Research Article

pubs.acs.org/journal/ascecg

Deep Eutectic Solvents as Azeotrope Breakers: Liquid−Liquid

Extraction and COSMO-RS Prediction
Andreia S. L. Gouveia,†,‡ Filipe S. Oliveira,† Kiki A. Kurnia,§ and Isabel M. Marrucho*,†,‡
†
Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, 2780-157 Oeiras, Portugal
‡
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Avenida Rovisco Pais, 1049-001 Lisboa, Portugal
§
Department of Chemical Engineering, Universiti Teknologi PETRONAS, Seri Iskandar 32610, Perak, Malaysia
*
S Supporting Information
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ABSTRACT: The efficient and sustainable separation of azeotropic

mixtures remains a challenge in chemical engineering. In this work,
the performance of benign solvents, namely deep eutectic solvents
(DES), in the separation of aromatic−aliphatic hydrocarbon
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azeotropic mixtures via liquid−liquid extraction (LLE) was evaluated.

The DES studied in this work were based on different ammonium
salts (cholinium chloride, [Ch]Cl, benzylcholinium chloride, [BzCh]-
Cl, and tetrabutylammonium chloride, [N4444]Cl) as hydrogen bond
acceptor (HBA) and one organic acid (levulinic acid, LevA) as
hydrogen bond donor (HBD), always in the mole ratio of 1 HBA:2
HBD. The thermophysical properties, namely density and viscosity,
of the three used DES were measured in the temperature range T =
(293.15 up to 353.15) K and at atmospheric pressure. The phase
equilibria diagrams of all ternary systems were determined at T =
298.15 K and at atmospheric pressure using 1H NMR spectroscopy. The results showed that the introduction of a more
hydrophobic HBA in the DES promotes the improvement of the distribution coefficient, while playing with the aromaticity of the
DES leads to higher selectivity. In addition, the performance of the predictive conductor-like screening model for real solvent
(COSMO-RS) model in the description of these systems was also evaluated. COSMO-RS is capable of quantitatively predicting
the phase behavior and tie-lines for ternary mixtures containing DES as well as of estimating the trend of distribution ratio and
selectivity.
KEYWORDS: Deep eutectic solvents, Aromatic−aliphatic azeotropic mixtures, Liquid−liquid extraction, COSMO-RS

■ INTRODUCTION
In many areas of industry, particularly in the petrochemical
industry, solvent mixtures accumulate due to recycling
difficulties. Therefore, their efficient separation into pure
components is mandatory so that they can be reused. However,
many of these solvent mixtures contain azeotropes, whose
separation is still an issue in chemical engineering. In particular,
the separation of aromatic hydrocarbons, namely toluene,
benzene, xylenes, and others, from mixtures with aliphatic
hydrocarbons, still remains an enormous challenge, since these
compounds have close boiling points and several combinations
of them can form azeotropes.1
The conventional industrial processes commonly used in the
separation of aromatic and aliphatic hydrocarbon mixtures are
azeotropic or extractive distillation and liquid−liquid extraction
(LLE). LLE presents economic advantages compared to the
other processes, since it requires low energy demand. However,
the conventional extraction solvents typically used in industry
are organic solvents, such as sulfolane,2−4 tetraethylene glycol,5
and N-methylpyrrolidone (NMP),6 which require additional
investments and energy consumption for their recovery and are
considered toxic, volatile, and/or flammable.7 Consequently,
their replacement by greener alternatives has been a topic of
interest over the past several years. In this context, ionic liquids
(ILs), which are known for their exceptional combination of
properties, such as negligible vapor pressure, low flammability,
and high solvation capacity for a wide range of inorganic and
organic materials, have been proposed as candidates for the
replacement of conventional organic extractants. Due to their
properties, it is expected that the use of ILs in the extraction of
aromatics from aromatic/aliphatic mixtures leads to more
sustainable separation with less energy consumption and
smaller number of process steps. A large number of articles
have reported the use of different families of ILs, such as
imidazolium-, pyridinium-, or ammonium-based ILs. In
particular, imidazolium-based ILs combined with several
anions, such as [OAc]−, [SCN]− , [NTf2 ]−, [HSO 4]− ,
[CH3SO4]−, [C2H5SO4]−, [CF3SO3]− and others, have been
Received: July 5, 2016
Revised: August 25, 2016
Published: August 31, 2016

© 2016 American Chemical Society 5640 DOI: 10.1021/acssuschemeng.6b01542

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ACS Sustainable Chemistry & Engineering
Table 1. Chemical Structures of the HBA and HBD in the DES Studied in This Work as Well as the Mole Ratio and Respective
Molar Mass, M (g·mol−1)
deeply explored as suitable extraction solvents in the separation
of different aromatic/aliphatic hydrocarbon mixtures, and some
ILs showed higher separation factors than those of the
conventional sulfolane.8−17 Nevertheless, and despite their
promising and clear advantages, the environmental impact of
ILs has been shown as mostly dependent on the chemical
structure of the IL, which means that these fluids are not
universally green.18 Moreover, the complex ILs synthesis and
purification lead to a disadvantageous high cost of production
of some ILs.
Deep eutectic solvents (DES) have recently emerged as
potential alternatives to ILs, since their physicochemical
properties are similar to those of ILs.19,20 DES are mixtures
of a hydrogen bond acceptor (HBA), such as halide salts and,
typically, a hydrogen bond donor (HBD), viz. carboxylic acids,
alcohols, or amines, that present a much lower melting point
than the pure components. In addition, DES can be synthesized
from nontoxic, cheap, biodegradable, and biocompatible
materials, using simple methods or preparation, heating and
mechanical stirring, or grinding, without the need for further
purification steps. This fact is probably the main advantage of
DES over ILs. Recently, DES have been tested as extraction
solvents for the separation of aromatic/aliphatic mixtures. For
instance, DES based on tetrabutylphosphonium bromide and
ethyltriphenylphosphonium iodide as HBA and ethylene glycol
or sulfolane as HBD in the separation of toluene from n-
heptane were reported by Kareem et al.1,21 The same group
also tested DES based on methyltriphenylphosphonium
bromide as a salt and also ethylene glycol as HBD for the
separation of benzene from hexane.22 Generally, a similar or
higher performance of DES was observed compared to
conventional solvents or ILs. Moreover, Mulyono et al.23
studied DES based on an ammonium salt and sulfolane as HBD
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in the LLE of BTEX aromatics (benzene, toluene, ethyl-
benzene, and xylenes) from n-octane.
DES based on choline chloride and three different HBD,
such as ethylene glycol, levulinic acid, and glycerol, were already
reported by our group as promising alternatives to ILs in the
separation of ethanol/n-heptane mixtures, since remarkably
high selectivities and distribution coefficients were obtained.24
In this context, in this work we explore the performance of
sustainable DES based on three different salts, namely choline
chloride, benzylcholine chloride, and tetrabutylammonium
chloride, and levulinic acid as hydrogen bond donor, in the
separation of toluene from n-heptane via liquid−liquid
extraction at T = 298.15 K. The thermophysical properties
(density and viscosity) were also measured and discussed, since
they influence the mass transfer operations in extraction
processes.
In addition, the capability of the conductor-like screening
model for real solvent (COSMO-RS) to predict the phase
equilibrium of a ternary mixture containing DES was evaluated.
COSMO-RS is a quantum chemical based prediction
method25,26 that has been widely used to predict liquid−liquid
phase equilibria of binary and ternary mixtures containing ionic
liquids and hydrocarbon.27,28 However, to our knowledge, this
work is the first to address the capability of the model to predict
ternary phase diagrams containing DES.
■
EXPERIMENTAL SECTION
Materials. Choline chloride ((2-hydroxyethyl)trimethylammonium
chloride, ≥98 wt %), benzylcholine chloride (benzyl(2-hydroxyethyl)-
dimethylammonium chloride, ≥97 wt %), [N4444]Cl (tetrabutylam-
monium chloride, ≥97 wt %), and levulinic acid (98 wt %) were
purchased from Sigma-Aldrich. The chemical structures, respective
acronyms, and mole ratio of the DES used in this work are presented
in Table 1. The components of the azeotropic mixture, n-heptane and
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toluene, were purchased from Carlo Erba (99 wt %) and Sigma-
Aldrich (99.9 wt %), respectively, and were used without any further
purification.
Synthesis and Characterization of DES. In this work, three
DES, namely [Ch]Cl:LevA (DES1), [BzCh]Cl:LevA (DES2), and
[N4444]Cl:LevA (DES3), were synthesized in a mole ratio of 1 HBA:2
HDB using the grinding method,29 in which both components were
first mixed and then ground in a mortar with a pestle at room
temperature in order to obtain a homogeneous liquid. In order to
reduce the water and other volatile substance contents, the DES were
dried under vacuum (1 Pa) at room temperature for at least 3 days.
The water contents of the dried DES were measured by Karl Fischer
coulometric titration, and all the DES contained less than 0.5 wt %
H2O.
The thermophysical properties, namely density, ρ (kg·m−3), and
viscosity, η (Pa·s), of the synthesized DES were measured within the
temperature range (293.15 and 353.15) K and at atmospheric pressure
using an SVM 3000 Anton Paar rotational Stabinger viscometer-
densimeter. The standard uncertainty for the temperature is 0.02 K.
The repeatability values of density and viscosity of this equipment are
0.5 kg·m−3 and 3.5 × 10−6 Pa·s, respectively. Triplicates of each sample
were performed to ensure accuracy, and the reported results are
average values. Furthermore, the relative standard uncertainty in
density and viscosity was calculated by the ratio of the standard
deviation and the average of the three replicates of each sample, where
the highest relative standard uncertainty registered for the density and
dynamic viscosity measurements was 0.2 and 2 × 10−5, respectively.
LLE Measurements. The LLE consisted of two steps: in the first
step, preparation of calibration curves to determine the concentration
of toluene in n-heptane or the DES phase was carried out, while, in the
second step, the tie-lines for each one of the ternary mixtures were
determined.
The calibration curves were constructed using a binary mixture of n-
heptane + toluene and toluene + DES at different mole fractions,
depending on the solubility of toluene in the respective solvent. All the
binary mixtures were stirred using a magnetic stirrer for at least 1 h.
After the equilibrium, each sample was analyzed using 1H NMR
spectroscopy (Bruker Avance II+ 500 MHz NMR spectrometer) in
order to obtain the calibration curves, integration of the area under the
peak vs mole fraction. For the NMR analysis, the samples were placed
in NMR spectroscopy sealed tubes with dimethyl sulfoxide-d6
(DMSO-d6) as solvent. The deuterated solvent was not mixed with
the sample but kept inside a sealed capillary tube, which was then
introduced inside the NMR tube, minimizing the amount of solvent
required. The DMSO-d6 was used for the external lock of the NMR
magnetic field, and the greatest quantitative agreement was found
when selecting, for [C2mim][OAc], the peaks corresponding to the
imidazolium cation (for instance, the methyl group bonded to the
nitrogen atom of the imidazolium ring), and for the studied DES, the
peaks corresponding to their HBA (for DES1 and DES2, the peaks of
the methyl groups bonded to the nitrogen atom and, for DES3, the
peaks of the terminal methyl groups).
After the calibration curves were established, the next step was
determination of tie-lines for each ternary mixture. In this step, ternary
mixtures of known composition were prepared in vials and were
vigorously stirred by magnetic agitation for 1 h and left to reach
equilibrium for at least 24 h in an incubator at 25 °C to ensure the
complete phase separation. This period of time was checked to be
sufficient for reaching the equilibrium. Then, each phase was carefully
sampled to avoid cross-contamination of the phases, and both phases
were analyzed by 1H NMR spectroscopy using the capillary method
previously described to establish the calibration curves. The
composition of each phase was calculated by the previously obtained
calibration curves.
COSMO-RS Prediction. The conductor-like screening model for
real solvent developed by Klamt and co-worker30 is a predictive model
that integrates the concepts of quantum chemistry, dielectric
continuum models, electrostatic interactions, and statistical thermody-
namics. Numerous theoretical documents and evaluation of the
performance of many COSMO-RS applications can be found in the
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literature. In general, the model has been proven to correctly describe
the solvent−solute solvation behavior in a real solvent system
qualitatively and, to some extent, quantitatively.28 At the present
time, COSMO-RS represents one of the most efficient models to
predict the thermodynamic properties of a pure compound, such as an
ionic liquid, and its mixture with organic compounds. In this work, we
used this model to predict the LLE behavior between the studied DES
and aromatic and aliphatic compounds and to better understand the
mechanism underlying these separations.
The first step for the COSMO-RS calculation is to produce the
required .cosmo file for all compounds present in the ternary mixtures.
In this step, the continuum solvation COSMO calculations of
electronic density and molecular geometry were performed using the
TURBOMOLE 6.1 program package on the density functional theory
level, utilizing the BP functional B88-P86 with a triple-ζ valence
polarized basis set (TZVP) and the resolution of identity standard
(RI) approximation.31 After the calculation was finished, the produced
.cosmo file was then used as input for the next calculation.
In the second step, the estimation of the liquid−liquid equilibrium
of the studied ternary mixtures was performed with the COSMOtherm
program utilizing the parameter file BP_TZVP_C30_1302 (COSMO-
logic GmbH & Co KG, Leverkusen, Germany). The equilibrium for a
ternary liquid−liquid system is defined by the following equation:
xiIγi I = xiIIγi II (1)
where γi is the activity coefficient of component i in phase I or II, and
xi is the mole fraction of component i in phase I or II. Both γi and xi
are solely predicted using COSMO-RS. It should be highlighted that,
during all calculations, the DES is treated as a complex neutral
molecule.
■ RESULTS AND DISCUSSION
Density and Viscosity Measurements. The thermophys-
ical properties, namely density and viscosity, are significant
parameters that influence the selection of proper extraction
solvent in LLE, since, for instance, high viscosities lead to mass
transfer limitations and also operational costs related to liquid
pumping and dispersion problems. Bearing this in mind, the
thermophysical characterization of the studied DES was
performed in this work, except for DES1, whose thermophys-
ical properties were previously reported by our group.32 The
density, ρ (kg·m−3), and viscosity, η (Pa·s), values of the three
DES studied in this work are given in Table S1 in the
Supporting Information. Since the studied DES are composed
by the same HBD (levulinic acid), it allows us to study the
impact of HBA chemical structures toward the density and
viscosity of the obtained DES. As can be seen from Figure 1a,
DES2 has the highest density, closely followed by DES1, while
DES3 has the lowest density. The observed difference in the
density of the DES might be attributed to the different HBA.
DES1 and DES2 are formed by HBAs that contain one
hydroxyl group that enables the further establishment of
hydrogen bonds with HBD, leading to more close arrangement
between HBA and HBD and, ultimately, to higher density. On
the other hand, the lack of a hydroxyl group of the HBA in
DES3 is responsible for its lower density when compared to the
other two DES. Similar behavior was also observed previously
by Kroon et al.33 for DES based on choline chloride and
tetramethylammonium chloride as HBAs. Thus, the presence of
the hydroxyl group in the HBA forming the DES might have a
significant impact on its density.
The density of the studied DES decreases with increasing
temperaturea general trend observed for organic compounds
and ILs. The density decrement shows a linear behavior with
the temperature increment, and thus the density values were
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Figure 1. Experimental (a) density, (b) molar volume, and (c)
viscosity values for (diamonds) [Ch]Cl:LevA (1:2); (circles) [BzCh]-
Cl:LevA (1:2); and (triangles) [N4444]Cl:LevA (1:2) as a function of
temperature (T). The density and viscosity values of [Ch]Cl:LevA
(1:2) were taken from Florindo et al.29
fitted as a linear function of temperature, T (K), by the least-
squares method using the linear expression given by eq 2:
ρ = a + b(T ) (2)
where a and b are adjustable parameters and ρ is density. The
reliability of eq 1 was evaluated based on the correlation
coefficient, R2, and the relative standard deviation, σ, which was
calculated using the following equation:
N ⎛ ρ − ρ ⎞2
1
∑ ⎜⎜ ⎟
exp, i calc, i
σ= ⎟ model described in eq 5:
N i=1 ⎝
ρcalc, i ⎠ (3)
where ρexp,i is the experimental data, ρcalc,i is calculated from the
calculation, and N is the total number of experimental points.
The a and b parameters, along with the R2 and σ values, are
given in Table 2. From the correlation coefficient, R2, listed in
Table 2, and also the standard deviation values, it can be
concluded that the use of a linear function adequately describes
the measured density data for the studied temperature range.
From the temperature dependence of density, the molar
volumes (Vm) of the studied DES were calculated using eq 4:
M
Vm =
ρ (4)
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Table 2. Fitted Parameters of the Linear Expression Given
by Eq 2, Relative Standard Deviation, σ, and Respective
Correlation Coefficient, R2a
a (g·cm−3) b × 104 (g·cm−3−1)K σ R2
−4
DES 1 1.3324 −6.53 2.44 × 10 0.9994
DES 2 1.3472 −6.58 1.47 × 10−4 0.9998
DES 3 1.2034 −6.33 1.15 × 10−4 0.9999
a
Standard uncertainties u are u(a) = 0.002 and u(b) = 5 × 10−6.
where ρ corresponds to the density (g·cm−3) and M is the
molar mass (g·mol−1) of the DES. The calculated molar volume
values are given in Table S1 in the Supporting Information and
are depicted in Figure 1b. In general, the molar volumes of all
DES slightly increase with increasing temperature. Within the
studied temperature range, the molar volume can be ranked as
DES1 < DES2 < DES3. This rank of molar volumes of the
studied DES is similar to the rank of their molar mass, where
DES1 (123.95 g·mol−1) < DES2 (149.32 g·mol−1) < DES3
(170.05 g·mol−1). Thus, it is interesting to note that the
presence of different HBAs plays a minimal role in the molar
volume, since the differences between the molar volumes of the
studied DES are similar to those observed for the molar mass.
Regarding the viscosity of the studied DES, from Figure 1c, it
can be seen that DES2 presents the highest viscosity, followed
by DES3, and DES1 has the lowest viscosity values. The highest
viscosity of DES2 in comparison to DES1 might be attributed
to the presence of the aromatic ring in its structure that, besides
largely increasing the DES molar volume, might promote
additional π−π interactions. Unlike density, it seems that the
presence of a hydroxyl group in the HBA does not have a
significant impact on viscosity, since the viscosity of DES3 lies
in between that of DES1 and DES2. These intermediate
viscosity values might be attributed to the longer alkyl chains of
ammonium cation in the HBA of DES3, since and as already
observed in the literature,34 an increase in the alkyl chain length
of the quaternary ammonium cation increases the area of
contact between the molecules, which also leads to an increase
of the dispersive forces between the molecules and,
consequently, high viscosities.
Similar to density, the viscosity of the studied DES decreases
with increasing temperature. A very significant decrement of
viscosity is observed for DES2, from 2.026 Pa·s (at 293.15 K)
to 0.04 Pa·s (at 353.15 K) in the studied temperature range.
The experimental viscosity values were fitted as a function of
temperature, using the Vogel−Fulcher−Tammann (VFT)
Bη
ln η = A η +
(T − Cη) (5)
where η is the viscosity in mPa·s, T is the temperature in K, and
Aη, Bη, and Cη are adjustable parameters. The adjustable
parameters, which were determined from the fitting of the
experimental data, are listed along with the relative standard
deviation, σ, and the energy barrier of a fluid to shear stress, E
(kJ·mol−1) at T = 298.15 K, in Table 3. The σ values were
calculated using eq 3, and the energy barrier was determined
based on the viscosity dependence with temperature using eq 6,
as follows:35
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Table 3. Fitted Parameters of the VFT Expression Given by Eq 5, Relative Standard Deviation, σ, Respective Correlation
Coefficient, R2, and Energy Barrier Values at T = 298.15 K
Parameters
Aη (mPa·s) Bη (K) Cη (K) σ R2 E298.15K (kJ·mol‑1)
−4
DES 1 −2.198 869.6 184.0 3.53 × 10 1.0 40.8
DES 2 −2.767 1020.5 194.9 8.07 × 10−4 1.0 55.8
DES 3 −2.915 1000.4 185.9 9.44 × 10−4 1.0 47.5

Figure 2. Literature16 (black dots) and this work (blue dots) tie-lines of the n-heptane (1) + toluene (2) + [C2mim][OAc] (3) ternary system at
298.15 K.

⎛ ⎞ the literature and experimental (this work) tie-lines of this

∂(ln η) ⎜ B ⎟ ternary system at T = 298.15 K. As can be seen from Figure 2,
E=R = R ⎜ η
⎟ the tie-lines determined by 1H NMR spectroscopy are in good
∂ T
1
() ⎜ ⎛⎜ Cη2 2C ⎞⎟
⎜ 2 − T η + 1⎟ ⎟
⎝ ⎝T ⎠⎠ (6)
where η is the viscosity, T is the temperature, Bη and Cη are the
adjustable parameters obtained from eq 5, and R is the universal
gas constant.
The higher the energy barrier value, the more difficult it is for
the DES molecules to flow. This fact can be a direct
consequence of the size or entanglement of the molecules
and/or of the presence of stronger interactions, for instance, H-
bonding interactions and π−π interactions, in the fluid. From
Table 3, it can be observed that DES2, containing [BzCh]Cl as
HBA, presents a higher E value, due to the presence of the
aromatic ring in its structure, than DES1, which contains
[Ch]Cl as HBA. The E values of the three DES studied can be
ordered as follows: DES1 < DES3 < DES2, which are in
agreement with the experimental viscosity values obtained.
LLE Measurements. The use of 1H NMR spectroscopy as
quantification method for other ternary systems containing
ionic liquids was already tested and reported in the
literature.8,9,36,37 To further validate the NMR method used
in this work, the tie-lines of the ternary system n-heptane +
toluene + [C2mim][OAc] measured in this work were
compared to literature data that was obtained using a
conventional method.16 Figure 2 shows a comparison between
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agreement with those reported in the literature determined by
the conventional method at the same temperature (rmsd =
0.9%), which allow us to validate 1H NMR spectroscopy as
quantification method. In this context, the performance of
DES1, DES2, and DES3 in the specific separation of toluene
from n-heptane was studied using the validated methodology.
For all the studied ternary systems, the composition of each
one of the DES in the n-heptane-rich phases could be
considered to be negligible, since 1H NMR spectra showed
no detectable signals corresponding to DES. The 1H NMR
spectra of typical upper (heptane-rich phase) and bottom
phases (DES-rich phase) of the studied ternary systems are
provided in the Supporting Information (Figures S1−S6).
From these spectra, it can also be observed that the proportion
of all the DES is maintained for the three ternary systems and
also for all the studied compositions. This leads to the
conclusion that, contrary to what happens in aqueous
systems,38,39 dissociation of the DES in these organic solvent
mixtures is not observed, and thus, DES are suitable solvents to
carry out the proposed application.
The experimental liquid−liquid phase equilibria data of the
three ternary systems were measured at T = 298.15 K and
atmospheric pressure and are presented in Table 4 and plotted
through a ternary diagram in Figures 3, 4, and 5. It should be
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Table 4. Composition of the Experimental Tie-Lines, contamination in DES3 is very high, thus requiring a difficult
Toluene Distribution Coefficient (β2), and Selectivity (S) for solvent recovery stage. The recovery of entrainers is usually
the Ternary Systems at T = 298.15 Ka carried out using distillation. Therefore, thermal studies will be
required before the introduction of DES in a refinery.
Heptane-rich phase DES-rich phase
It can also be observed from Figures 3−5 that the tie-lines
x1 x2 x1 x2 β2 S obtained for all the studied ternary systems exhibit negative
Heptane (1) + Toluene (2) + DES1 (3) slopes, leading to distribution coefficients lower than unity;
0.9207 0.0793 0.0038 0.0079 0.100 23.90 consequently, a high amount of DES will be required for this
0.8205 0.1795 0.0089 0.0184 0.103 9.47 extraction. Despite the fact that DES are cheap and easy to
0.7380 0.2620 0.0056 0.0277 0.106 13.93 synthesize, this drawback can be overcome by recovering and
0.6765 0.3235 0.0057 0.0367 0.113 13.46 reusing the extraction solvent.
0.6263 0.3737 0.0046 0.0474 0.127 17.27 Distribution coefficient, β, and selectivity, S, are the two
0.5504 0.4496 0.0059 0.0553 0.123 11.47 crucial parameters broadly used in the evaluation of extraction
0.4968 0.5032 0.0050 0.0608 0.121 12.01 solvent suitability to perform LLE. Thus, these two parameters
0.4392 0.5608 0.0023 0.0640 0.114 21.79 were calculated from the experimental data as follows:
0.3632 0.6368 0.0020 0.0672 0.106 19.16
0.3090 0.6910 0.0020 0.0713 0.103 16.18 x 2downphase
β2 =
0.2609 0.7391 0.0014 0.0742 0.100 18.97 x 2upperphase (7)
0.2125 0.7875 0.0011 0.0746 0.095 18.30
Heptane (1) + Toluene (2) + DES2 (3) ⎛ x upperphase ⎞⎛ x downphase ⎞
0.9314 0.0686 0.0080 0.0231 0.337 39.11 S = ⎜⎜ 1downphase ⎟⎟⎜⎜ 2upperphase ⎟⎟
0.8358 0.1642 0.0092 0.0324 0.198 17.90 ⎝ x1 ⎠⎝ x 2 ⎠ (8)
0.7503 0.2497 0.0102 0.0418 0.167 12.31 where xupper phase
and xupper phase
are the mole fractions of heptane
1 2
0.6844 0.3156 0.0063 0.0500 0.158 17.21 and toluene in the upper phase (heptane-rich phase),
0.6199 0.3801 0.0058 0.0625 0.164 17.57 respectively, and xdown phase
and xdown phase
are the mole fractions
1 2
0.5637 0.4363 0.0057 0.0745 0.171 16.92 of heptane and toluene in the lower phase (DES-rich phase).
0.5075 0.4925 0.0055 0.0875 0.178 16.39 The distribution coefficient and selectivity values are also listed
0.4520 0.5480 0.0048 0.1036 0.189 17.80 in Table 4 and represented as a function of the toluene mole
0.3703 0.6297 0.0038 0.1171 0.186 18.12
fraction in the aliphatic-rich phase in Figures 6 and 7,
0.3127 0.6873 0.0035 0.1211 0.176 15.74
respectively.
Heptane (1) + Toluene (2) + DES3 (3)
Taking into account that the distribution coefficient
0.9455 0.0545 0.0524 0.0405 0.742 13.41
determines the quantity of DES required for the extraction
0.8634 0.1366 0.0506 0.0671 0.491 8.38
process and that selectivity is related to the ability of DES to
0.7792 0.2208 0.0533 0.1060 0.480 7.02
extract the toluene in preference to n-heptane, the ideal
0.7276 0.2724 0.0514 0.1354 0.497 7.04
extraction solvent should have both high distribution coefficient
0.6693 0.3307 0.0557 0.1588 0.480 5.77
and selectivity values, since high distribution coefficients
0.5963 0.4037 0.0544 0.1960 0.486 5.32
correspond to lower operating costs and high selectivity values
0.5483 0.4517 0.0598 0.2211 0.489 4.49
lead to fewer number of extraction stages required in the
0.4813 0.5187 0.0642 0.2554 0.492 3.69
process.
0.4038 0.5962 0.0647 0.3055 0.512 3.20
From Figures 6 and 7, it can be seen that DES3 presents
0.3390 0.6610 0.0650 0.3374 0.510 2.66
lower selectivity but higher distribution coefficient values
0.2819 0.7181 0.0681 0.3816 0.531 2.20
compared to DES1 and DES2. The selectivity values can be
0.2302 0.7698 0.0707 0.4246 0.552 1.80
ordered as follows: DES3 < DES1 < DES2, which are in
0.1439 0.8561 0.0706 0.4944 0.578 1.18
agreement with the trend observed for the experimental density
0.0778 0.9222 0.0622 0.5884 0.638 0.80
values. In addition, the density difference between both phases
0.0447 0.9553 0.0481 0.6141 0.643 0.60
a
is very important, since large density differences permit higher
Standard uncertainties u are u(T) = 0.02 K, u(x) = 0.0001. equipment capacities. Although in the present work we did not
measure the density of the phases in equilibrium but only of the
highlighted that the compositions of both phases in equilibrium pure DES, the composition of the DES rich phase is very high
were calculated using calibration curves established in this in DES (usually around 0.85−0.95). Thus, the density
work. difference between the DES-rich phase and the phase rich in
From Figures 3 and 4, it can be seen that DES1 and DES2 toluene and n-heptane is most probably sufficiently large, since
are nearly immiscible to n-heptane. Also, although the solubility the DES density values, at 298.15 K, range from 1015 kg·m−3 to
of these two DES in toluene is very similar, DES2 presents a 1151 kg·m−3 for the three systems studied while the density
slightly higher solubility value, due to the presence of the values of the phase rich in toluene and n-heptane are in
aromatic ring in the HBA. Moreover, a different behavior was between those of the pure compounds, at 298.15 K (ρn‑heptane =
found when the HBA was changed to a quaternary ammonium 679 kg·m−3 and ρtoluene = 872 kg·m−3). Moreover, the presence
salt with higher hydrophobicity, [N4444]Cl. DES3 containing of the aromatic ring in the HBA of DES2 leads to high
this salt as HBA presents higher solubility in toluene compared distribution coefficient and selectivity values when compared to
to DES1 and DES2, as can be seen in Figure 5. The very low DES1, containing [Ch]Cl as HBA. In this case only the
solubility of the studied DES1 and DES2 in the heptane-rich aromaticity is under discussion because the two DES were
phase minimizes the loss of the DES and, consequently, the prepared at the same mole ratio and also have the same HBD.
contamination of the refined stream. However, the cross- Moreover, the introduction of hydrophobicity in the DES,
5645 DOI: 10.1021/acssuschemeng.6b01542
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ACS Sustainable Chemistry & Engineering Research Article

Figure 3. Tie-lines for a ternary mixture of {heptane + toluene + DES1} at T = 298.15 K and p = 0.1 MPa. Symbols: (circles, ), experimental data;
(squares, - - -), COSMO-RS.

Figure 4. Tie-lines for a ternary mixture of {heptane + toluene + DES 2} at T = 298.15 K and p = 0.1 MPa. Symbols: (circles, ), experimental
data; (squares, - - -), COSMO-RS.

selecting a HBA based on a quaternary ammonium salt, caused
an enhancement of the distribution coefficient values.
The experimental selectivity and distribution coefficient
values were compared to the literature data and are plotted
in Figures 8a and b, respectively. Although a direct comparison
cannot be exactly made, since the distribution coefficients and
selectivities of DES and most of the ILs presented in Figures 8a
5646
and b were obtained at a different temperature (T = 313.15 K),
it can be observed that the distribution coefficients and
selectivities of the systems studied in this work are of the same
order of magnitude of the literature values. Nevertheless, the
selectivity and distribution coefficients of the DES tested in this
work are higher than the literature values for DES.
DOI: 10.1021/acssuschemeng.6b01542
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ACS Sustainable Chemistry & Engineering Research Article

Figure 5. Tie-lines for a ternary mixture of {heptane + toluene + DES3} at T = 298.15 K and p = 0.1 MPa. Symbols: (circles, ), experimental data;
(squares, - - -), COSMO-RS.

Figure 6. Distribution coefficient (β2) values as a function of the mole
fraction of toluene in the n-heptane-rich phase at 298.15 K for the
ternary systems: (diamonds) n-heptane + toluene + DES1); (circles)
n-heptane + toluene + DES2); and (triangles) n-heptane + toluene +
DES3). The closed and open symbols represent experimental and
COSMO-RS prediction, respectively.
Figure 7. Selectivity (S) values as a function of the mole fraction of
toluene in the n-heptane-rich phase at 298.15 K for the ternary
systems: (diamonds) n-heptane + toluene + DES1; (circles) n-heptane
+ toluene + DES2; and (triangles) n-heptane + toluene + DES3. The
closed and open symbols represent experimental and COSMO-RS
prediction, respectively.

COSMO-RS Prediction. The LLE data of the three systems

studied in this work was predicted using COSMO-RS the ternary mixtures at both phases predicted using COSMO-
calculations. The COSMO-RS model combines a number of RS is given in Table S2 in the Supporting Information. In order
quantum chemical calculations with statistical thermodynamics to evaluate the performance of COSMO-RS to predict the
in order to determine and predict the thermophysical liquid−liquid phase equilibria of the studied ternary systems,
properties and phase behavior of fluids.40 Two different the root-mean-square deviation (rmsd) between the exper-
approaches can be considered for DES using COSMO-RS imental and predicted data was determined using the following
calculations: the independent-ion model ([C] + [A]), in which equation:
the DES is treated as an equimolar mixture, or the ion-paired
I
model ([CA]), in which the DES is considered as a whole rmsd = 100[∑ ∑ (xiexp,
,n − xipred
,n
,I 2
)
neutral molecule. In this work, the COSMO-RS calculations i n
were performed assuming that DES are a whole neutral II 1/2
molecule. The concentration of each one of the compounds in + (xiexp,
,n − xipred
,n
, II 2
) /2NR ] (9)

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ACS Sustainable Chemistry & Engineering
Figure 8. (a) Selectivity (S) and (b) distribution coefficient (β2) values
of the systems studied in this work (green bars) and systems reported
in the literature (gray bars),13,14,16,17,21 at T = 298.15 K (for DES1,
DES2, DES3, and [C2mim][OAc]) and T = 313.15 K (for the remain
DES and ILs) and toluene mole fraction in the upper phase ≈0.1.
where x is the mole fraction of compound i, R is the total
number of compounds (R = 3), n is the tie-line number, and N
is the total number of experiments. The rmsd values for the
studied systems are also shown in Table S2 in the Supporting
Information.
The results for COSMO-RS prediction for the studied
ternary systems are depicted in Figures 3−5 along with the
experimental data. COSMO-RS provides an excellent quanti-
tative prediction of the shape and size of the miscibility gap and
of the binodal curves and tie-lines for the ternary systems
composed by DES1 and DES2. The differences between the
predicted values and the experimental data are more significant
for the ternary systems with DES3 (rmsd = 3.9%), as the
immiscibility region decreases when compared with the systems
containing DES1 (rmsd = 0.9%) and DES2 (rmsd = 0.6%). The
obtained phase diagrams, using both experimental data and
COSMO-RS, are of type 2, presenting a partial miscibility in
two pairs of compoundsthat is DES + heptane and DES +
toluene. For the ternary phase containing DES1 and DES2, the
predicted binodal curves at the heptane-rich phase (upper
phase) lie close to the edge of the phase diagram due to low
solubilities displayed by the studied DES, as also evident from
the NMR method used in this work. On the other hand, the
phase diagram containing DES3 shows a noticeable miscibility
gap domain when compared to the other two DES. This might
be addressed due to its low polarity, which results from the
large alkyl chains and the absence of a hydroxyl group in the
HBA of DES3, and a subsequent increase of the dispersion
forces, thus enhancing the miscibility of DES3 and n-heptane.
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Research Article
The change in the distribution ratio and selectivity with the
concentration of toluene in the heptane-rich phase was also
estimated with COSMO-RS using eqs 7 and 8, respectively.
The estimated distribution ratio and selectivity predicted using
COSMO-RS are plotted in Figures 6 and 7, respectively,
together with the values obtained from experimental data.
COSMO-RS was able to capture the low and inferior to 1
distribution ratio values, as obtained from experimental data. As
mentioned before, these values resulted from negative tie-line
slopes (cf. Figures 3−5), meaning that large volumes of DES
are required for the extraction process.
Regarding selectivity, COSMO-RS was also able to produce a
similar trend of selectivity values to that obtained from
experimental data (provided in Table S2 in the Supporting
Information). In general, the selectivity values estimated using
COSMO-RS are superior to unity, thus confirming the
potential use of the studied DES as solvent from the extraction
process when applied to aromatic−aliphatic hydrocarbon
separation. Furthermore, the model has correctly described
the higher selectivity of DES1 and DES2 toward the aromatic−
aliphatic separation than of DES3, as observed experimentally.
It seems that the presence of a polar group, namely hydroxyl, is
responsible for an increase in the selectivity of the studied DES
toward aromatic−aliphatic separation.
■ CONCLUSIONS
In this work, DES based on three different salts as hydrogen
bond acceptors and a common hydrogen bond donor were
synthesized and their thermophysical properties, namely
density and viscosity, were analyzed, since these two parameters
influence the selection of a suitable extraction solvent in
liquid−liquid extraction processes. It was observed that the
DES containing a −OH group in the HBA present higher
densities compared to quaternary ammonium-based DES.
Afterward, their performance as extraction solvents in the
separation of toluene from n-heptane via liquid−liquid
extraction was evaluated, and it was concluded that the
presence of an aromatic ring in the HBA of DES leads to
high distribution coefficients and selectivities. However, the
distribution coefficient values can be enhanced with the
introduction of a more hydrophobic HBA, for instance, a
quaternary ammonium salt. Also, it was shown that the DES3
presents higher solubility in toluene compared to the other two
studied DES. A balance between the selectivity and the
coefficient distribution is always needed in order to select the
ideal extraction solvent for a specific extraction process. For the
studied ternary systems, COSMO-RS can satisfactorily describe
the trend observed for the phase diagrams and tie-lines slopes,
with rmsd varied between 0.5 and 3.9%. In addition, COSMO-
RS was also able to capture the trend of distribution ratio and
selectivity as observed experimentally. The prediction results
here reported show that COSMO-RS model can be successfully
applied to the a priori screening of DES to be used as solvent in
separations of aromatic−aliphatic hydrocarbon mixtures.
■
ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.6b01542.
Experimental density, viscosity, and calculated molar
volume of the synthesized DES. Typical 1H NMR spectra
DOI: 10.1021/acssuschemeng.6b01542
ACS Sustainable Chem. Eng. 2016, 4, 5640−5650
ACS Sustainable Chemistry & Engineering
of both upper and bottom phases of the ternary system:
n-heptane + toluene + DES. Composition of the tie-lines,
toluene distribution coefficient (β2) and selectivity (S),
predicted using COSMO-RS, as well as the root-mean-
square deviation (rmsd) between the experimental and
predicted data (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*Tel: +351-21-4469724. Fax: +351-21-4411277. E-mail ad-
dress: imarrucho@itqb.unl.pt.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
I.M.M. acknowledges FCT/MCTES (Portugal) for a contract
under Investigador FCT 2012. This work was partially
supported by FCT through the project PTDC/QEQ-FTT/
1686/2012 and R&D unit, UID/Multi/04551/2013 (Green-
IT). The NMR spectrometers are part of the National NMR
Facility supported by Fundação para a Ciência e a Tecnologia
(RECI/BBB-BQB/0230/2012).
■
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