Separation and Purification Technology 269 (2021) 118713

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Separation and Purification Technology

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

Extractive distillation using ionic liquids-based mixed solvents combined

with dividing wall column
Guoxuan Li a, Shengli Liu a, Gangqiang Yu b, Chengna Dai b, *, Zhigang Lei a, c
a
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Box 266, Beijing 100029, China
b
Faculty of Environment and Life, Beijing University of Technology, Beijing 100124, China
c
School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, China

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

Keywords: To further reduce the energy consumption, investment and operating costs of the extractive distillation (ED)
Extractive distillation process, this study focuses on the process intensification by the combination of ionic liquids-based mixed en­
Dividing wall column trainers and dividing wall column (DWC) for methanol/ethanol/water separation process. Based on the process
Ionic liquids-based mixed entrainers
simulation results, energy efficiency, economic and environmental impact assessments were carried out and
Energy-saving
UNIFAC-Lei model
compared with the benchmarked ED process using ethylene glycol as entrainer. The ternary ED process using the
ionic liquids-based mixed entrainer can reduce the total annual cost (TAC) by about 5.98% and the energy
consumption by 2.93%. The TAC and energy consumption for the proposed ternary ED process with DWC using
the ionic liquids-based mixed entrainer can be reduced by 7.81% and 4.52%, respectively. The novel ED process
shows the high energy efficiency, low economy cost and low CO2 emissions with a great industrial application
prospect when compared to the benchmarked process.

1. Introduction
Ethanol, as an important basic chemical raw material or fuel, is
widely used in chemical, energy and pharmaceutical fields. In the
context of the current soaring international oil price and shortage of
petroleum energy, it is of great strategic significance to develop fuel
ethanol to replace petroleum products or as an additive to gasoline. The
production process of ethanol is often accompanied by by-products of
water and methanol. Ethanol and water are azeotropic systems, and
ethanol and methanol are systems with similar boiling points. Therefore,
it is of great significance to separate water and methanol from ethanol to
prepare high-quality anhydrous ethanol.
Liquid-liquid extraction is suitable for the separation of mixture with
high partition coefficient [1,2]. Distillation is the most commonly used
mixture separation method due to its unique superiority in operation
and control [3]. Pressure-swing distillation is often used to separate
pressure sensitive mixtures [4,5]. Extractive distillation (ED), as a spe­
cial distillation separation technology, is an effective method to separate
azeotropic system or close-boiling mixtures, which plays an extremely
important role in the chemical and pharmaceutical industries [6–8].
Arifin et al. [9] studied the economic performance of isopropanol
extractive distillation dehydration process using dimethyl sulfoxide
(DMSO) as entrainer. The results showed that the TAC and steam cost of
the process were significantly lower than the competitive design process
of heterogeneous azeotropic distillation. Wang et al. [10] proposed a
sequential iterative automatic optimization method to explore the effect
of operating pressure on energy consumption and economy of the ED
process. When compared to the optimized process under atmospheric
pressure, the ED process can reduce 60.1% in energy-saving and 47.0%
in TAC. Yang et al. [11] proposed an optimization method based on the
global optimization model for ternary ED separation of ethyl acetate/
ethanol/water ternary non-ideal system. The results show that the TAC,
exergy loss and CO2 emissions of the triple-column ED process are
obviously lower than other ternary ED process. Luyben [12] used
pressure-swing distillation and ED to separate acetone/methanol binary
system. The results show that the TAC of ED process is 15% lower than
that of pressure-swing distillation.
Energy-saving of distillation process is an eternal theme in the field
of separation. The conventional energy-saving methods of ED include
searching for highly selective entrainers [13–15], determining the
optimal distillation sequence [16,17] and operating parameters [18].
Traditional ED generally uses single entrainer, and mixed entrainers has
gradually become the mainstream of extractive distillation due to its
advantages of good separation effect and low energy consumption [19].
In our previous work [20], we explored ethylene glycol (EG) and ionic

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

https://doi.org/10.1016/j.seppur.2021.118713
Received 19 February 2021; Received in revised form 31 March 2021; Accepted 31 March 2021
Available online 8 April 2021
1383-5866/© 2021 Elsevier B.V. All rights reserved.
G. Li et al. Separation and Purification Technology 269 (2021) 118713

Nomenclature ACC annual capital cost

AOC annual operating cost
b the availability function CDC conventional distillation column
h enthalpy, [kJ/kmol] CTED conventional ternary extractive distillation
n the mole flow rate [kmol/s] DMAC dimethylacetamide
s molar entropy, [kJ/kmol K] DMF N,N-dimethylformamide
α the ratio of molar masses of CO2 DMSO dimethyl sulfoxide
η thermodynamic efficiency DWC dividing wall column
hProc the latent enthalpy of utility steam ED extractive distillation
λProc the latent heat of utility steam EDC extractive distillation column
C% the carbon content in the fuel EDWC extractive dividing wall column
Ex exergy consumption of the system, [kW] EDWC-TED extractive dividing wall column ternary extractive
LW the lost work distillation
NHV the net heating value with unit mass fuel combustion EG ethylene glycol
QC heat duty of condensers, [kW] MC main column
QFuel the total heat released by fuel combustion, (kW) NMP N-Methyl pyrrolidone
QProc the heat duty of reboiler SC side column
QR heat duty of reboilers, [kW] SRC solvent recovery column
TC the corresponding temperature of condensers, [K] TAC total annual cost
T0 the surrounding temperature, [K] TCTED thermally coupled ternary extractive distillation
TR the corresponding temperature of reboilers, [K] VLE vapor–liquid equilibrium
Wmin the minimum separation work [EMIM][DCA] 1-ethyl-3-methylimidazolium dicyanamide
Ws the shaft work, [kW] [EMIM][NO3] 1-ethyl-3-methylimidazolium nitrate
[EMIM][MeSO3] 1-ethyl-3-methylimidazolium methanesulfonate
Abbreviations
A-DWC azeotropic dividing-wall column

liquid as mixed solvents for the separation of ethanol/water, which
reduced the amount of entrainer by 20% and energy consumption by
11.53% when compared to that using EG as single entrainer. Zhao et al.
[21] studied the separation of tetrahydrofuran/ethanol/water ternary
azeotropic system with DMSO, EG and their mixed solvents as en­
trainers. The TAC of the mixed entrainers distillation process is reduced
by 6.55% and 31.88% when compared to the distillation process with
DMSO and EG as single-entrainer, respectively. Therefore, the usage of
mixed entrainer maybe a potential strategy for ED process to reducing
the energy.
Recently, some new energy-saving technologies have been put for­
ward for extractive distillation. Ma et al. [22] studied the separation of
ethyl acetate/ethanol/water ternary mixture by thermally coupled
ternary extractive distillation (TCTED) with ionic liquid as entrainer.
The results show that TCTED process can reduce TAC and CO2 emis­
sions. Yu et al. [23] investigated a triple-column model of azeotropic
dividing-wall column (A-DWC) for heterogeneous azeotropic distillation
of tert-butyl alcohol dehydration process. Compared to the original two-
column model, the optimized A-DWC can save energy by 23.80% and
reduce TAC by 19.93%. Shi et al. [24] proposed a new process flow
consisting of two single-dividing-wall extractive distillation columns for
the efficient separation of acetone/methanol/butanone/tert-butanol.
Compared to the traditional four-column extractive distillation process,
the new process can reduce TAC by 12.50% and CO2 emissions by
24.23%. Gao et al. [25] found that the vapor recompression-assisted
dividing wall column with a middle partition has higher energy effi­
ciency than traditional DWCS. Wu et al. [26] separated the 1,2-pro­
panediol + 1,3-butanediol + 1,4-butanediol system with great similarity
in molecular structure and properties by using the DWC, and the energy-
saving was more than 47%. Singh et al. [27] used heat-pump assisted
distillation to recover bioethanol from fermentation broth. The results
showed that the unit energy consumption of bioethanol was reduced by
38%. A lot of research has been done on the selection of solvents and the
innovation of energy-saving technology. However, there are few reports
on the separation of ternary low-carbon alcohol mixture by using the
mixture of ionic liquid and traditional solvent as entrainer.
In this work, we proposed a novel extractive dividing wall column
ternary extractive distillation (EDWC-TED) process for separating the
low-carbon alcohol mixture of methanol/ethanol/water, in which a
mixture of ionic liquid and traditional solvent was used as an entrainer
combined with dividing wall column. Thermodynamic efficiency, CO2
emissions and TAC of the EDWC-TED process and the benchmarked
triple-column extractive distillation process using EG as entrainer were
performed to assessment energy efficiency, environmental impact and
economic feasibilities of the different configurations processes.
2. Performance evaluation methods
According to the simulation results and performance evaluation
methods, thermodynamic efficiency, TAC, and CO2 emissions for the
different configurations processes were investigated in this work.
2.1. Thermodynamic efficiency evaluation
The thermodynamic efficiency (η) is an important criterion to esti­
mate the utilization ratio of process effective energy. The thermody­
namic efficiency of distillation process is written as
Wmin
η = (1)
Wmin + LW
where Wmin is the minimum separation work, [kJ/h]. LW is the lost
work, [kJ/h].
For the distillation process, the state of the feed and the product are
constant, so Wmin is constant. The value of the Wmin is defined as the
difference between the total effective energy of the product stream and
the total effective energy of the feed stream, which can be described by
∑ ∑
Wmin = nb− nb (2)
out of system into system
where n and b are the mole flow rate [kmol/s] and the availability
function, respectively. The availability function b can be described by
b = h − T0 s (3)

2
G. Li et al. Separation and Purification Technology 269 (2021) 118713

y (Mass fraction of methanol in vapor phase)

y (Mass fraction of methanol in vapor phase)
1.0 1.0
(a) (b)

0.8 0.8

0.6 0.6

EG EG
0.4 DMSO 0.4 DMSO
DMF DMF
DMAC DMAC
0.2 NMP 0.2 NMP

0.0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
x (Mass fraction of methanol in liquid phase) x (Mass fraction of methanol in liquid phase)

1.0
y (Mass fraction of ethanol in vapor phase)

(c)

0.8

0.6

EG
0.4 DMSO
DMF
DMAC
0.2 NMP

0.0
0.0 0.2 0.4 0.6 0.8 1.0
x (Mass fraction of ethanol in liquid phase)
Fig. 1. The effects of different solvents on the VLE data for methanol/ethanol (a), methanol/water (b), and ethanol/water (c).

where h is enthalpy, [kJ/kmol]; s is molar entropy, [kJ/kmol K]; and
T0 is the surrounding temperature, [K].
For the distillation system, the constant temperature heat source
mainly includes reboiler and condenser. The distillation column absorbs
heat from the reboiler at a high temperature, and releases heat from the
condenser at a low temperature, which is similar to a heat engine that
generates separation work. The total effective energy input is given by
∑ T0
Ex = Wmin + LW = QR (1 − )−
into system
TR out system
where Ex presents exergy consumption of the system, [kW]; QR and
QC are the heat duty of reboilers and condensers, [kW]; TR and TC are the
corresponding temperatures, [K]; and Ws is the shaft work, [kW].
2.2. Economic evaluation
TAC including annual capital cost (ACC) and annual operating cost
(AOC) is generally used as the economic evaluation criterion for process
design. Based on the Douglas’s economic model [28], the minimum TAC
is taken as the objective function, and the sequential iterative algorithm
[29,30] is used for optimization. It can be described by
TAC ($/year) = ACC + AOC
The total capital cost, including the costs of distillation columns and
heat exchangers, is calculated annually, and this period is generally
defined as the plant life.
Total capital cost
ACC = (6)
Plant life time
where the plant life time is assumed to be 3 years. The relevant
economic calculation models and hypotheses refers to the literature
[31].
AOC refers to the cost of utility engineering, including the steam
∑ T0
QC (1 − ) − Ws (4) costs and cooling water costs. It can be expressed by
TC
AOC = steam costs + cooling water costs (7)
2.3. CO2 emissions evaluation
As one of the most important greenhouse gases, the emission of CO2
has played a huge role in promoting global warming. Hence, it is
increasingly urgent to control the CO2 emission. The energy required by
distillation column and its heat exchange network is directly or indi­
rectly from the combustion of fossil fuel. Typical fossil fuels mainly
include heavy oil, natural gas and coal. Therefore, the reduction of en­
ergy consumption in distillation process not only means the reduction of
TAC, but also a reduction of greenhouse gas emissions.
CO2 emissions were applied to evaluate the environmental perfor­
(5)
mance of different configurations processes. Assuming that air is
excessive and no CO is produced, CO2 emissions (kg/h) are calculated by
[32]

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G. Li et al. Separation and Purification Technology 269 (2021) 118713

[OMIM]+ [HMIM]+
[BEP]+ [PMIM]+ -2
0
[HMPY] + [OMIM]+ -1
1
[HMIM]+ [EMIM]+ 0
[BMPIP]+ 2 [EMP]+
1
[BMP]+ 3 [BMPY]+
2
+ +
[DMAEP] 4 [BMIM]
3
[BMPY]+ [BEIM]+
+ +
[BEIM] [EMMIM]
[BMIM]+ [DMAEP]+
[PMIM]+ [HMPY]+
+
[EMMIM] [BMP]+
[EMIM]+ [BMPIP]+
[EMP]+ [BEP]+

[I]-
[Tf2n]-
[BF4]-
[DCA]-

[Ben]-

[SbF6]-
[I3]-
[NO3]-

[ClO4]-
[C4F7O2]-
[Cl]-

[BF4]-

[MeSO3]-
[I3]-

[Ac]-
[C4F7O2]-

[ClO4]-

[I]-

[Br]-
[Br]-

[Tf2n]-

[Cl]-
[Ben]-
[AC]-

[NO3]-

[SbF6]-
[MeSO3]-

[DCA]-

(a) (b)
Fig. 2. The selectivity of different ionic liquids for ethanol/water system (a); Common logarithms of the solubility of different ionic liquids for water (b) at 298.15 K.

QFuel C% 3. Modeling and simulation

[CO2 ] = ( )( )α (8)
NHV 100
3.1. Selection of entrainer
where QFuel is the total heat released by fuel combustion, (kW). C% is
the carbon content in the fuel. NHV is the net heating value with unit
3.1.1. Screening of traditional organic solvents
mass fuel combustion. α is the ratio of molar molecular mass of CO2 and
For extractive distillation, the selection of solvent is very important.
C12, and the value is 3.67.
The high-performance solvent can effectively decrease the process en­
In the distillation system, superheated steam is used either for indi­
ergy consumption and TAC [33,34], and thus the selection of entrainer
rect heating purposes or as a direct stripping medium. Superheated
has attracted more attention. The relative volatility is an important
steam is usually produced by burning fossil fuels in a boiler. In this work,
criterion for the initial selection of entrainer [35]. In order to select the
heavy fuel oil is assumed to supply stream heat. The NHV and C% values
most suitable solvent, five common used solvents (i.e., DMSO, EG, N,N-
of heavy fuel oil are 39771 kJ/kg and 86.5, respectively. QFuel is
dimethylformamide (DMF), dimethylacetamide (DMAC) and N-Methyl
calculated by
pyrrolidone (NMP)) were selected as candidate entrainers. The effects of
QFuel =
QProc
(hProc − 419)
TFTB − T0
(9) different solvents on the vapor-liquid equilibrium (VLE) for methanol/
λProc TFTB − TStack ethanol, methanol/water and ethanol/water systems were studied using
where QProc is the heat duty of reboiler. λProc (kJ/kg) and hProc (kJ/ Aspen Plus software (Fig. 1). Each solvent can make the azeotrope
kg) are the latent heat and enthalpy of utility steam. TFTB, TStack and T0 disappear, but EG has the best effect on the relative volatility under the
are the flame temperature of the boiler, the stack temperature, and the same solvent feed flow. Therefore, EG was selected as entrainer to
environmental temperature, respectively. For the boiler feed water, the separate methanol/ethanol/water ternary mixture in this study.
input temperature and enthalpy values of 373.15 K and 419 kJ/kg were
adopted. 3.1.2. Screening of ionic liquids
The selectivity of solvents is defined as the ratio of infinite dilution
activity coefficients of i component and j component [36].
γ∞
Sij∞ = i
(10)
γ∞
j

The suitability capacity of solvent is defined as [28]

1
∞
Cj,solvent = (11)
γ∞
j

In most cases, selectivity and solubility may exhibit opposite trends.

That is, if the solvent has a high selectivity for the separation, the sol­
ubility may be low. Hence, a suitable entrainer should make a balance
between these two factors. For the ternary system of low-carbon alco­
hols, the entrainer should not have a negative effect on the separation of
non-azeotropic components in addition to meeting the above re­
quirements for azeotropic composition.
As an efficiently priori thermodynamic model irrespective of exper­
imental data, the COSMO-RS model has received wide attention for
predicting some important thermodynamic properties (e.g., phase
equilibrium, vapor pressure, gas solubility, and activity coefficient) of
the binary and ternary mixture systems. Hence, the selectivity and sol­
ubility of ionic liquids for ethanol/water were studied using COSMO-RS
model [37–39] in this work. The results showed that both selectivity and
Fig. 3. The relative volatility of ethanol (1)-water (2) using solubility were mainly affected by anions of ionic liquids (Fig. 2).
different extractant.

4
G. Li et al.
Fig. 4. The flowsheet and optimal operating conditions of CETD with EG as single entrainer. (Streams are in mole fraction.)
Combining selectivity and solubility, ionic liquids containing [Ac]− ,
[MeSO3]− , [NO3]− and [DCA]− were selected. However, ionic liquids
containing [Ac]− are easily decomposed when heated [40,41]. Ac­
cording to Fig. 2(a), it is found that the selectivity of 1-ethyl-3-methyl­
imidazolium methanesulfonate ([EMIM][MeSO3]), 1-ethyl-3-
methylimidazolium nitrate ([EMIM][NO3]) and 1-Ethyl-3-methylimida­
zolium dicyanamide ([EMIM][DCA]) is stronger than other ionic liq­
uids. However, the melting point (311 K) of [EMIM][NO3] is relatively
high [42], while the viscosity (205.2 cP at 293.15 K) of [EMIM][MeSO3]
is very high [43,44], which limits their industrial application. The
selectivity of methanol to water in [EMIM][DCA] was 1.35 as predicted
by the COSMO-RS model, indicating that [EMIM][DCA] was conducive
to the separation of methanol and water. In this work, [EMIM][DCA]
was selected as the entrainer with the following good physical properties
as well: low melting point (252 K) [45], high decomposition tempera­
ture (569.7 K) [46], low density (1.08 g/cm3) [46] and low viscosity (17
cP at 298.15 K) [47].
It can been seen from Fig. 3 that both [EMIM][DCA] and EG can
make the azeotropic point of the ethanol–water system disappear (α12＞
1 at x1 = 0.9). Furthermore, the effect of [EMIM][DCA] on relative
volatility is greater than that of EG at x1 = 0.9. Therefore, both organic
solvents and ionic liquids can promote alcohol-water separation.
3.2. Process design
Aspen Plus (V10.0) was applied to explored the process of combined
EDWC with the mixture of ionic liquids and traditional organic solvents
as entrainer. The UNIFAC-Lei model [48,49], where the binary inter­
action parameters are given in Tables S1-S3 in Supporting Information,
was used to describe the phase behavior of the system. The fresh feed
flow rate is set at 100 kmol/h with the composition (mole fraction) of
17.3% methanol, 75.2% ethanol, and 7.5% water. All the column
pressure is 1 atm, and the pressure drop is 0.0068 atm. RadFrac module
is used for the extractive distillation column (EDC), conventional
distillation column (CDC), solvent recovery column (SRC), main column
(MC) and side column (SC). Flash module is used to simulate flash tank.
5
Separation and Purification Technology 269 (2021) 118713
Pump module is used for the transfer pump and Heater module is used
for the heat exchanger.
3.2.1. CTED using EG as entrainer
For the separation of low-carbon alcohol ternary system, the con­
ventional ternary extractive distillation process (CTED) includes an
extractive distillation column (EDC), a conventional distillation column
(CDC) and a solvent recovery column (SRC), as shown in Fig. 4. The low-
carbon alcohol mixture of methanol/ethanol/water system and the
solvent are sent to EDC. The introduction of entrainer leads methanol
and ethanol together moving to the top of EDC, water and entrainer
together flowing to the bottom of EDC. The methanol and ethanol
mixture obtained at the top of EDC are then sent to CDC. Methanol
product with high purity is produced in the overhead distillate and
anhydrous ethanol can be produced at the bottom of the CDC. The
bottom obtained stream at EDC containing water and entrainer are sent
into SRC to recovery the entrainer. At the top of the SRC water con­
taining impurities is produced, and the entrainer is regenerated at the
bottom and then is recycled back to EDC. In order to make up for the loss
of trace entrainer in the distillate streams of CDC and SRC, a small
amount of fresh entrainer supplement stream was added. For the con­
ventional ternary extractive distillation process (CTED), the design
variables including the number of the theoretical stages (NT1), fresh feed
stage (NF1), entrainer feed stage (NFE1) and entrainer flow rate (EF1) of
the extractive distillation column (EDC); the number of the theoretical
stages (NT2) and feed stage (NF2) of the conventional distillation column
(CDC); and the number of the theoretical stages (NT3) and feed stages
(NF3) of the solvent recovery column (SRC). For the CTED optimization,
the sequential iterative optimization procedure is shown in Figure S1 in
Supporting Information, and Fig. 4 shows the flowsheet of CTED with EG
as a single entrainer under optimal operating conditions based on
minimum TAC.
Fig. 5 shows the profile of liquid composition in three different col­
umns of CTED process using EG as single entrainer. In EDC, the
composition of ethanol reaches the maximum value during the stripping
process, and then decreases to the bottom of the column, which indicates
G. Li et al. Separation and Purification Technology 269 (2021) 118713

1.0 1.0
(a) Methanol (b)
Ethanol
0.8 Water 0.8
EG Methanol
Ethanol
Water

x (mole fraction)
x (mole fraction)

0.6 0.6 EG

0.4 0.4

0.2 0.2

0.0 0.0
0 5 10 15 20 25 30 0 5 10 15 20 25 30 35 40 45 50 55 60
Stage of EDC Stage of CDC

1.0
(c)

0.8
Methanol
x (mole fraction)

Ethanol
0.6 Water
EG

0.4

0.2

0.0
0 2 4 6 8 10 12 14 16 18 20
Stage of SRC
Fig. 5. The profile of liquid composition in the CTED process using EG as single entrainer.

that there is a remixing effect in the EDC. The composition of the CDC
and SRC is normal. In the CDC, the light component (methanol) is
enriched to the top of the column, and the heavy component (ethanol) is
enriched to the bottom of the column. In the SRC, the light component
(water) is concentrated toward the top of the column, and the heavy
component (EG) is concentrated toward the bottom of the column.
3.2.2. CTED using ionic liquids as entrainers
Based on the same exploration method, the CTED process using the
green solvent ([EMIM][DCA]) as single entrainer was explored. It is
worth mentioning that the CETD process using [EMIM][DCA] as the
entrainer includes an EDC, a CDC and a Flash tank (Flash 1), as shown in
Fig. 6. In this process, only one vacuum flash tank is needed to regen­
erate the entrainer [EMIM][DCA]. The separation process of the mixture
in EDC and CDC is the same as the CETD process with EG as single
entrainer. The bottom stream of the EDC containing [EMIM][DCA] and
water is sent to the flash tank. After a flash evaporation operation, the
[EMIM][DCA] with high-purity (>99.99% in mole fraction) is recovered
at the bottom of the flash tank and recycled back to the top of the EDC.
The impurities (i.e., water, ethanol, and trance methanol) are produced
at the top of the flash tank. Also, a small amount of entrainer supple­
mentary stream was added to make up for the loss of trace entrainer in
the CDC and Flash distillate streams. Fig. 6 shows the optimal operating
conditions of CETD with [EMIM][DCA] as single entrainer on the basic
of the minimum TAC, which are obtained using the sequential iterative
optimization procedure as the same as EG process (Figure S2).
The liquid composition profile in two different columns of the CTED
process using [EMIM][DCA] as a single entrainer is shown in Fig. 7. As in
the CTED process with EG as the single entrainer, the composition of
ethanol in EDC reaches the maximum value during the stripping process
and then decreases to the bottom of the column, which indicates that
there is a remixing effect in EDC. For the composition of CDC is normal,
the light component (methanol) is enriched to the top of the CDC. The
heavy component (ethanol) is enriched toward the bottom of CDC.
3.2.3. CTED using ionic liquids-based mixed solvent as entrainer
In terms of Fig. 3 that both [EMIM][DCA] and EG can make the
azeotropic point of the ethanol–water system disappear (α12＞1 at x1 =
0.9). The appropriate solvent ratio will affect the TAC of the whole
process. Different from the CTED using single solvent, the CTED with
mixed solvents need to determine the optimal ratio of mixed solvents
beforehand. Based on the optimization sequence shown in Figure S3
(Support Information), the separation process of mixed solvents with
different proportions was optimized by taking the amount of single
solvent as the initial value. Due to the large relative molecular weight
and high boiling point of the ionic liquid, the larger the proportion in the
mixed solvents, the higher the heat duty at the bottom of the SRC, and
the required operating costs will be very large. Therefore, only the cases,
where the mole fraction of [EMIM][DCA] in the mixed solvent is less
than 60%, are considered.
The optimum mixed entrainer (EG 70% + [EMIM][DCA] 30%)
composition ratio can be determined according to Fig. 8. The process of

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G. Li et al. Separation and Purification Technology 269 (2021) 118713

64.6 oC
75.1 oC
1786.32 kW
1982.57 kW 8.6591 kmol/h
2 2
0.1364 [EMIM][DCA]
22.8409 kmol/h
Ⅰ 0.8628 Water
0 [EMIM][DCA]
3 92.5 kmol/h 0.0001 Methanol
0.0001 Water
trace [EMIM][DCA] 0.0007 Ethanol
0.9950 Methanol
0.0001 Water
Ⅱ 0.0049 Ethanol
0.1870 Methanol
0.8129 Ethanol
1.1591 kmol/h EDC 20
1 [EMIM][DCA] 25 oC
15 CDC
ID1=1.06m ID2=0.97m 950.86 kW
100 kmol/h Flash 1
RR1=1 RR2=9.52 0.05 atm
0.075 Water Ⅲ 221.85 oC
0.173 Methanol 525.38 kW
0.752 Ethanol 22 54
75.181 kmol/h
0 [EMIM][DCA] 22.8409 kmol/h
175.3 C o 31.5 kmol/h o
78.3 C
0.0001 Water 0.9999 [EMIM][DCA]
2890.11 kW 0.7620 [EMIM][DCA] 1790.10 kW
0.0009 Methanol 0.0001 Water
0.2379 Water
0.9990 Ethanol trace Methanol
trace Methanol
trace Ethanol
0.0001 Ethanol

Fig. 6. The flowsheet and optimal operating conditions of CETD with [EMIM][DCA] as single entrainer. (Streams are in mole fraction.)

1.0 1.0
(a) (b)

0.8 0.8
Methanol
x (mole fraction)

Ethanol
x (mole fraction)

0.6 0.6 Water

Methanol
Ethanol
Water
0.4 [EMIM][DCA] 0.4

0.2 0.2

0.0 0.0
0 4 8 12 16 20 24 0 5 10 15 20 25 30 35 40 45 50 55 60
Stage of EDC Stage of CDC

Fig. 7. The profile of liquid composition in the CTED process using [EMIM][DCA] as single entrainer.

using mixed solvent is the same as the process of using single solvent EG,
which mainly includes three columns of EDC, CDC and SRC. The flow­
sheet with optimal operating parameters is demonstrated in Fig. 9.
Additional solvents are applied to balance the micro loss of entrainers in
the triple-column distillation process. Fig. 10 shows the liquid compo­
sition profile in the three columns using mixed entrainer (70% EG +
30% [EMIM][DCA], in mole fraction). The ethanol in the EDC first in­
creases and then decreases, which means that remixing occurs. The final
separation purity of EG and [EMIM][DCA] in SRC reached 99.99%.
3.2.4. EDWC-TED using the mixture of ionic liquids and EG as entrainer
A traditional CTED process (as shown in Fig. 9) mainly consists of
one EDC, one CDC and one SRC, and there is a condenser and a reboiler
for each column. When evaluating the process performance of different
configurations, it is necessary to control the proportion of mixed sol­
vents to be equal. Therefore, the mixed solvent (EG 70% + [EMIM]
[DCA] 30%) is used for EDWC-TED process and CTED process. On the
basis of the optimization process of CTED using mixed solvent, the novel
energy-saving technology of extractive dividing wall column ternary
extractive distillation (EDWC-TED), where the EDC and SRC were
coupled, was explored to further reduce the energy consumption and
investment cost. In this work, the EDWC-TED was modeled using the
twin column model, which has been widely adopted for the simulation
of thermally coupled ternary extractive distillation [22–24,50], repre­
sented by a main column (MC) attached with a side column (SC). Similar
to the CTED processes, the mixed entrainer is introduced into the MC at
the upper section and the methanol/ethanol/water ternary mixture is
fed at the middle part. At the lower section of the MC partial vapor
mainly containing water and EG is drawn out and enters into the bottom
of SC, where the heat of the stream itself can be utilized to separate the
mixture and the reboiler is not needed anymore. At the top of SC water is
obtained and the entrainer in liquid phase is sent back into MC. At the
top of MC the methanol and ethanol mixture can be obtained and then
sent to CDC as the same as in CTED process. Different from CTED, in

7
G. Li et al.
17.0
TAC (×105$/year)
16.5
16.0
15.5
40 50 60 70 80
Mole fraction of EG in mixed entrainer (%)
Fig. 8. The relationship between TAC of the extractive distillation process and
different mixed solvent ratios.
EDWC-TED process, two more variables (i.e., the side-extraction posi­
tion and the flow rate) need to be considered. Thus, for the EDWC-TED,
the design variables including the number of the theoretical stages
(NT1), ternary mixture feed stage (NF1), entrainer feed stage (NFE1) and
entrainer flow rate (EF1), the side-extraction stage (NSE) and flow rate
(FR) of MC; the number of the theoretical stages (NT3) of SC, and the
number of the theoretical stages (NT2) and feed stage (NF2) of the CDC.
For the process optimization of EDWC-TED, the sequential iterative
optimization process is shown in Figure S4, and the optimal operating
parameters of EDWC-TED process with ionic liquids-based mixed
entrainer is demonstrated in Fig. 11.
The profile of liquid composition in the three columns of the EDWC-
TED process using mixed solvents (70% EG + 30% [EMIM][DCA]) is
shown in Fig. 12. The CDC obtained methanol with purity of 99.5% and
ethanol with purity of 99.9%. EG in SC finally flows back to MC from the
bottom of the SC.
Fig. 9. The flowsheet and optimal operating conditions of CETD using [EMIM][DCA] and EG as mixed entrainer. (Streams are in mole fraction.)
Separation and Purification Technology 269 (2021) 118713
4. Results and discussion
4.1. Effect of relative volatility on process energy saving
In the extractive distillation process, changing the relative volatility
of the mixed composition is the first step to achieve energy saving in the
process. Fig. 13 shows the relative volatility changes on different trays of
the extractive distillation column during the extractive distillation pro­
cess with different entrainers configurations under the optimal oper­
ating conditions. It can be seen from Fig. 13(a) and (b) that the relative
volatility of the mixed components changes more obviously when using
the green solvent ionic liquid as single entrainer than using EG as single
entrainer, showing the great potential of using ionic liquids as en­
trainers. Fig. 13(c) shows the relative volatility change in the extractive
90 distillation column of the CTED process using mixed entrainer (70% EG
+ 30% [EMIM][DCA]). Although the relative volatility change of the
process is slightly lower than that of the CTED process using single ionic
liquid as entrainer, the relative volatility of the process is greatly
improved when compared to the CTED process using single EG as
entrainer. Fig. 13(d) shows the change of relative volatility in MC of
EDWC-TED process using ionic liquid and EG mixed entrainer, consis­
tent with that in Fig. 13(c).
4.2. Process performance evaluation
Generally speaking, the usage of traditional organic solvents would
have higher environmental burdens, while the usage of ionic liquids
would undertake higher capital cost due to their high price. In this work,
we go a further step to make a quantitative comparison among the above
mentioned four processes (CTED using single entrainer (EG or [EMIM]
[DCA]), CTED using EG + [EMIM][DCA] mixed entrainer, and EDWC-
TED using EG + [EMIM][DCA] mixed entrainer) in terms of TAC, CO2
emission and thermodynamic efficiency. Fig. 14 shows the process
performance analysis of different configurations, and the detailed values
can be seen in Tables S4 and S5 in Supporting Information.
Fig. 14(a) and (b) show the economic performance and energy
8
G. Li et al. Separation and Purification Technology 269 (2021) 118713

1.0 1.0
(a) (b)

0.8 0.8
Methanol

x (mole fraction)

x (mole fraction)
0.6 0.6 Ethanol
Methanol Water
Ethanol [EMIM][DCA]
0.4 Water 0.4 EG
[EMIM][DCA]
EG
0.2 0.2

0.0 0.0
0 2 4 6 8 10 12 14 16 18 20 22 0 5 10 15 20 25 30 35 40 45 50
Stage of EDC Stage of CDC

1.0
(c)

0.8
(mole fraction)

0.6 Methanol
Ethanol
Water
0.4 [Emim][DCA]
EG
x

0.2

0.0
0 2 4 6 8 10 12 14 16 18 20
Stage of SRC

Fig. 10. The profile of liquid composition in the CTED process using [EMIM][DCA] and EG as entrainer.

92.5 kmol/h
74.3 oC 10ppm EG
trace [EMIM][DCA] 64.6 oC
1490.67 kW
0.0006 Water
0.006 kmol/h 0.1870 Methanol 1855.07 kW
1 EG 0.8123 Ethanol
2 2
o
I 97.4 C 17.36 kmol/h
475.05 kW trace EG
3
trace [EMIM][DCA]
2 trace Water
II
7.506 kmol/h 0.9953 Methanol

ID1=1.11 m
SC 0.0001 EG 0.0047 Ethanol
100 kmol/h 11 trace [EMIM][DCA] 23
RR1=0.5
0.075 Water 0.9923 Water
MC CDC ID2=0.99 m
0.173 Methanol trace Methanol
III 8 RR2=9.9
0.752 Ethanol 0.0076 Ethanol
27
25 oC
IV
683.65 kW
ID3=0.44 m 45
31
37.994 kmol/h RR3=4.5
0.6999 EG 75.14 kmol/h
213.9 oC 78.3 oC 10ppm EG
0.3000 [EMIM][DCA]
2827.68 kW 1861.39 kW trace [EMIM][DCA]
0.0001 Water
trace Methanol 0.0007 Water
trace Ethanol 0.0002 Methanol
0.9990 Ethanol

Fig. 11. The flowsheet and optimal operating conditions of EDWC-TED with [EMIM][DCA] and EG as mixed entrainer. Streams are in mole fraction.

9
G. Li et al. Separation and Purification Technology 269 (2021) 118713

1.0 1.0
(a) Methanol
Ethanol (b)
Water
0.8 0.8
[Emim][DCA]
Methanol
EG

x (mole fraction)

x (mole fraction)
Ethanol
0.6 Water
0.6
[Emim][DCA]
EG

0.4 0.4

0.2 0.2

0.0 0.0
0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35 40 45 50
Stage of EDC Stage of CDC

1.0
(c)

0.8
x (mole fraction)

Methanol
0.6 Ethanol
Water
[Emim][DCA]
0.4 EG

0.2

0.0
0 1 2 3 4 5 6 7 8 9
Stage of SC

Fig. 12. The profile of liquid composition in the EDWC-TED process using [EMIM][DCA] and EG as mixed entrainer.

5 6
(a) (b) α Methanol-Water
α Methanol-Water
α
α 5 Ethanol-Water
4 Ethanol-Water
α Methanol-Ethanol
Relative volatility (α )

α Methanol-Ethanol
Relative volatility (α )

4
3
3
2
2

1
1
I II III I II III
0 0
0 4 8 12 16 20 24 28 32 0 4 8 12 16 20 24
Stage of EDC Stage of EDC

6 6
(c) α (d) α Methanol-Water
Methanol-Water
α α
5 Ethanol-Water 5
Ethanol-Water

α α Methanol-Ethanol
Methanol-Ethanol
Relative volatility (α )

Relative volatility (α )

4 4

3 3

2 2

1 I II III 1
I II III IV
0 0
0 2 4 6 8 10 12 14 16 18 20 22 0 4 8 12 16 20 24 28 32
Stage EDC Stage of MC

Fig. 13. The relative volatility of different tray positions in extractive distillation column with different entrainer processes, CTED using EG as entrainer (a); CTED
using [EMIM][DCA] as entrainer (b); CTED using EG + [EMIM][DCA] as entrainer 10 (c); EDWC-TED using EG and [EMIM][DCA] as entrainer (d).
G. Li et al.
Fig. 14. Process performance analysis of different configuration TAC (a); Qtotal (kW) (b); thermodynamic efficiency (η) (c); CO2 emissions (d).
consumption of different process configurations. The CTED using EG as
single entrainer was chosen as the benchmarked process. For the CTED
using [EMIM][DCA] process, only requires two columns and one flash
tank to complete the separation requirements. Thus, it can make a
reduction on the operating costs and equipment costs of CTED using
ionic liquids when compared to the benchmarked process. It should be
noting that the entrainer cost was not considered during the estimation
of TAC. The use of mixed entrainer can further reduce the TAC and
energy consumption by about 5.98% and 2.93%, respectively. The new
proposed CTED process with ionic liquid and EG mixed solvent as
entrainer requires the lowest TAC and energy consumption by saving
7.81% and 4.52%. Therefore, the process using mixed entrainer based
on ionic liquids can effectively decrease TAC and energy consumption.
EDWC has obvious advantages in equipment investment and operation
cost, which lays a theoretical foundation for its further commercial
application.
Fig. 14(c) and (d) show the thermodynamic efficiency (η) and CO2
emissions for different processes, exhibiting reverse trends. That is, the
lower the thermodynamic efficiency, the higher the CO2 emissions.
When compared to the benchmarked process, the use of the mixed
entrainer can reduce the CO2 emissions from 1660.17 to 1611.48 kg/h.
Using EDWC-TED the CO2 emissions can be further reduced by 4.52%.
Generally, the thermodynamic efficiency of distillation column is about
10% [15]. However, ethanol and water can form binary azeotrope, and
ethanol and methanol are close-boiling mixture. Thus, for the separation
of methanol/ethanol/water ternary system, not only efficient entrainer
is needed, but also plenty of thermal energy is required. The thermo­
dynamic efficiency of all processes in this study is less than 10%.
Moreover, the thermodynamic efficiency of EDWC-TED using mixed
entrainer is the highest due to the efficient utilization of stream latent
heat at the bottom of MC, improving by 82.86% when compared to the
11
Separation and Purification Technology 269 (2021) 118713
benchmarked process. This demonstrates that the EDWC-TED using
mixed solvents has the high thermodynamic efficiency as well as the
significant advantages in economy and environment.
5. Conclusion
This research focuses on the process intensification of combining an
ionic liquids-based mixed entrainer with a dividing wall column for
methanol/ethanol/water ternary extractive distillation separation pro­
cess. TAC, thermodynamic efficiency, and CO2 emissions of CTED and
EDWC-TED processes based on the mixed entrainer of ionic liquids are
calculated from the perspective of economy, energy efficiency and
environmental effect. When compared to CTED using mixed entrainer
and single entrainer, the process using ionic liquids-based mixed
entrainer has good performance in changing the relative volatility of
mixed alcohol ternary azeotropic system, and has significant advantages
in energy saving and economy. CTED process using the mixed entrainer
can reduce the TAC by about 5.98% and the energy consumption by
2.93%. The remixing effect of EDC is the main factor affecting energy
consumption. The DWC reduces the remixing effect of the azeotropic
composition, thereby reducing the process energy consumption and
operating costs. EDWC-TED using the ionic liquids-based mixed
entrainer is the most energy-saving process and has significant economic
and environmental advantages. The TAC and energy consumption are
reduced by 7.81% and 4.52%, respectively. EDWC process is a produc­
tion scheme superior to CDC process in terms of economy, energy saving
and environmental protection. As an important energy-saving technol­
ogy, the commercial promotion and application of the EDWC using ionic
liquids-based mixed entrainer has important development prospects.
G. Li et al.
CRediT authorship contribution statement
Guoxuan Li: Methodology, Investigation, Writing - original draft.
Shengli Liu: Data curation. Gangqiang Yu: Writing - review & editing.
Chengna Dai: Supervision, Methodology, Writing - review & editing.
Zhigang Lei: Supervision, Project administration, Writing - review &
editing.
Declaration of Competing Interest
None.
Acknowledgements
This work is financially supported by the National Natural Science
Foundation of China under Grant (No. U1862103).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.seppur.2021.118713.
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