene +1-ethyl-3-
methyl imidazolium bis(trifluoromethylsulfonyl)imide
([emim][Tf2N]) is shown in Figure 7 at two different
temperatures in mole and mass fractions. There is very little
difference in the data at 298.15 K and 313.15 K, from the
groups of Arce et al.84 and Garcia et al.,176 respectively, and tie
lines have similar slope. When compared with the results of
Corderi ́ et al. at 298.15 K, there is a small variation in the
compositions of the lower phase and the slopes of their tie lines
are different than the other groups when the toluene
composition is over 0.2 mole fraction. These differences [hmim][Tf2N] systems, from the work of Arce et al.84 at 298.15
could lead to significant variation in the selectivities. When K and Garcia et al.104 at 313.15 K. As noted previously for the
compositions are shown in mass fractions, the difference data in the ternary diagram of Figure 7, the selectivities
between the different experimental values is more difficult to calculated from Corderi ́ et al.93 will underestimate the values
distinguish because the values are dominated by the high for [emim][Tf2N] compared to the other researchers, but show
molecular weight of [emim][Tf2N]. similar distribution ratios at low toluene compositions. When
In Figure 8, the effect of the length of the alkyl chains of the the distribution ratios are recalculated in terms of the mass
imidazolium cation (1-alkyl-3-methylimidazolium) on the fractions, the values are decreased dramatically, as expected, due
selectivity and the distribution ratio of toluene at two different to the high molecular weights of the ionic liquids.
temperatures (298.15 and 313.15 K) are explored. The effect of The selectivities for the different [Cxmim][Tf2N] ionic
temperature on the selectivity and distribution ratio is very liquids is [hmim] < [bmim] < [emim] < [mmim], which means
small, as seen in the heptane + toluene + [emim][Tf2N] and that a longer alkyl chain decreases the selectivity. The
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Table 4. Properties of [emim]+ Ionic Liquids Used in Liquid−liquid Extraction of Aromatics from Aliphatics at 298.15 K
solvents MW (g·mol−1) ρ (g·cm−3) μ (mPa·s) σ (mN·m−1) ref
a a
sulfolane 120.17 1.26 10.35 47.95a 172, 200
[SCN]− 169.25 1.11684 22.15 57.76 202
[OAc]− 170.21 1.09778 132.91 42.9 203
[TCM]− 201.23 1.08162 15.02 50.94 118, 204
[DCA]− 177.21 1.10198 19.90 40.3 203
[CH3SO3]− 206.26 1.2398 155 45.1 205, 206
[ESO4]− 236.29 1.24018 101.42 46.9 203
[DEP]− 264.26 1.146 320.89 34.46 207
[Tf2N]− 391.31 1.51900 32.99 35.2 208, 209
toluene 92.14 0.86 0.56 27.76 188,191
heptane 100.20 0.68 0.39 19.63 188,191
a
At 303.15 K.

0.799), Dx,heptane = 0.294 (Dw,heptane = 0.144) and Dx,toluene =

Figure 7. Liquid−liquid equilibrium of the ternary heptane + toluene
+ [emim][Tf2N] system in (a) molar compositions and (b) mass
compositions at 298.15 K (black square) Arce et al.,84 (red circle)
Corderi ́ et al.; and at 313.15 K (blue triangle) Garcia et al.104
distribution ratio of toluene follows the opposite trend: a longer
alkyl chain increases the distribution ratio. This difference can
be explained because the ionic liquids with longer alkyl chains
increase the aromatic solubility, but also increases the aliphatic
solubility. This directly affects the distribution ratios, causing a
larger effect for the aliphatic than the aromatic. For example,
Garcia et al.104 report Dx,heptane = 0.180 (Dw,heptane = 0.085) and
Dx,toluene = 0.786 (Dw,toluene = 0.370), producing S = 4.36, for
xβtoluene = 0.816 (wβtoluene = 0.803) when using [bmim][Tf2N].
However, with [hmim][Tf2N] at xβtoluene = 0.812 (wβtoluene =
1691
0.823 (Dw,toluene = 0.404), obtaining a S = 2.80. At these
conditions, the change achieved by increasing the alkyl chain
length from butyl to hexyl is ΔDx,heptane = 0.114 (ΔDw,heptane =
0.059), ΔDx,toluene = 0.037 (ΔDw,toluene = 0.034) and ΔS =
−1.56, from which one can conclude that the effect on the
heptane mole distribution ratio is three times greater (twice in
the case of mass fraction) than the effect on the toluene
distribution ratio.
Figure 9 shows the selectivity and toluene distribution ratio
for separating toluene from heptane for ionic liquids with the
[emim]− cation and a variety of different anions. The results are
compared with sulfolane. The sulfolane data selected for
comparison was the data that showed the higher selectivity and
distribution ratio of toluene compared with other values from
literature.36 In terms of selectivity, all the ionic liquids
presented in Figure 9 are competitive with sulfolane, since
the lowest value of selectivity for ionic liquids is for
[emim][Tf2N], which is very close to the sulfolane curve.
The highest selectivity is when [emim][SCN] is used, with
selectivities over 90 at the lowest compositions. High
selectivities are also observed with [emim][CH3SO3] and
[emim][DCA]. In the case of the toluene mole distribution
ratio comparison, only three ionic liquids are competitive with
sulfolane: [emim][DEP], [emim][TCM], and [emim][Tf2N].
Ionic liquids with the highest selectivities fall far below the
sulfolane curve in terms of distribution ratio, which means that
a large amount of solvent would be required for separating the
aliphatic/aromatic mixture. The problem with [emim][Tf2N] is
the higher concentration of aliphatic dissolved in the ionic
liquid. In general, the ionic liquids presented in Figure 9 show
better or comparable selectivities to sulfolane, but just
[emim][TCM], [emim][DEP], and [emim][Tf2N] have a
higher or similar mole distribution ratio of toluene. The main
disadvantage of using [emim][DEP] is its high viscosity.
However, [emim][TCM] and [emim][Tf2N] may be viable
alternatives to replace sulfolane. For mass fraction distribution
ratios, the values for all the ionic liquids fall below the sulfolane
line. Once again, this is due to the high molecular weight of the
ionic liquids. Consequently, a larger mass of ionic liquid than
sulfolane would be necessary to separate heptane from toluene,
which could increase operating and capital costs.
To overcome the general trend for ionic liquids of high
selectivity but low distribution ratio, Larriba et al.158,159
proposed using a mixture of ionic liquids: one with high
selectivity, such as [emim][DCA], and another with high
toluene distribution ratio, such as [4empy][Tf2N]. There is still
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Figure 8. Effect of the cation alkyl chain length on the (a) selectivity,
(b) distribution factor in mole fraction basis, and (c) distribution
factor in mass fraction basis versus composition of toluene in the
upper raffinate phase for the heptane + toluene + [Cxmim][Tf2N]
system. Solid symbols, 298.15 K; open symbols, 313.15 K; (open
green diamond) [mmim][Tf2N];104 (solid black square) [emim]-
[Tf2N];84 (solid gray square) [emim][Tf2N];93 (open black square)
[emim][Tf2N];104 (open red triangle) [bmim][Tf2N];176 (solid blue
circle) [hmim][Tf2N];91 (open blue circle) [hmim][Tf2N].104
a need to expand the knowledge of ionic liquids for use in
aromatic/aliphatic separation processes in order to improve the
mass distribution ratios using low cost ionic liquids. A broader
overview on the use of different ionic liquids in several types of
aliphatic/aromatic mixtures and the effect of diverse
modifications in the molecules on the distribution ratio and
selectivity is analyzed in the work of Ferreira et al.177
■
AROMATIC + IONIC LIQUID BINARY SYSTEMS
After the liquid−liquid separation is performed for the
aliphatic/aromatic mixture, the extract composed mainly of
1692
Review
Figure 9. Effect of the anion on the (a) selectivity and (b) distribution
factor in mole fraction basis and (c) distribution factor in mass fraction
basis versus composition of toluene in the upper raffinate phase for the
heptane + toluene + [emim]+ cation-based ionic liquids systems. Solid
symbols, 298.15 K; open symbols, 313.15 K. (Solid black square)
[Tf2N]−;84 (open black square) [Tf2N]−;104 (solid blue circle)
[DEP]−;87 (solid green diamond) [OAc]−;92 (open orange triangle)
[CH 3 SO 3 ] − ; 107 (open purple star) [CF 3 SO 3 ] − ; 107 (cross)
[CHF2CF2SO3]−;107 (solid red inverted triangle) [ESO4]−;113 (open
red inverted triangle) [ESO4]−;41 (×) [SCN]−;117 (asterisk)
[DCA]−;118 (dash) [TCM]−;118 and (black square with line)
sulfolane.36
the extraction solvent and the aromatic has to be separated to
obtain a pure aromatic and to recover the solvent for reuse in
the process. This separation, as mentioned above, is usually
done by direct distillation or solvent stripping followed by
distillation. For ionic liquids solvents, the separation by
distillation should be easier due to the high thermal stability
and low volatility of the ionic liquids. Despite the large number
DOI: 10.1021/acs.jced.6b00077
J. Chem. Eng. Data 2016, 61, 1685−1699
Journal of Chemical & Engineering Data
of studies of liquid−liquid equilibrium of ionic liquids and
aromatics, heats of mixing and excess properties for these
binary systems are extremely scarce.178−180
Aromatics have a large solubility in ionic liquids but a
miscibility gap is commonly observed. The high solubility of
aromatics in, for example, imidazolium ionic liquids with alkyl
chains is attributed to interactions of the strong electrostatic
fields of the aromatic rings in both the ionic liquid and the
toluene, where the van der Waals interactions of the toluene
with nonpolar chains on the cation of the ionic liquid are also
an important component of the wide mutual miscibility.181,182
According to Holbrey et al.183 this behavior supports the
formation of clathrates, because a small interaction produces
miscibility or immiscibility of the binary system and strong
interactions produce the crystallization of the salt, but in this
case there is a partial miscibility. Further understanding in this
topic is needed because, for example, some ionic liquids, such
as [P66614][Tf2N], are completely miscibility with benzene,86 so
the clathrate theory is not applicable for this case.
The solubility of the ionic liquid in the aromatic-rich phase is
very low or even not detectable, depending on the nature of the
ionic liquid and the aromatic in the binary mixture. Several
works suggest the appearance of an upper critical solution
temperature (UCST) in different combinations of [Tf2N]−
ionic liquids with aromatics.184−187 Lachwa et al.186 reported
liquid−liquid equilibrium for binary systems, including
[Cnmim][Tf2N] + benzene, toluene, and α-methylstyrene
where the UCST is also observed and a detectable
concentration of ionic liquid is detected over 300 K for
benzene and over 390 K for α-methylstyrene in [hmim][Tf2N].
An increase in the alkyl chain length for the imidazolium cation
produces a decrease in the immiscibility area due to the
increasing aromatic solubility in the ionic liquid.
■ The authors declare no competing financial interest.
SUMMARY
Ionic liquids are potentially competitive alternatives to
currently used organic solvents for successfully separating
aromatics from aliphatics. Many ionic liquids have densities and
surface tensions that would be acceptable. For the [emim]+
cation, there are several choices of anions (e.g., [SCN]−,
[DCA]−, [TCM]− and [Tf2N]−), which yield ionic liquids with
sufficiently low viscosities (only 2 or 3 times that of sulfolane).
Some anion−cation combinations show comparable or better
selectivity than sulfolane, but the challenge of decreasing the
amount of solvent used due to their low mass distribution ratio
is still an issue to consider. The [emim]+ based ionic liquids
with better selectivities than sulfolane involve [SCN]−,
[CH3SO3]−, and [DCA]− anions. Selectivities of [emim][SCN]
and [emim][DCA] are over four times that of sulfolane but
their mass distribution ratios are only about 30% of the value
for sulfolane. The [emim]+ ionic liquids with the best mass
distribution ratios have the following anions: [TCM]−,
[Tf2N]−, and [DEP]−. [emim][TCM] and [emim][Tf2N]
have double the selectivity of sulfolane, but their mass
distribution ratios are still a bit lower (0.64 and 0.52 times
the value of the sulfolane, respectively). Nonetheless, [emim]-
[Tf2N] and [emim][TCM] appear to be the better choices for
heptane/toluene separation from among the ionic liquids
considered in this work, due to their high selectivity and
reasonably high mass distribution ratios.
Selectivity is very sensitive to small variations in the
experimental liquid−liquid equilibrium compositions, so large
differences can be observed under certain conditions when
1693
Review
calculating the selectivity of a system using data from different
authors, even when no significant variations are detected in the
ternary phase equilibrium diagrams. Selectivity remains the key
parameter for choosing a better extraction solvent. As suggested
by the results shown here, the mole fraction basis is the best
way to present the ternary liquid−liquid equilibrium diagrams
because it is more sensitive to changes when the extraction
solvent has a high molecular weight, but the mass fraction basis
is recommended for presentation of distribution ratios, due to
its importance in defining the mass of solvent required to
perform the separation.
Further studies are needed to evaluate if the ionic liquid
solvent can be recovered and reused in the process. Finally, the
economic feasibility of the liquid−liquid extraction using an
ionic liquid with the recovery of the ionic liquid solvent using
different techniques needs to be explored in more depth in
order to determine the real applicability of ionic liquids for
aliphatic−aromatic separations.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: jfb@nd.edu. Tel.: +1 (574) 631-5847. Fax: +1 (574)
631-8366.
Present Address
†
Laboratory of Thermodynamics, Departament of Biochemical
and Chemical Engineering, Technische Universität Dortmund,
Emil-Figge-Str. 70, D-44227 Dortmund, Germany
Funding
We acknowledge support from the University of Notre Dame
Incropera-Remick Fund for Excellence.
Notes
■
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1699 DOI: 10.1021/acs.jced.6b00077

J. Chem. Eng. Data 2016, 61, 1685−1699