Article

Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX pubs.acs.org/jced

Separation of Dimethyl Carbonate and Methanol by Deep Eutectic

Solvents: Liquid−Liquid Equilibrium Measurements and
Thermodynamic Modeling
Xiaowei Liu,§,† Dongmei Xu,§,† Baotao Diao,† Jun Gao,*,† Lianzheng Zhang,† Yixin Ma,†
and Yinglong Wang‡
†
College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, China
‡
College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
*
S Supporting Information

ABSTRACT: To separate the mixture of dimethyl carbonate and

methanol, two deep eutectic solvents (DESs), choline chloride with
glycerol and ethylene glycol, with the molar ratio of 1:2 were prepared
to separate dimethyl carbonate from the mixture by liquid−liquid
extraction. The liquid−liquid equilibrium (LLE) data for the ternary
systems of dimethyl carbonate + methanol + DESs were determined
at temperature of 298.15 and 308.15 K under 101.3 KPa. The
measured tie-line data were validated by the Bachman equation, and
the correlation coefficients (R2) were all close to 1. Meanwhile, the distribution coefficient and selectivity were calculated from
the experimental results. The LLE experimental data were correlated using the nonrandom two-liquid (NRTL) model, and the
correlated results agree well with the LLE experimental data. Also, the parameters of the NRTL model were regressed.

1. INTRODUCTION et al. reported the liquid−liquid equilibrium for the system of

Dimethyl carbonate (DMC) as an important chemical has a
wide range of applications which can be used in the production
of pharmaceuticals, fragrances, coatings and refined hydro-
carbons, and applied as an important solvent in industry. Also,
it can be used as an agent of methylation and carbonylation in
synthesis. Moreover, DMC is applied as a moderate octane
enhancer in the field of fuel, which can be an alternative
additive to MTBE (methyl tert-butyl ether).1
However, in the production process of DMC, methanol is
used as a raw material and cannot react completely in the
synthesis of DMC. Most of the unreacted methanol is
recovered and reused. Because methanol can form azeotrope
with DMC, it is difficult to separate DMC with high purity
from the mixture of DMC and methanol. There are some
technologies to separate the mixture of DMC and methanol
such as azeotropic distillation, pressure-swing distillation,
extractive distillation, membrane separation, and low temper-
ature crystallization,2 but these technologies have some
disadvantages in costs, energy consumption, and environment
protection.
Until now, for the separation of DMC and methanol, some
research works about the phase equilibrium for the mixture of
DMC and methanol have been reported.1,3−6 Hwang reported
the liquid−liquid equilibria for ternary system of DMC +
methanol + water at 298.15 K.1 Esteban reported the liquid−
liquid equilibria for the ternary systems DMC + methanol +
glycerol.3 Pan et al. reported the separation of DMC +
methanol azeotrope using alkane extractants and presented the
equilibria for the systems of DMC + methanol + alkanes.4 Cai
DMC + methanol +1-alkyl-3-methylimidazolium dialkylphos-
phate.5 Li et al. reported the isobaric vapor−liquid equilibrium
for the system of DMC + methanol + 1-ethyl-3-methylimida-
zoliumtetrafluoroborate/1-octyl-3-methylimidazolium tetra-
fluoroborate.6
In recent years, deep eutectic solvents (DESs) as a new
generation of green solvents have displayed practical and
potential applications such as biodiesel purification,7 drug
solubilization,8 CO2 absorption,9−11 and separation of azeo-
tropic mixtures.12,13 To our knowledge, there has been no
report about the liquid−liquid equilibria for the systems of
DMC + methanol + DESs. In this work, two DESs were
prepared with choline chloride and glycerol/ethylene glycol,
and the ternary phase equilibria of DMC + methanol + DESs
were explored for the separation of the mixture DMC +
methanol.
2. EXPERIMENTAL SECTION
2.1. Chemicals. The chemicals used in this work were
choline chloride, dimethyl carbonate, methanol, glycerol, and
ethylene glycol, which were analytical grade and purchased
commercially. Choline chloride before used was dried under
vacuum drying oven, the other chemicals were used without
further purification. The CAS number, purity, and supplier
about the chemicals are listed in Table 1.
Received: September 29, 2017
Accepted: February 28, 2018

© XXXX American Chemical Society A DOI: 10.1021/acs.jced.7b00858

J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 1. Chemicals Used in This Work were taken out by syringes and put into sample bottles as quick
as possible for analysis.
CAS purity (wt analysis
name number %) method supplier 2.3. Analysis. The samples were analyzed using gas
methanol 67-56-1 ≥99.50b GCa Tianjin Bodi Chemical chromatograph (Lunan GC SP-6890) equipped with a packed
Co., Ltd. column (Porapak Q 3 mm × 2 m) and a thermal conductivity
dimethyl 616-38-6 ≥99.00b GCa Tianjin Kaixin Chemical detector TCD (Shandong Rui Hong Chemical Co., Ltd.),
carbonate Co., Ltd. which was linked to an N2000 GC workstation developed by
choline 67-48-1 ≥99.00b Shandong Xiya Chemical
chloride Co., Ltd. Zhejiang University. The carrier gas was hydrogen with purity
glycerol 56-81-5 ≥99.00b GCa Chengdu Kelong of 99.999%, and the flow rate was 50 mL/min. The
Chemical Reagent Co. temperature of injector, column, and detector were set at
Ltd.
433.15, 403.15, and 443.15 K, respectively. Before analyzing the
ethylene 107-21-1 ≥99.99b GCa Qingdao Shijixing
glycol Chemical Reagent Co., samples, GC was calibrated by the standard mixtures which
Ltd. were prepared by an analytical balance (Kern and Sohn ABS-
a
Gas chromatography. bAnalysis by the supplier. 220−4) with a precision of 0.0001 g. For analysis of DESs, the
gravimetric method was applied. The concentrations of the
DES samples were determined by the sample mass difference
before and after vaporizing the solvents in a drying oven at
2.2. Apparatus and Procedure. To prepare the DES, 373.15 K (DZF6050, Shanghai Yiheng) until the weight was
choline chloride was dried in a vacuum drying oven at 313.15 K kept constant.16 Each sample was analyzed three times to
for at least 2 days before it was used. Then, choline chloride ensure the reliability of the experimental data, and the average
and glycerol (DES 1) and choline chloride and ethylene glycol
values were adopted. The integrity of the two DESs distributed
(DES 2) with the molar ratio of 1:2 were mixed in a round-
between two equilibrium phases was validated by the spectra of
bottom flask. The mixture was stirred at 348.15 K until a clear 1
liquid appeared. For the measurement of LLE, the ternary H NMR, which are provided in Figures S1−S10 in the
mixture DMC + methanol + DES was placed in a sealed 25 mL Supporting Information.
round-bottom flask with a magnetic stirrer (JJ-1-40W,
Changzhou Danrui Experimental Instrument Equipment Co., 3. RESULTS AND DISCUSSION
Ltd.). The apparatus for the LLE experiment was reported in 3.1. LLE Experimental Data. The LLE data for the ternary
our previous work.14 During the preparation of the ternary
systems DMC + methanol + DESs were measured at 298.15
mixture, the volume of DMC was fixed, and the volumes of
and 308.15 K under 101.3 kPa, which were expressed as mole
DES and methanol varied with one increased and the other
decreased correspondingly to ensure the entire two-phase fraction and are listed in Tables 2 and 3. The feed compositions
region could be covered as much as possible.15 The prepared for the systems DMC + methanol + DESs are listed in the
mixture was stirred vigorously for 6 h to mix sufficiently, and Tables S1 and S2 in the Supporting Information. The phase
then the mixture was settled for 12 h in a thermostat water bath diagrams of the ternary systems are presented in Figures 1 and
(SYC-15C, Nanjing Huchuan Electronic Equipment Co., Ltd.), 2, which are classified as Treybal’s II with one partially miscible
which was kept at constant temperature, to reach the system.17,18 From Figure 1, the temperature has an obvious
equilibrium state. At equilibrium, the mixture was divided effect on the biphasic region for the ternary system of DMC +
into two layers: the upper layer was DMC-rich phase, and the methanol + DES 1 and has a slight effect for the ternary system
lower layer was DES-rich phase. The samples of both phases DMC + methanol + DES 2, as shown in Figure 2.

Table 2. Experimental LLE Data (Expressed as Mole Fraction), Solute Distribution (D), and Selectivity (S) for the Ternary
System DMC (1) + Methanol (2) + DES 1 (3) at T = (298.15 and 308.15 K) under 101.3 KPaa
DMC-rich phase DES 1-rich phase
T/K xI1 xI2 xI3 xII1 xII2 xII3 S D
298.15 0.8699 0.0000 0.1301 0.0182 0.0000 0.9818
0.8163 0.0450 0.1387 0.0185 0.0067 0.9748 6.5696 0.1489
0.7459 0.0869 0.1672 0.0197 0.0131 0.9672 5.7078 0.1507
0.7120 0.1207 0.1673 0.0198 0.0182 0.9620 5.4222 0.1508
0.6850 0.1404 0.1746 0.0202 0.0212 0.9586 5.1204 0.1510
0.6524 0.1644 0.1832 0.0205 0.0248 0.9547 4.8008 0.1509
0.6184 0.1927 0.1889 0.0210 0.0291 0.9499 4.4469 0.1510
308.15 0.9031 0.0000 0.0969 0.0112 0.0000 0.9888
0.9022 0.0008 0.0970 0.0114 0.0001 0.9885 9.8925 0.1250
0.8926 0.0029 0.1045 0.0142 0.0004 0.9854 8.6702 0.1379
0.8800 0.0119 0.1081 0.0162 0.0018 0.9820 8.2166 0.1513
0.8607 0.0297 0.1096 0.0171 0.0045 0.9784 7.6263 0.1515
0.8460 0.0431 0.1109 0.0184 0.0065 0.9751 6.9341 0.1508
0.8314 0.0554 0.1132 0.0199 0.0084 0.9717 6.3347 0.1516

a
The superscript I represents the DMC-rich phase; II represents the DES 1-rich phase, and the subscripts 1, 2, and 3 indicate DMC, methanol, and
DES 1, respectively. Standard uncertainties: u(T) = 0.05 K, u(p) = 0.1 kPa, and u(x) = 0.0063.

B DOI: 10.1021/acs.jced.7b00858
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Journal of Chemical & Engineering Data Article

Table 3. Experimental LLE Data (Expressed as Mole Fraction), Solute Distribution (D), and Selectivity (S) for the Ternary
System DMC (1) + Methanol (2) + DES 2 (3) at T = (298.15 and 308.15 K) under 101.3 KPaa
DMC-rich phase DES 2-rich phase
T/K xI1 xI2 xI3 xII1 xII2 xII3 S D
298.15 0.8361 0.0000 0.1639 0.0047 0.0000 0.9953
0.7381 0.0843 0.1776 0.0052 0.0100 0.9848 16.8378 0.1186
0.6945 0.1256 0.1799 0.0054 0.0151 0.9795 15.4620 0.1202
0.6725 0.1452 0.1823 0.0055 0.0176 0.9769 14.8209 0.1212
0.6450 0.1690 0.1860 0.0057 0.0207 0.9736 13.8602 0.1225
0.6189 0.1915 0.1896 0.0059 0.0236 0.9705 12.9274 0.1232
0.5901 0.2167 0.1932 0.0061 0.0267 0.9672 11.9192 0.1232
308.15 0.8613 0.0000 0.1387 0.0007 0.0000 0.9993
0.8184 0.0338 0.1478 0.0009 0.0034 0.9957 91.4714 0.1006
0.7886 0.0564 0.1550 0.0012 0.0060 0.9928 69.9113 0.1064
0.7503 0.0861 0.1636 0.0017 0.0097 0.9886 49.7227 0.1127
0.7269 0.1044 0.1687 0.0020 0.0123 0.9857 42.8203 0.1178
0.7003 0.1244 0.1753 0.0026 0.0149 0.9825 32.2609 0.1198
0.6671 0.1502 0.1827 0.0042 0.0180 0.9778 19.0346 0.1198
a
The superscript I represents the DMC-rich phase; II represents the DES 2 phase, and the subscripts 1, 2, and 3 indicate DMC, methanol, and DES
2, respectively. Standard uncertainties: u(T) = 0.05 K, u(p) = 0.1 kPa, and u(x) = 0.0050.

The distribution coefficient (D) and selectivity (S) were

calculated from the experimental data by the following
expressions:19,20

x 2II
D=
x 2I (1)

(x 2II/x 2I)
S=
(x1II/x1I) (2)

where x1 and x2 refer to the mole fractions of DMC and

Figure 1. Phase diagrams for the ternary mixture DMC + methanol +
DES 1: (■−■), experimental tie-line data; (△--△), correlated results
using the NRTL model. (a) T = 298.15 K, (b) T = 308.15 K.
Figure 2. Phase diagrams for the ternary mixture DMC + methanol +
DES 2: (■−■), experimental tie-line data; (△--△), correlated results
using the NRTL model. (a) T = 298.15 K, (b) T = 308.15 K.
C DOI: 10.1021/acs.jced.7b00858
methanol, respectively; the subscripts I and II refer to the
DMC-rich phase and the DES-rich phase, respectively.
The values of distribution coefficient and selectivity are
presented in Tables 2 and 3. The distribution coefficient and
selectivity versus the concentration of methanol in the DMC-
rich phase are presented in Figures 3 and 4. The values of the
selectivity are greater than 1 as shown in Figure 4, which
indicate that the separation of DMC from the mixture DMC +
methanol by the DESs selected in this work is feasible. The
values of the distribution coefficient and selectivity for the
ternary system DMC + methanol + DES 2 are greater than
those of DMC + methanol + DES 1, which indicate that DES 2
has extraction ability better than that of DES 1. Because the
methanol content in the feed compositions was lower, the
distribution coefficient was near constant when the feed
compositions changed. Meanwhile, due to the reason, the
distribution coefficient of the investigated systems was also
slightly affected by the temperature change. Same phenomenon
can be observed in the references.5,21 And the higher
temperature for the same system, the higher values of the
selectivity are, which implies that the higher temperature is
helpful in separating DMC from the mixture DMC + methanol.
To compare and evaluate the extraction performance of DES 1,
1-alkyl-3-methylimidazolium dialkylphosphate,5 and water,1 the
values of D and S were plotted in Figures S11 and S12 in the
Supporting Information.
3.2. Data Reliability. The experimental tie-line data were
validated by the Bachman equation,19,22 which is expressed as
follows:
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Figure 3. Distribution coefficient values for the systems: (a) DMC +

methanol + DES 1 (■, 298.15 K; □, 308.15 K) and (b) DMC + Figure 4. Selectivity values for the systems: (a) DMC + methanol +
methanol + DES 2 (●, 298.15 K; ○, 308.15 K). DES 1 (■, 298.15 K; □, 308.15 K) and (b) DMC + methanol + DES
2 (●, 298.15 K; ○, 308.15 K).
⎛ xI ⎞
x1I = a + b⎜ 1II ⎟
⎝ x3 ⎠ (3) where xi is the mole fraction of component i, Bij is the binary
parameter, and αij is the nonrandomness parameter.
where the superscript I represents the DMC-rich phase; II To optimize the binary parameters of the NRTL, the
represents the DES-rich phase, and the subscripts 1 and 3 objective function (OF) is defined as follows:
indicate DMC and DES. a and b are the parameters of the exp cal 2
Bachman equation. OF = min ∑ ∑ ∑ (xijk − xijk )
The correlated results of the Bachman equation are given in k j i (7)
Figure 5, and the correlation coefficients R2 were all close to exp cal
where x and x are the experimental and calculated values
unity. The parameters a and b of the Bachman equation are and the subscripts i, j, and k refer to the component, phase, and
listed in Table 4. tie-line, respectively.
3.3. Data Correlation. For the LLE data correlation, the In this work, the root-mean-square deviation (RMSD) was
NRTL model was adopted and is presented as follows:23,24 applied to evaluate the NRTL model, which is as follows:
∑j τjiGjixj xjGij⎛ ∑ xτ G ⎞ ⎛ ∑ ∑ ∑ (x exp − x cal)2 ⎞1/2
∑ ⎜⎜τij − l l lj lj ⎟⎟
RMSD = ⎜ ⎟
ln γ = + k j i ijk ijk
∑k Gkixk ∑k Gkjxk ⎝ ∑k Gkjxk ⎠ (4) ⎜ ⎟
j
⎝ 6 n ⎠ (8)
Δgij Bij where x is the mole fraction and n is the number of tie-lines.
τij = = τij ≠ τji The calculated results for the ternary systems DMC +
RT T (5)
methanol + DESs are presented in Table 5 and plotted in
Figures 1 and 2. The values of the RMSD between the
Gij = exp( −αijτij) αij = αji (6) experimental and calculated values are less than 0.05, which
D DOI: 10.1021/acs.jced.7b00858
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Journal of Chemical & Engineering Data Article

Table 5. Binary Parameters of the NRTL Model and RMSD

Values for the Ternary Systems
binary interaction parameters
T/K i−j Bij/K Bji/K α RMSD
DES 1 (1) + methanol (2) + DMC (3)
298.15 1−2 497.290 268.270 0.2 0.0018
1−3 1062.953 212.246
2−3 −382.392 681.253
308.15 1−2 −180.690 1656.676 0.2 0.0025
1−3 1105.521 297.922
2−3 −604.096 719.963
DES 2 (1) + methanol (2) + DMC (3)
298.15 1−2 938.298 −11.277 0.2 0.0036
1−3 1492.250 94.683
2−3 241.209 154.838
308.15 1−2 1768.968 −574.766 0.2 0.0375
1−3 1885.472 193.707
2−3 −648.286 2389.072

of the correlation (R2) are all close to 1. Meanwhile, the

Figure 5. Correlation results by the Bachman equation for the ternary
systems: (a) DMC + methanol + DES 1 (■, 298.15 K; ●, 308.15 K)
and (b) DMC + methanol + DES 2 (□, 298.15 K; ○, 308.15 K).
Table 4. Constants of the Bachman Equation and
Correlation Factor for the Ternary Systems
R2
distribution coefficient and selectivity were calculated from the
LLE data. According to the values of the distribution coefficient
and selectivity, the two DESs can separate DMC from the
mixture of DMC + methanol, and DES 2 provided better
extraction ability than DES 1. Because the methanol content in
the feed composition was lower, the distribution coefficient was
near constant when the feed composition changed. The
temperature had a more obvious effect on the selectivity than
did the distribution coefficient. In addition, the NRTL model
was applied to correlate the LLE data for the two ternary
systems, and the RMSD values were less than 0.05, indicating
that the NRTL model could give good correlation for the
experimental LLE data.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jced.7b00858.
Feed compositions (mole fraction) for the system DMC
(1) + methanol (2) + DESs (3) (PDF)

■
system T/K a b
DMC + methanol + DES 1 298.15 0.0738 0.9348 0.9999
308.15 0.1839 0.8083 0.9995 AUTHOR INFORMATION
DMC + methanol + DES 2 298.15 0.0599 0.9338 0.9999 Corresponding Author
308.15 0.0652 0.9248 1.0000 *E-mail: gao@sdust.edu.cn; Telephone: + 86 532 86057103.
ORCID
Dongmei Xu: 0000-0002-5770-0513
indicates that the calculated results by the NRTL model are in
Jun Gao: 0000-0003-1145-9565
agreement with the experimental LLE data. Meanwhile, the
optimized binary interaction parameters for the NRTL model Yinglong Wang: 0000-0002-3043-0891
can be helpful in developing the separation process for the Author Contributions
§
mixture of DMC + methanol. D.X. and X.W.L. contributed equally.
Funding
4. CONCLUSION Financial support from National Natural Science Foundation of
For separation of the mixture DMC + methanol, two deep China (Project 21306093) is gratefully acknowledged.
eutectic solvents based on choline chloride and glycerol/ Notes
ethylene glycol were prepared as extractants in this work, and The authors declare no competing financial interest.
the liquid−liquid equilibrium data for the ternary systems
DMC + methanol + DESs were measured at temperature
298.15 and 308.15 K under 101.3 KPa. The validity of the tie-
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F DOI: 10.1021/acs.jced.7b00858
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