Chemical Engineering Research and Design 184 (2022) 402–418

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Chemical Engineering Research and Design

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Deep eutectic solvents as entrainers in extractive

distillation – A review
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⁎
Maximilian Neubauer, Thomas Wallek, Susanne Lux
Graz University of Technology, Institute of Chemical Engineering and Environmental Technology, NAWI Graz,
Inffeldgasse 25C, 8010 Graz, Austria

a r t i c l e i n f o a b s t r a c t

Article history: One of the most common techniques for separating azeotropes and close-boiling mixtures
Received 13 April 2022 is extractive distillation, where the relative volatility of the components to be separated is
Received in revised form 31 May altered by adding an entrainer. In recent years, deep eutectic solvents have emerged as a
2022 new class of entrainers in extractive distillation. Similar to the related class of ionic li­
Accepted 10 June 2022 quids, deep eutectic solvents combine the high separation capability of solid salts with the
Available online 14 June 2022 simple handling of liquids, additionally exhibiting low to negligible vapour pressures and
non-flammability. Compared to ionic liquids, deep eutectic solvents offer advantages in
Keywords: terms of toxicity issues but also solvent costs. In this review, the current state of research
Extractive distillation regarding deep eutectic solvents in extractive distillation spanning from vapour-liquid-
Azeotropes equilibrium measurements and thermodynamic modelling of the corresponding systems
Deep eutectic solvents to general entrainer feasibility considerations and process simulations is presented and
Vapour-liquid-equilibrium critically evaluated. Additionally, future prospects and comments on unresolved issues
measurements are provided.
Process simulation © 2022 The Authors. Published by Elsevier Ltd on behalf of Institution of Chemical
Engineers.
CC_BY_4.0

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
1.1. Extractive process feasibility assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
1.2. Process synthesis, design, optimization and control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
2. History and current state of research. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
2.1. VLE measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
2.1.1. Ethanol – water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
2.1.2. IPA – water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407
2.1.3. Other systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
2.2. Process simulations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
3. Evaluation of the current state of research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
3.1. Screening and modelling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
3.2. Process simulations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411
3.3. Entrainer feasibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 412
3.3.1. Miscibility gaps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 412
3.3.2. Thermal stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413
3.3.3. Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413

⁎
Corresponding author.
E-mail address: susanne.lux@tugraz.at (S. Lux).
https://doi.org/10.1016/j.cherd.2022.06.019
0263-8762/© 2022 The Authors. Published by Elsevier Ltd on behalf of Institution of Chemical Engineers.
CC_BY_4.0
 Chemical Engineering Research and Design 184 (2022) 402–418 403

3.4. Comparison with other solvent types. . . . . . 413

Nomenclature
3.4.1. Minimum amounts . . . . . . . . . . . . . . 414
General 3.4.2. Price . . . . . . . . . . . . . . . . . . . . . . . . . . 414
BOD biological oxygen demand 4. Conclusion and future prospects . . . . . . . . . . . . . . 415
DES deep eutectic solvents Declaration of Competing Interest . . . . . . . . 415
HBA hydrogen-bond acceptor Acknowledgement . . . . . . . . . . . . . . . . . . . . . 415
HBD hydrogen-bond donor Appendix A Supporting information. . . . . . . 415
ILs ionic liquids References . . . . . . . . . . . . . . . . . . . . . . . . . . . 415
NADES natural deep eutectic solvents
NMR nuclear magnetic resonance
NRTL Non-Random-Two-Liquid
TAC total annualized cost 1. Introduction
UNIFAC Universal Quasichemical Functional Group
Activity Coefficients “It may form an azeotrope” – a sentence chemical engineers
UNIQUAC Universal Quasichemical normally do not like to hear. And it is hardly surprising, since
VLE vapour-liquid-equilibrium the separation of azeotropes is technically more challenging
and energy intensive as opposed to the zeotropic case.
Deep eutectic solvent components Numerous techniques have been developed to separate
CC choline chloride azeotropic mixtures, including membrane and special dis­
EG ethylene glycol tillation processes like pressure swing distillation, hetero­
G glycerol azeotropic rectification and extractive distillation (Chen
GA glycolic acid et al., 2005; Mahdi et al., 2015). In extractive distillation, an
IPA 2-propanol additional component, the so-called entrainer, is added to
LA lactic acid the mixture to be separated. The task of the entrainer is to
LVA levulinic acid alter the relative volatilities of the mixture components by
MA malic acid different interactions with them, in order to eliminate the
MCA malonic acid azeotropic point and make separation feasible. Since an op­
TBAB tetrabutylammonium bromide timized process design utilizing an average entrainer may be
TEG triethylene glycol much more expensive than an average design utilizing the
TMAC tetramethylammonium chloride optimal entrainer, the choice of the entrainer is a critical step
Ur Urea (Laroche et al., 1991). Up to now, four classes of entrainers are
known: conventional liquids, solid salts, mixtures of con­
Ionic liquids ventional liquids with solid salts, and ionic liquids (ILs). A
[Bmim] 1-butyl-3-methylimidazolium short description listing advantages and disadvantages ac­
[Emim] 1-ethyl-3-methylimidazolium cording to Lei et al. (2003) is shown in Table 1.
[EMpy] 1-ethyl-3-methylpyridinium When using conventional liquids as entrainers, large
[MEA] 2-hydroxy-ethylammonium amounts are needed (entrainer/feed mass ratios up to 5 – 8).
[BF4] tetrafluoroborate Still, conventional liquid entrainers are widely utilized in
[Br] bromide industry, simply owing to the easy handling and operation of
[Cl] chloride liquids when compared to solid salts or solids in general (Lei
[EtSO4] ethylsulphate et al., 2003). Extractive distillation with ionic liquids (ILs) is
[hexanoate] hexanoate also feasible (Lei et al., 2003, 2014). ILs have received con­
[N(CN)2] dicyanamide siderable attention in recent years, seen by many as solvents
[OAc] acetate of the future (Earle and Seddon, 2000; Rogers and Seddon,
[OTf] trifluoromethanesulfonate 2003). However, many aspects of ILs have been brought into
question lately, such as the costly production as well as
Symbols possible toxicity and biodegradability issues, latter especially
∞ infinite dilution concerning imidazolium-based and fluorinated ILs (Kunz and
C capacity Häckl, 2016; Chen and Mu, 2021; Kudłak et al., 2015; Zhao
K vapour-liquid distribution ratio et al., 2007). Deep eutectic solvents (DES) are a relatively new
P pressure class of entrainers in extractive distillation. The connection
P0 pure component vapour pressure between DES and extractive distillation was first made in
S selectivity 2014 by Rodríguez et al. (2015), even though DES are known
T temperature since 2003.
w mass fraction In 2003, Abbott et al. (2003) first came up with the term
x mole fraction liquid phase “deep eutectic solvent”, when discovering unusually deep
x' mole fraction liquid phase on entrainer free melting point depressions in choline chloride/urea mixtures.
basis Since then, substantial research has been devoted to this
y mole fraction vapour phase topic, with an increasing trend observable, as shown in Fig. 1.
α relative volatility Yet, the term DES is often vaguely defined and no gen­
γ activity coefficient erally accepted definition exists. One common definition for
η dynamic viscosity DES is that they result from the combination of a hydrogen-
bond donor (HBD) and hydrogen-bond acceptor (HBA) to form
an eutectic mixture with unusually deep melting points
404 Chemical Engineering Research and Design 184 (2022) 402–418

Table 1 – Advantages and disadvantages of different entrainer classes (Lei et al., 2003)
Entrainer Advantages Disadvantages

Liquids (“traditional
organic solvents”)
Solid salts
Liquid + solid salt
Ionic liquids
+ easy handling and operation
+ high separation capability, small amounts
needed
+ non-volatile, no contamination of overhead
product
+ easy handling and operation of liquids
combined with high separation capability of solid
salts
+ easy handling and operation of liquids
combined with high separation capability of solid
salts
+ non-volatile, no contamination of overhead
product
- low separation capability, large amounts needed
- possible contamination of overhead product
- solids handling: dissolution and transport issues
- corrosion
- solubility of solid salts in liquid solvents often limited,
low number of systems where application possible
- possible contamination of overhead product
- often complex synthesis
- high price
- often toxicity issues

flammability is also a beneficial property of DES (Ramón and

Fig. 1 – Number of publications over the years, data
generated with results count for "deep eutectic solvent" in
Web of Science.
(Hansen et al., 2021; Smith et al., 2014; El Achkar et al., 2021).
A prominent example is the combination of choline chloride
and urea, both solids at room temperature, as reported by
Abbott et al. (2003). When brought into contact, a liquid at
room temperature is obtained. However, this definition of
DES is not satisfactory from a scientific point of view, and
some researchers have called for a stricter definition of DES,
especially concerning the term “deep”. Martins et al. (2019)
propose to define a “deep eutectic” as a mixture of pure
components where the eutectic temperature is lower than in
an ideal mixture. Accordingly, the melting point depression
should then be defined as the difference between real and
ideal eutectic point. For further information on the history,
definition and properties of DES, the reader is referred to the
abundant literature available (Hansen et al., 2021; Smith
et al., 2014; El Achkar et al., 2021; Martins et al., 2019; Ramón
and Guillena, 2019; Marcus, 2019; Liu et al., 2015; Warrag and
Kroon, 2019; Francisco et al., 2013; Płotka-Wasylka
et al., 2020).
Coming back to extractive distillation - what makes DES
interesting for this application? Similar to ILs, DES combine
the easy handling and operation of liquids with the high
separation capability of solid salts due to their partly ionic
nature while exhibiting low to negligible vapour pressures
(Shahbaz et al., 2016). Latter is desirable in the entrainer re­
generation step of the extractive distillation process in terms
of energy demand, furthermore solvent loss and emissions
are minimized. In contrast to volatile organic solvents, non-
Guillena, 2019; Marcus, 2019). Compared to ILs, DES have
several advantages. For one, the preparation is easy by
simply combining the starting materials with no further
purification required. This is usually achieved by mixing the
starting materials at elevated temperatures until a homo­
genous liquid is obtained. With the starting materials in
general being relatively cheap this keeps the price of DES
lower in comparison to ILs (Płotka-Wasylka et al., 2020;
Florindo et al., 2014). Concerning toxicity and biodegrad­
ability, DES are thought to be more environmentally friendly
than ILs (Kudłak et al., 2015; Płotka-Wasylka et al., 2020),
especially in the case of DES composed of primary metabo­
lites like amino acids, organic acids, sugars, or choline deri­
vatives, which are called natural deep eutectic solvents
(NADES) (Paiva et al., 2014).
The question is now: How can DES be integrated into the
framework of extractive distillation?
For an answer as coherent as possible it is beneficial to
give a short outline on this framework as described by
Gerbaud et al. (2019).
1.1. Extractive process feasibility assessment
The entrainer selection is a critical step in extractive dis­
tillation. One of the most widely used selection criteria is the
selectivity SAB which is derived from the relative volatility
yA
0
KA xA A PA
AB = = yB = 0 (1)
KB B PB
xB
presuming the validity of the simplified equilibrium condi­
tion yi P = x i i Pi0 . Under the assumption that the ratio of the
pure component vapour pressures for components A and B is
roughly constant for small changes in temperature, the re­
lative volatility is only influenced by introduction of an en­
trainer E which changes the ratio of the activity coefficients.
This ratio is defined as the selectivity SAB
AE
SAB = (2)
BE
For easier comparison and screening purposes often the
selectivity at infinite dilution is used
A
SAB = (3)
B
 Chemical Engineering Research and Design 184 (2022) 402–418
Another ranking criterion is the product of selectivity and
capacity at infinite dilution
P = SAB CBE (4)
where the capacity is given by
1 of the ethanol – water azeotrope. Four DES were tested with
CBE = (5)
B
This product, also termed solvent power, correlates better
with the total annualized cost (TAC) than the selectivity
alone as suggested by Kossack et al. (2007).
The minimum amount of entrainer needed to break the
azeotrope is also of interest. It is calculated as the amount
necessary above which the uni-volatility condition AB = 1
is eliminated on an entrainer-free base. Residue curve maps
are also a valuable tool in the feasibility assessment, where
the intersection point of the uni-volatility curve AB = 1 with
the triangle edge corresponds to the minimum amount of
entrainer needed (Gerbaud et al., 2019).
1.2. Process synthesis, design, optimization and control
After the feasibility assessment and entrainer selection,
process synthesis, design and optimization are carried out.
This includes column configuration and operation modes,
finding the optimal operating parameters and an appropriate
control structure as well as economic optimization. Since it
would be beyond the scope of this review, this will not be
covered in detail here and the reader is referred to the lit­
erature (Gerbaud et al., 2019). So as already asked above: How
can DES be integrated into the framework of extractive dis­
tillation? DES follow the same feasibility criteria and con­
siderations as for conventional extractive distillation with
heavy-boiling entrainers and therefore can be handled with
the literature available (Gerbaud et al., 2019). This means that
process flowsheets for extractive distillation with DES are
similar to flowsheets when using conventional solvents.
The differences lie in the availability and generation of
fundamental thermodynamic properties and, most im­
portantly, the application of predictive models (e.g. for the
calculation of activity coefficients at infinite dilution for
screening purposes). For most common organic solvents
these properties are readily available in databanks and
literature, or can be computed with relatively low effort
with existing predictive models, whereas for many DES the
data concerning basic properties is scarce and often not
available. However, this data is a prerequisite for feasibility
assessment and process design/simulation. Additionally,
taking into account the multitude of possible combinations
between DES constituents, which makes the experimental
determination of various parameters a tedious and time-
consuming procedure, the need for accurate and reliable
predictive models becomes obvious. These issues will be
discussed in detail later. First, in the following chapter the
history and current state of research concerning DES in
extractive distillation will summarized. Subsequently,
the current state of research will be critically evaluated,
followed by a conclusion and comments on the future
prospects of this topic. The aim of this paper is to provide a
comprehensive review on all aspects of DES as entrainers in
extractive distillation.
405
2. History and current state of research
Even though DES were first mentioned in 2003, the connec­
tion to extractive distillation was not made until 2014, when
Rodríguez et al. (2015) were the first to evaluate DES as po­
tential entrainers in extractive distillation for the separation
regard to the elimination of the azeotropic point. While lactic
acid (LA) – choline chloride (CC) (molar ratio 2:1) shifted the
azeotropic point towards the pure ethanol side, malic acid
(MA) – CC (1:1), glycolic acid (GA) – CC (3:1) and GA – CC (1:1)
were able to break the azeotrope (Rodríguez et al., 2015).
Since then a number of papers has been published, mainly
focusing on vapour-liquid-equilibrium (VLE) measurements
and thermodynamic modelling. Concerning process simula­
tion, very few papers exist to date.
This chapter is divided into two parts, VLE measurements
and process simulations. Although an experimental section
involving actual distillation with DES in columns would be of
interest, there exists only one paper who dealt with batch
extractive distillation in addition to a process simulation
investigation. Therefore, the only experiment of this kind to
date will be included in the process simulation section.
2.1. VLE measurements
To give an overview, a summary of azeotropic systems ex­
amined via VLE measurements is presented in Table 2.
Some general observations can be made. Firstly, it is
striking that the overwhelming majority of papers deals with
choline chloride-based DES. And secondly, about 60% of pa­
pers have been focusing on two systems: ethanol – water and
IPA – water. Therefore, these two systems will be discussed
separately while research regarding the other systems will be
summarized.
2.1.1. Ethanol – water
The industrially important ethanol – water system exhibits a
low-boiling azeotrope (351.3 K, 1 atm) at a composition of
89.7 mol% (95.7 wt%) ethanol (CRC Handbook of Chemistry
and Physics, 2016).
It was also the first system to be examined in extractive
distillation with DES by Rodríguez et al. (2015). They in­
vestigated four DES: LA – CC (2:1), MA – CC (1:1), GA – CC (3:1)
and GA - CC (1:1). LA – CC was not able to break the azeo­
trope, while the other DES successfully eliminated the
azeotropic point. A pseudo-pure component approach was
used for thermodynamic modelling, where each DES was
treated as one inseparable component. The non-random-
two-liquid (NRTL) model was used to correlate the VLE data
and obtain binary interaction parameters for pseudo-binary
water – DES respectively ethanol – DES systems. The pseudo-
ternary systems were then modelled with these parameters.
However, systematic errors were found for all systems,
which the authors ascribed to the non-consideration of
ternary interactions when using parameters obtained from
pseudo-binary systems (Rodríguez et al., 2015).
Gjineci et al. (2016) studied the separation of the ethanol –
water azeotrope with ILs and DES. The DES studied were urea
(Ur) – CC (2:1) and triethylene glycol (TEG) – CC (3:1), both
were found to eliminate the azeotropic point. VLE measure­
ments and biodegradability tests for biological oxygen de­
mand (BOD) via a VELP BOD manometric apparatus were
 406

Table 2 – Overview of azeotropic system - entrainer combinations investigated via VLE measurements, ratios in brackets represent molar ratios.
Azeotropic system Entrainer Subsystem VLE Entrainer Temperature [K] Pressure [kPa] Reference
Type fractions

Polar
ethanol - water lactic acid (LA) - choline chloride (CC) (2:1) ethanol - LA:CC (2:1) PT 10 – 20 mol% 292.84–351.40 5.01–101.45 Rodríguez et al., 2015
water - LA:CC (2:1) PT 10 – 20 mol% 313.82–372.60 6.29–99.95 (Rodríguez et al., 2015)
ethanol - water - LA:CC (2:1) Txy 20 mol% 351.11–371.47 100 (Rodríguez et al., 2015)
malic acid (MA) – choline chloride (1:1) ethanol - MA:CC (1:1) PT 10 – 20 mol% 291.72–351.00 4.90–99.71
water - MA:CC (1:1) PT 10 – 20 mol% 312.53–373.52 6.20–93.75 (Rodríguez et al., 2015)
ethanol - water - MA:CC (1:1) Txy 20 mol% 351.09–372.39 100 (Rodríguez et al., 2015)
glycolic acid (GA) – choline chloride (1:1) ethanol - GA:CC (1:1) PT 10 – 20 mol% 292.23–350.97 5.01–99.96 (Rodríguez et al., 2015)
water - GA:CC (1:1) PT 10 – 20 mol% 308.87–370.86 4.96–101.31 (Rodríguez et al., 2015)
ethanol - water - GA:CC (1:1) Txy 20 mol% 351.09–369.39 100 (Rodríguez et al., 2015)
glycolic acid – choline chloride (3:1) ethanol - GA:CC (3:1) PT 10 – 20 mol% 292.06–351.40 4.93–101.27 (Rodríguez et al., 2015)
water - GA:CC (3:1) PT 10 – 20 mol% 308.01–372.62 4.98–99.95 (Rodríguez et al., 2015)
ethanol - water - GA:CC (3:1) Txy 20 mol% 350.92–370.07 100 (Rodríguez et al., 2015)
urea (Ur) - choline chloride (2:1) ethanol - Ur:CC (2:1) Tx 0 – 60 wt% 351.45–357.55 101.3 (Peng et al., 2017)
water - Ur:CC (2:1) Tx 0 – 83 wt% 373.15–395.33 101.3 (Peng et al., 2017)
ethanol - water - Ur:CC (2:1) Txy 5–10 wt% 351.58–352.03 101.3 (Gjineci et al., 2016)
ethanol - water - Ur:CC (2:1) Txy 10–30 wt% 352.51–375.77 101.3 (Peng et al., 2017)
triethylene glycol (TEG) - choline chloride (3:1) ethanol - water - TEG:CC (3:1) Txy 5–15 wt% 351.73–352.28 101.3 (Gjineci et al., 2016)
ethylene glycol (EG) - choline chloride (2:1) ethanol - water - EG:CC (2:1) Txy 10–80 wt% 356.61–371.34 101.3 (Zhang et al., 2019)
methanol - ethanol - water - EG:CC (2:1) Txy 5 – 65 mol% 349.07–369.11 101.3 (Shu et al., 2020)
glycerol (G) - choline chloride (2:1) ethanol - G:CC (2:1) Txy 0 – 91 mol% 305.2–348.5 11.3 (Souza et al., 2021)
water - G:CC (2:1) Txy 0 – 79 mol% 321.5–348.5 11.3 (Souza et al., 2021)
ethanol - water - G:CC (2:1) Txy 50 mol% 306.0–337.3 11.3 (Souza et al., 2021)
ethanol - water - G:CC (2:1) Txy 10–80 wt% 352.10–378.50 101.3 (Li et al., 2021)
2-propanol (IPA) - water glycolic acid – choline chloride (3:1) IPA - GA:CC (3:1) PT 5 – 10 mol% 306.8–355.3 10–100 (Rodriguez and Kroon, 2015)
water - GA:CC (3:1) PT 5 – 10 mol% 319.7–372.8 10–100 (Rodriguez and Kroon, 2015)
IPA -water - GA:CC (3:1) Txy 5 – 10 mol% 354.3–372.0 100 (Rodriguez and Kroon, 2015)
lactic acid - choline chloride (2:1) IPA - LA:CC (2:1) PT 5 – 10 mol% 307.2–354.5 10–100 (Rodriguez and Kroon, 2015)
water - LA:CC (2:1) PT 5 – 10 mol% 319.5–371.6 10–100 (Rodriguez and Kroon, 2015)
IPA -water - LA:CC (2:1) Txy 5 – 10 mol% 353.6–371.5 100 (Rodriguez and Kroon, 2015)
Chemical Engineering Research and Design 184 (2022) 402–418

glycerol - choline chloride (2:1) IPA -water - G:CC (2:1) Txy 10–80 wt% 353.86–370.05 100 (Zhang et al., 2017)
ethylene glycol - choline chloride (2:1) IPA -water - EG:CC (2:1) Txy 10–80 wt% 355.43–373.29 101.3 (Zhang et al., 2018)
triethylene glycol - choline chloride (3:1) IPA -water - TEG:CC (3:1) Txy 3–15 wt% 354.77–376.25 101.3 (Jiang et al., 2019a)
acetonitrile - water glycolic acid – choline chloride (3:1) acetonitrile - GA:CC (3:1) Tx 0 – 60 mol% 354.7–376.5 101.3 (Sharma et al., 2018)
water - GA:CC (3:1) Tx 0 – 39 mol% 373.1–388.0 101.3 (Sharma et al., 2018)
acetonitrile - water - GA:CC (3:1) Txy 5–15 mol% 356.0–376.6 101.3 (Sharma et al., 2018)
glycolic acid – tetramethylammonium chloride acetonitrile - GA:TMAC (3:1) Tx 0 – 60 mol% 354.7–381.4 101.3 (Sharma et al., 2019)
(TMAC) (3:1)
water - GA:TMAC (3:1) Tx 0 – 39 mol% 373.1–398.8 101.3 (Sharma et al., 2019)
acetonitrile - water - GA:TMAC (3:1) Txy 5–15 mol% 357.3–383.4 101.3 (Sharma et al., 2019)
malic acid – choline chloride (1:1) acetonitrile - MA:CC (1:1) Tx 0 – 48 mol% 354.7–374.3 101.3 (Sharma et al., 2020)
water - MA:CC (1:1) Tx 0 – 29 mol% 373.1–385.6 101.3 (Sharma et al., 2020)
acetonitrile - water - MA:CC (1:1) Txy 5–15 mol% 356.4–378.7 101.3 (Sharma et al., 2020)
(continued on next page)
 Chemical Engineering Research and Design 184 (2022) 402–418 407

conducted. Further, 1H‐NMR measurements to study the

reusability of the DES were carried out. Universal-quasi­
chemical (UNIQUAC) and NRTL models were used to corre­
late the ternary VLE data directly, with the results reported to
(Jiang et al., 2019b)
(Jiang et al., 2019b)

2021b)
2021b)
2021b)
2021b)
2021b)

(Bai et al., 2021b)

(Bai et al., 2021b)

(Bai et al., 2021a)

(Bai et al., 2021a)

(Bai et al., 2021a)

be in good agreement with experimental results. Concerning
(Qiu et al., 2021)

(Qiu et al., 2021)

biodegradability, values of organic carbon degraded ranged

al.,
al.,
al.,
al.,
al.,
from 85.6% in case of Ur - CC (2:1) to 42.8% for the IL 2-hy­
droxy ethylammonium acetate. After five boiling cycles
et
et
et
et
et
(Bai
(Bai
(Bai
(Bai
(Bai
at 110 °C for 1.5 – 2 h, no change in chemical structure of the
DES was found, which was confirmed by 1H‐NMR measure­
ments (Gjineci et al., 2016).
The influence of Ur - CC (2:1) on the ethanol – water
azeotrope was also studied by Peng et al. (2017), however
101.3
101.3
101.3

101.3

101.3

101.3
101.3
101.3
101.3
101.3

101.3

101.3

101.3

101.3
over a broader concentration range than Gjineci et al. (2016).
with the ranges depicted in Table 2. Pseudo-binary interac­
tion parameters for water – DES respectively ethanol – DES
362.94–373.43
362.55–372.53
418.55–470.75

402.85–414.45

353.25–353.85

353.25–353.85
353.25–353.85
353.25–353.85
353.25–353.85
353.25–353.85

353.25–353.85

353.25–353.85

353.25–353.85

353.25–353.85
systems were reported. As the calculation of pseudo-ternary
VLE with parameters obtained from pseudo-binary VLE
measurements is in general not satisfactory, as also reported
by Rodriguez and Kroon (2015), additionally the pseudo-
ternary systems were correlated directly with the NRTL
model. As a result, two NRTL parameter sets were reported.
5–15 mol%
5–15 mol%
10–80 wt%

10–80 wt%

10 mol%

10 mol%
15 mol%
20 mol%
10 mol%

10 mol%

10 mol%

10 mol%

10 mol%

One set for the pseudo-binary systems, and one for the
5 mol%

pseudo-ternary system (Peng et al., 2017).

Zhang et al. (2019) studied the mixed entrainer ethylene
glycol (EG) - CC at different molar ratios, where the mixed
Txy
Txy
isoamylalcohol - ethylenglycol - water- Txy

isoamylalcohol - ethylenglycol - water- Txy

benzene - cyclohexane - LVA:TBAB (2:1) Txy

Txy
Txy
Txy
Txy
Txy

benzene - cyclohexane - LVA:TBAB (3:1) Txy

benzene - cyclohexane - LVA:TBAB (4:1) Txy

Txy

Txy

entrainer EG – CC (2:1) was also a DES. The addition of choline

chloride increased the relative volatilities leading to im­
benzene - cyclohexane - LVA:TBAB (2:1)
benzene - cyclohexane - LVA:TBAB (2:1)
benzene - cyclohexane - LVA:TBAB (2:1)
benzene - cyclohexane - LVA:TBAB (2:1)
benzene - cyclohexane - LVA:TBAB (1:1)

benzene - cyclohexane - EG:TBAB (2:1)

proved entrainer performance comparable or better than ILs

benzene - cyclohexane - LVA:CC(2:1)

for the same separation task. In this work, for the first time in
allyl alcohol - urea - Ur:CC (2:1)
allyl alcohol - water- G:CC (1:1)

extractive distillation entrainer studies with DES, the qua­

ternary approach for correlation of VLE data with the NRTL
model was used, with the modelling results found to be in
good agreement with experimental data (Zhang et al., 2019).
The influence of EG – CC besides other mixed entrainers on
the ternary system water – methanol – ethanol was studied
MCA:CC (2:1)

by Shu et al. (2020).

G:CC (2:1)

A DES consisting of glycerol (G) – CC (2:1) was tested for

applicability in the ethanol-water separation by Souza et al.
(2021). VLE data was correlated by NRTL and UNIQUAC
models to obtain binary interaction parameters for the
pseudo-binary systems water - DES respectively ethanol -
malonic acid (MCA) – choline chloride (2:1)

tetrabutylammoniumbromide (TBAB) (2:1)

DES. Similar to the work of Rodriguez and Kroon (2015), it

was reported that the representation of the pseudo-ternary
levulinic acid - choline chloride (2:1)
tetrabutylammoniumbromide (1:1)

tetrabutylammoniumbromide (3:1)

tetrabutylammoniumbromide (4:1)

tetrabutylammoniumbromide (2:1)

systems with the parameters obtained by correlation of

glycerol - choline chloride (1:1)

glycerol - choline chloride (2:1)

pseudo-binary systems was not satisfactory. This was at­

urea - choline chloride (2:1)

tributed to neglecting ternary interactions as well as the

application of the pseudo-pure component approach (Souza
levulinic acid (LVA) -

et al., 2021).
Li et al. (2021) also studied the system G – CC (2:1) –
ethylene glycol -
levulinic acid -

levulinic acid -

levulinic acid -

ethanol – water. However, they used a quaternary approach

for correlation of VLE data. A reduction of the minimum
entrainer mole fraction by 40% as compared to glycerol alone
was reported (Li et al., 2021), as graphically depicted in Fig. 2.

2.1.2. IPA – water

Table 2 – (Continued)

Next to the ethanol – water system, the IPA – water system is

ethylenglycol - water

benzene - cyclohexane

also of industrial relevance, exhibiting a low-boiling azeo­

allyl alcohol - water

trope (353.7 K, 1 atm) at a composition of 67.4 mol% (87.3 wt%)

isoamylalcohol -

IPA (CRC Handbook of Chemistry and Physics, 2016).

Non-polar

The first investigation of a DES as entrainer for the se­

paration of the IPA – water azeotrope was conducted by
Rodriguez and Kroon (2015). LA – CC (2:1) and GA – CC (3:1)
were investigated as entrainers. It was found that these DES
408 Chemical Engineering Research and Design 184 (2022) 402–418
Fig. 2 – Relative volatility of ethanol (1) to water (2) in
relation to entrainer mole fraction xs at ethanol mole
fraction x1 = 1 (entrainer free basis) and P = 101.3 kPa (Li
et al., 2021), solid line: ethanol (1) + water (2) + glycerol (3)
+ choline chloride (4), dashed line: ethanol (1) + water (2)
+ glycerol (3).
were not able to break the azeotrope at the concentrations
studied, however a shift of the azeotropic point towards the
pure IPA side was observed. The VLE data was correlated by
the NRTL model, with parameters obtained from pseudo-
binary systems not being able to accurately describe the
pseudo-ternary systems. Pseudo-ternary VLE data was also
fitted directly, with adequate results reported. Here, for each
entrainer mole fraction investigated (0.05 and 0.1) a different
set of binary interaction parameters was reported (Rodriguez
and Kroon, 2015).
Zhang et al. (2018) studied the mixed solvent EG – CC at
different ratios as well as the DES G – CC (2:1) (Zhang et al.,
2017) in regard to the IPA – water azeotrope. Again their mod­
elling approach was to correlate the quaternary system with
the NRTL model in both works, with satisfactory agreement
with the experimental data. The azeotrope was eliminated at a
minimum entrainer mass fraction of 0.142 for G – CC (2:1) and
0.157 for EG – CC (2:1). Concerning the glycerol-based DES, this
corresponds to a reduction of 38% compared to pure glycerol as
entrainer, which is also graphically depicted in Fig. 3.
Jiang et al. (2019a) applied the COSMO-RS (conductor like
screening model for real solvents) for the screening of 19 cho­
line chloride-based DES for the separation of the IPA – water
azeotrope. Based on the product of selectivity and capacity as
selection criterion, which they termed performance index (PI),
TEG – CC (3:1) was chosen as entrainer to be investigated. VLE
measurements and pseudo-ternary correlation with the NRTL
model revealed that the azeotropic point is eliminated at an
entrainer mass fraction of 10 wt% (Jiang et al., 2019a).
2.1.3. Other systems
Relatively few other systems than ethanol – water and IPA –
water have been studied up to now. The research concerning
these systems is summarized in this section.
Fig. 3 – Relative volatility of IPA (1) to water (2) in relation to
entrainer weight fraction ws at IPA mole fraction x1 = 1
(entrainer free basis) and P = 100 kPa (Zhang et al., 2017),
solid line: IPA (1) + water (2) + glycerol (3) + choline chloride
(4), dashed line: IPA (1) + water (2) + glycerol (3).
Sharma et al. investigated the acetonitrile – water azeo­
trope. The following DES were tested: GA – CC (3:1) (Sharma
et al., 2018), GA – tetramethylammonium chloride (TMAC)
(3:1) (Sharma et al., 2019) and MA – CC (1:1) (Sharma et al.,
2020). Pseudo-binary and pseudo-ternary VLE measurements
were conducted and the data of the pseudo-ternary systems
were directly correlated by the NRTL model. All three DES
were found to break the azeotrope. The recoverability of the
DES was also studied by FT-IR, comparing the spectra before
and after several boiling cycles in a rotary evaporator, with
no significant changes in the spectra reported. However, a
drop in performance for MA – CC (1:1) was observed, which
was explained by possible esterification of malic acid with
choline chloride during the process.
The allyl alcohol – water system was studied by Jiang et al.
(2019b). Two DES, G – CC (1:1) and Ur – CC (2:1) were tested for
their applicability as entrainer. Pseudo-ternary VLE data was
measured and correlated directly by the NRTL model. Both
DES were reported to eliminate the azeotropic point (Jiang
et al., 2019b).
The only non-polar azeotropic system investigated until
now is the benzene – cyclohexane system. Bai et al. (2021a)
studied the influence of three hydrophobic DES: levulinic
acid – tetrabutylammonium bromide (TBAB) (2:1), EG – TBAB
(2:1) and levulinic acid – CC (2:1). Pseudo-ternary VLE data
was measured for all three DES – azeotrope systems and
correlated by the NRTL model, where levulinic acid – TBAB
(2:1) was found to break the azeotrope (Bai et al., 2021a).
In a follow up paper, Bai et al. (2021b) studied the influ­
ence of levulinic acid – TBAB (1:1, 2:1, 3:1, 4:1) on the benzene
– cyclohexane azeotrope at different molar ratios. The DES
with the ratio 2:1 was found to break the azeotrope at the
concentrations studied. Subsequently, pseudo-ternary VLE
data for different entrainer mole fractions (0.05; 0.1; 0.15; 0.2)
was reported and correlated with the NRTL model, with four
 Chemical Engineering Research and Design 184 (2022) 402–418
different parameter sets given for the four investigated en­
trainer mole ratios (Bai et al., 2021b).
The ternary azeotrope isoamylalcohol – ethylene glycol –
water was investigated by Qiu et al. (2021) with regard to
extractive distillation by means of quantum-chemical cal­
culations. The interactions of the system with different en­
trainers were examined, including the deep eutectic solvents
G – CC (2:1) and malonic acid – CC (2:1). VLE data was reported
for the corresponding systems isoamylalcohol – ethylene
glycol – water – DES, however no correlation with thermo­
dynamic models was attempted and no statements about
entrainer performance based on experimental results were
made (Qiu et al., 2021).
2.2. Process simulations
Seven research papers dealing with simulation of the ex­
tractive distillation process with DES were found; five con­
cerning the separation of ethanol – water and two
concerning the IPA – water azeotrope.
Ma et al. (2017) investigated the system ethanol – water
with GA – CC (3:1) as entrainer through simulation in Aspen
Plus and a batch distillation experiment. Entrainer recovery
was carried out in a flash tank at 0.004 kPa and 423 K. A
sensitivity analysis was carried out for the determination of
the main design variables and the process was finally opti­
mized via a heat exchanger network. The NRTL model was
used, with binary interaction parameters for DES – ethanol
and DES – water taken from Rodríguez et al. (2015). A re­
duction in specific energy consumption per kilogram ethanol
produced by 46.6% and 15.9% compared to the traditional
entrainer ethylene glycol – potassium acetate respectively
the ionic liquid [EMIM][BF4] was reported. The batch experi­
ments were carried out in a packed column with a length of
1.5 m. As feed, an ethanol – water mixture with an ethanol
molar fraction of 0.85 was used. High purity ethanol in the
distillate with mole fractions ranging from 0.970 to 0.995
depending on reflux ratio and entrainer/feed ratio was ob­
tained (Ma et al., 2017).
Simulation of ethanol - water separation with the DES Ur –
CC (2:1) was studied by Han and Chen (2018). Like Ma et al.
(2017) they used the NRTL model, with parameters from Peng
et al. (2017). For optimization of the simulation a sequential
iterative strategy was used. In contrast to Ma et al. (2017) an
entrainer recovery column was used instead of a flash tank,
since the proposed pressure for the flash vessel (0.004 kPa) by
Ma et al. was deemed to be difficult to reach in an industrial
setting. The process was simulated for both the DES and the
traditional solvent ethylene glycol, with savings in TAC by
14.61% for the DES-based process compared to EG. Ad­
ditionally, through combination of the preconcentration
section with the entrainer recovery in a single column, fur­
ther savings in TAC by 29.48% for the EG-based process and
17.42% for the DES-based process could be realised (Han and
Chen, 2018).
The separation of the ethanol – water azeotrope with Ur –
CC (2:1) was also studied by Fontana et al. (2021). A reduction
in the specific energy consumption by 27 – 43% for the DES-
based process depending on solvent flow rates between 28
and 31.2 kmol/h was reported when compared to the con­
ventional entrainer ethylene glycol. This study is the only
one so far dealing with rate-based simulation for extractive
distillation with DES, with 62% more stages required and an
increase in TAC by 8.4% compared to the equilibrium stage
409
simulation. Here for the first time a novel approach con­
cerning the thermodynamic modelling was used, where two
different sets of NRTL binary interaction parameters were
used for the extractive column and the entrainer regenera­
tion column (Fontana et al., 2021). The parameters were
taken from Peng et al. (2017).
A comprehensive study on the extractive distillation of
ethanol – water with Ur – CC (2:1) was conducted by Shang
et al. (2019). The NRTL model was used for modelling, with
binary interaction parameters obtained by Peng et al. (2017).
The COSMO-RS model was used to compare and explain
differences in separation performance between glycerol, the
DES Ur – CC (2:1) and the IL [EMIM][BF4]. Optimization of the
extractive distillation process via a multi-objective genetic
algorithm showed a better separation performance of the
DES compared to glycerol and [EMIM][BF4] (Shang et al., 2019).
A detailed investigation on control structures for the ex­
tractive distillation of ethanol – water with Ur – CC (2:1) was
carried out by Pan et al. (2019a). A multi-objective genetic
algorithm was used for optimization of the process, with
heat intensification incorporated for further savings in en­
ergy. Five control schemes were evaluated in terms of con­
trollability and energy efficiency (Pan et al., 2019a).
De et al. (2019) investigated the separation of the IPA –
water azeotrope with three different entrainers: glycerol,
glycerol + MgCl2 and glycerol – CC (2:1). The symmetric
eNRTL (electrolyte non-random-two-liquid) model was
chosen for thermodynamic modelling with parameters re­
gressed partly from measured VLE data and partly from data
available in literature. A reduction in TAC by 32.5% and 21.4%
for the saline entrainer glycerol + MgCl2 respectively glycerol
– CC (2:1) as compared to glycerol alone as well as a decline in
specific energy consumption (SEC) by 33.9% and 24.1% was
reported (De et al., 2019).
Cui et al. (2020) evaluated the extractive distillation pro­
cess for IPA dehydration. The traditional process with the
conventional solvent ethylene glycol was compared with
DES-based processes utilizing G – CC (2:1) and EG – CC (2:1) as
entrainers. For modelling, the NRTL model was used, with
parameters taken from Zhang et al., (2017, 2018). So far, this
is the only simulation utilizing the quaternary approach,
treating the system as consisting of four separate compo­
nents. Savings in TAC by 30.3% and 30.9% for G – CC (2:1) and
EG – CC (2:1) compared to ethylene glycol were reported. The
environmental impact was also compared, with the results
in favour of the DES-based processes (Cui et al., 2020).
3. Evaluation of the current state of research
3.1. Screening and modelling
Screening of entrainers in regard to separation performance
is usually the first step in the development of an extractive
distillation process. It becomes even more important when
using DES as entrainers, since the combination of different
HBAs and HBDs yields a very large number of possible can­
didates, similar to ILs. Screening of DES is not trivial since
there is a lack of predictive models. In contrast to DES, pre­
dictive models have been developed specifically for ILs, as for
instance the UNIFAC-Lei model (Lei et al., 2009) which is
continuously revised with an extending parameter matrix
(Lei et al., 2012; Dong et al., 2020). For many DES components,
especially the ionic part (e.g. choline chloride), group
410 Chemical Engineering Research and Design 184 (2022) 402–418

parameters are missing. Therefore, UNIFAC has not been

used for predicting VLE in extractive distillation with DES up
to now.
Predictive models for conventional molecules like UNIFAC
with its various modifications are well established. Also,
experimental data like activity coefficients at infinite dilu­
tion, which are the basis for most screening procedures, are
often readily available in databanks for conventional com­
ponents. Even integrated software packages exist for
screening, utilizing databanks and/or predictive models, e.g.
the software Entrainer Selection by the Dortmund Databank.
For DES-based systems, few experimental data concerning
activity coefficients at infinite dilution is available to date.
To the best of our knowledge, the only predictive model
available for an at least qualitative screening of DES is the
COSMO-RS model via estimation of activity coefficients at
infinite dilution, as applied by Jiang et al. (2019a) for the se­
paration of the IPA – water azeotrope. Only the molecular
structure is needed as input, with no experimental data re­
quired. A detailed description of this model can be found in
literature (Klamt, 1995, 2011). In the case of extractive dis­
Fig. 4 – Pseudo-ternary data points for the ethanol (1) –
tillation with DES, few screening procedures have been uti­
lized by now, with the choice of the entrainer made rather water (2) – [CC – Ur (1:2)] (3) system from (Peng et al., 2017),
randomly. In general, the COSMO-RS model is widely used 30 wt% CC – Ur ( ), 20 wt% CC – Ur ( ), 10 wt% CC – Ur ( );
for screening procedures in various DES applications lines: NRTL calculations with parameters regressed from
(Hizaddin et al., 2016; Liu and Zhang, 2022; Hadj-Kali et al., pseudo-binary measurement data; NRTL parameters from
2017; Jeliński and Cysewski, 2018; Salleh et al., 2017; Gouveia (Peng et al., 2017); calculation conducted in Aspen Plus V11
et al., 2016; Cheng et al., 2018; Wojeicchowski et al., 2020). with NRTL set 2 (see Table S2 supporting information).
For VLE modelling of systems containing DES, various
approaches can be found in literature (González De Castilla
et al., 2020; Alkhatib et al., 2020). These range from activity
coefficient models and classical equations of state (EoS) to
more sophisticated approaches derived from the statistical
associating fluid theory (SAFT). Since the topic of this review
is extractive distillation with DES and not thermodynamic
modelling of DES in general, the discussion in this section is
restricted to models which were actually used in extractive
distillation with DES. For more detailed information on the
thermodynamic modelling of DES, the reader is referred to
the literature (González De Castilla et al., 2020; Alkhatib et al.,
2020). For modelling VLE of systems containing DES, the
standard NRTL model is widely used. The majority of papers
follows a pseudo-pure component approach, treating the
DES as one single molecular entity. Binary interaction para­
meters obtained from fitting VLE data of the pseudo-binary
systems (component 1 – DES, component 2 – DES) do not
yield satisfying results for the description of the pseudo-
ternary systems (Rodríguez et al., 2015; Peng et al., 2017;
Souza et al., 2021), very likely due to neglection of ternary
interactions, with the binary interactions not dependent on
other mixture components. Exemplary this is shown for two Fig. 5 – Pseudo-ternary data points for the ethanol (1) –
systems in Figs. 4 and 5. water (2) – [CC – G (1:2)] (3) system, 50 mol% CC – G (◆);
Therefore, in literature, the pseudo-ternary systems are dashed line: UNIQUAC calculation, dashed-dotted line:
sometimes correlated directly for constant entrainer frac­ NRTL calculation; calculations with parameters regressed
tions (Rodríguez et al., 2015; Rodriguez and Kroon, 2015; Bai from pseudo-binary measurement data (Souza et al., 2021).
et al., 2021a, 2021b), which has the drawback that the para­
meter set is only valid for this single point. However, there is
also the approach to simultaneously correlate ternary VLE the measured range and also reproducing the azeotropic
data for several constant entrainer fractions (Peng et al., point of ethanol – water with sufficient accuracy as depicted
2017; Jiang et al., 2019a; Sharma et al., 2018, 2019, 2020; Jiang in Figs. 6 and 7.
et al., 2019b). For instance, Peng et al (Peng et al., 2017). cor­ However, the question of validity for these parameters
related pseudo-ternary VLE data for three constant entrainer arises beyond the measured and thus fitted entrainer frac­
fractions (10, 20 and 30 wt%) with the NRTL model, with the tions. Indeed, this is a challenge for simulation of columns,
parameters depicting the measured VLE data quite well in as poor parameters which do not describe experimental VLE
 Chemical Engineering Research and Design 184 (2022) 402–418
Fig. 6 – Pseudo-ternary data points for the ethanol (1) –
water (2) – [CC – Ur (1:2)] (3) system from (Peng et al., 2017),
30 wt% CC – Ur ( ), 20 wt% CC – Ur ( ), 10 wt% CC – Ur ( );
lines: NRTL calculations with parameters regressed from
pseudo-ternary measurement data; NRTL parameters from
(Peng et al., 2017); calculation conducted in Aspen Plus V11
with NRTL set 1 (see Table S2 supporting information).
Fig. 7 – Enlarged section of Fig. 6; pseudo-ternary data
points for the ethanol (1) – water (2) – [CC – Ur (1:2)] (3)
system from (Peng et al., 2017), 30 wt% CC – Ur ( ), 20 wt% CC
– Ur ( ), 10 wt% CC – Ur ( ); lines: NRTL calculations with
parameters regressed from pseudo-ternary measurement
data; NRTL parameters from (Peng et al., 2017); calculation
conducted in Aspen Plus V11 with NRTL set 1 (see Table S2
Supporting information); azeotropic point prediction:
T = 351.3 K; xEthanol = 0.894 (literature (CRC Handbook of
Chemistry and Physics, 2016): T = 351.3 K, xEthanol = 0.897).
411
data accurately can lead to questionable results in regard to
process design (Gmehling et al., 2019). The quaternary
modelling approach or individual constituent approach
seems to yield better results in terms of depicting experi­
mental VLE data. However, the applicability of this approach
for process simulation is questionable. The special properties
of a DES arise from the complex molecular interactions of
HBA and HBD (Hansen et al., 2021); if the components are
added separately into the database of a process simulator, it
is doubtful that this depicts reality sufficiently, since the
physical and transport properties of the DES like viscosity are
not represented, even if the VLE is projected more accurately
in comparison to the pseudo-pure component approach,
which will be discussed in more detail later. This was also
pointed out by other authors; H. Zhang et al. investigated
aqueous solutions of CC – Ur (1:2) regarding excess molar
volumes and viscosity and suggested treating the DES in this
case as a pseudo-component to be the more appropriate
approach (Zhang et al., 2021).
3.2. Process simulations
Few process simulations of extractive distillation with DES
are available at the moment, with only two systems (ethanol
– water, IPA – water) studied. Since DES are not available in
commercial process simulator databases, they have to be
entered as user-defined components. Scalar thermodynamic
properties like critical temperature, pressure and volume, as
well as normal boiling point and acentric factor, are either
taken from literature or estimated, mostly with a combina­
tion of the modified Lydersen-Joback-Reid method and Lee-
Kesler mixing rules as described by Mirza et al. (2015).
Temperature dependent properties like heat capacities, va­
pour pressures or viscosity are either regressed from ex­
perimental data or also estimated. Regarding the choice of
the thermodynamic model, the NRTL model is used ex­
clusively until now, owing to the availability of binary in­
teraction parameters for this model in the literature.
Since the thermodynamic model chosen and the para­
meters used are the core part of any simulation, a closer look
has to be taken on this topic. In their work regarding the
ethanol – water azeotrope separation with GA – CC (3:1), Ma
et al. (2017) used parameters from Rodríguez et al. (2015).
Here, the NRTL model was fitted to pseudo-binary VLE data
at a constant entrainer mole fraction (20 mol%). From a
modelling perspective, this means that the parameters are
only valid for this exact entrainer mole fraction. However, in
the simulation of Ma et al. (2017), the entrainer mole fraction
inside the separation column varies between 0 and ap­
proximately 65 mol%, which should be considered, ad­
ditionally taking into account the fact that parameters
obtained from fitting pseudo-binary data do not yield sa­
tisfying results for the description of ternary VLE (Rodríguez
et al., 2015; Peng et al., 2017; Souza et al., 2021).
Regarding the simulation of ethanol – water separation
with Ur – CC (2:1), Han and Chen (2018), Shang et al. (2019)
and Pan et al. (2019b) used NRTL parameters from Peng et al.
(2017), which were fitted to pseudo-ternary VLE data for en­
trainer fractions of 10, 20 and 30 wt% corresponding to a
maximum mole fraction of 19 mol% for a DES – ethanol
mixture. In this range the data is depicted quite well by the
model, however the validity outside this range must be
412 Chemical Engineering Research and Design 184 (2022) 402–418
questioned. In the work of Han and Chen (2018), entrainer
mole fractions inside the separation column up to 40 mol%
and in the simulation of Shang et al. (2019) and Pan et al.
(2019b) up to 65 mol% are reported, which is a significant
deviation from the range the parameters were correlated to.
Fontana et al. (2021) also used parameters from Peng et al.
(2017), but as already described in Section 2, two different
NRTL sets were used. In the separation column, parameters
from fitting pseudo-ternary VLE data were used, and in the
entrainer regeneration column, parameters from pseudo-
binary measurements were used. Since in the regeneration
column, only water and DES are present, this approach may
be justified and is further supported by comparing the ex­
perimental data with calculations from different parameter
sets, which shows good agreement, as shown in Fig. 8.
However, the maximum mole fraction in the separation
column simulated by Fontana et al. (2021) is still above
50 mol%, thus the same considerations concerning the
parameter validity for this concentration range should be
taken into account.
The only research group up to now using the quaternary
or individual constituent approach in process simulation of
extractive distillation with DES was the team of Cui et al.
(2020). The extractive distillation of the IPA – water azeotrope
with conventional entrainer EG and DES CC – G (1:2) as well
as CC – EG (1:2) was investigated (Cui et al., 2020). For the
simulation, choline chloride was entered as user-defined
component and the thermodynamic model chosen was the
NRTL model, with parameters from Zhang et al. (2017, 2018).
As mentioned in Section 3.1., caution should be taken when
treating the DES as “conventional mixture” of two compo­
nents, especially considering transport properties, for in­
stance viscosity. In Fig. 9, experimental and calculated
(mixture of two separate components) viscosities of CC – G
Fig. 8 – Boiling curve of water in relation to DES CC – Ur (1:2)
content, experimental points (◆) from (Peng et al., 2017);
solid line: NRTL calculation with parameters from pseudo-
ternary measurements (set 1), dashed line: NRTL
calculation with parameters from pseudo-binary
measurements (set 2); parameters from (Peng et al., 2017);
plotting conducted in Aspen Plus V11 with NRTL sets 1 and
2 (see Table S2 Supporting information).
Fig. 9 – Experimental (◇) (Abbott et al., 2011) vs calculated
mixture viscosity (calculated in Aspen Plus V11) (▲) for CC –
G (1:2).
(1:2) are compared. The calculation of the mixture viscosity
was conducted in Aspen Plus V11, with choline chloride en­
tered as user-defined component and the same viscosity data
(see Supporting information Table S1) used as by Cui
et al. (2020).
There is a significant deviation between the calculated
and the experimental values, with the experimental values
being higher up to a factor of more than 3. Issues like this
should be kept in mind when conducting but also evaluating
process simulations with DES. Viscosity is an important
transport quantity in distillation, influencing mass transfer
and thus also the separation efficiency (Bradtmöller and
Scholl, 2015; Mahiout and Vogelpohl, 1987; Böcker and Ronge,
2005). Especially for rate-based modelling approaches, using
viscosities that depict the real system as well as possible are
needed in order to achieve meaningful results. Nevertheless,
the influence on the simulation results of Cui et al. (2020) is
expected to be low, since an equilibrium stage approach was
used, not taking into account mass transfer phenomena,
which may be affected by higher viscosities.
3.3. Entrainer feasibility
While most research groups up to now have focused on the
general ability of a DES entrainer to break the azeotrope,
which is undoubtedly the key point, less information is
available about general feasibility criteria like miscibility
gaps or thermal stability. Nevertheless, knowledge about
these properties is essential for process design, strongly in­
fluencing the decision of the final entrainer choice.
3.3.1. Miscibility gaps
One important aspect in extractive distillation is the mis­
cibility of the entrainer with the system of interest, as mis­
cibility gaps may set the boundaries for the design of feasible
process ranges. In extractive distillation, miscibility of the
entrainer with the azeotropic system is generally preferred,
whereas in heterogeneous azeotropic distillation liquid-li­
quid splitting is encountered on some column trays at least
(Springer et al., 2003).
In the case of deep eutectic solvents, little information is
available up to now even concerning the most investigated
systems ethanol – DES and IPA – DES, for instance in form of
ternary diagrams. Zhang et al. (2018) observed liquid-liquid
splitting during VLE measurements of IPA – water with EG –
 Chemical Engineering Research and Design 184 (2022) 402–418 413

CC (4:3) in the IPA-rich region (IPA fraction on entrainer-free

basis 95 mol%) of the VLE, due to salting out effects by cho­
line chloride (Zhang et al., 2018). Miscibility gaps may be
expected in more systems, since choline chloride, which is
the HBA in the majority of examined DES until now, has only
limited solubility in aliphatic alcohols like IPA (Zhang et al.,
2018) and also acts as salting out agent (Zafarani-Moattar
et al., 2019). Additionally, considering that in many papers
only small total entrainer fractions up to a certain limit were
considered (see Table 2), there is lack of information about
the whole concentration range.

3.3.2. Thermal stability

Attention should also be paid to the thermal stability of the
entrainer, in order to avoid decomposition during the pro­
cess. Operating columns at lower pressure to decrease
boiling points can help to mitigate this issue. Nevertheless,
accurate and reliable experimental data is needed for process
design.
In the case of Ur – CC (2:1), there is some discrepancy
between the results of different research groups. In the
process simulations that cover this type of DES, maximum
temperatures in the sump of the extractive distillation
column respectively the entrainer regeneration column of
493 K (Han and Chen, 2018), 418 K (Shang et al., 2019; Pan
et al., 2019b), and 451 K (Fontana et al., 2021) are reported.
Thermal decomposition was not considered by Han and
Chen (2018), while Shang et al. (2019), Pan et al. (2019b) and
Fontana et al. (2021) designed the process based on a de­
composition temperature of 484 K, as reported by Chemat
et al. (2016) in 2016. However, in a more recent study by
Gilmore et al. (2019) from 2019, thermal decomposition of Ur
– CC (2:1) at temperatures as low as 363 K is reported. It was
also found that samples of Ur – CC (2:1) exposed to elevated
temperatures (353.15 − 363.15 K) for extended periods of time
had a strong ammoniacal odor and crystalline solids were
deposited on the walls of the sample containers. Information
like this is critical and must be considered prior the design of
the process. Some authors did report on the reusability of
DES after solvent recycling (Gjineci et al., 2016; Sharma et al.,
2018, 2019, 2020). However, the number of cycles and thus
the time periods of exposing the DES to higher temperatures
were rather low, as for instance in the experiment of Gjineci
et al. (2016), where Ur – CC (2:1) and TEG – CC (3:1) were
subjected to five boiling cycles with a duration of 1.5 - 2 h.
However, in a real application, the cycling solvent would be
subjected to elevated temperatures for weeks or months.
3.3.3. Viscosity
In extractive distillation, viscosity is an important transport
quantity, directly influencing mass transfer and thus the
number of stages in a column, with further consequences on
process cost. In general, DES are solvents with rather high
viscosity (AlOmar et al., 2016; Liu et al., 2019; Gygli et al., 2020;
Gajardo-Parra et al., 2020), which is a disadvantage in ex­
tractive distillation. However, each DES has to be evaluated
specifically since surprising phenomena have been observed
for choline chloride-based DES with glycerol and diols as
HBD. In the case of glycerol, the viscosity is reduced sig­
nificantly by adding choline chloride, while in the case of
ethylene glycol the viscosity increases, which is depicted in
Figs. 10 and 11. This effect is attributed to the break-up of the
three-dimensional interaction of H-bonds in glycerol by ad­
dition of choline chloride, resulting in a system which is less
Fig. 10 – Viscosity of glycerol (•) (Segur and Oderstar, 1951)
and CC – G (1:2) (○) (Abbott et al., 2011).
Fig. 11 – Viscosity of ethylene glycol (▲) (Gajardo-Parra
et al., 2020) and CC – EG (1:2) (△) (Gajardo-Parra et al., 2020).
ordered. This is also backed up by a decrease in density,
while for diol-based systems (e.g. ethylene glycol) this is not
the case (Gajardo-Parra et al., 2020; Abbott et al., 2011).
This again shows the complex behaviour of DES, which
may have beneficial or adverse implications as shown for
glycerol and ethylene glycol, and the need for reliable ex­
perimental data for process design. Another example, which
supports the argument for tedious inquiry of transport
properties, which should in fact be part of any good process
design routine but more so in the case of DES-based pro­
cesses, is the CC – Ur system, where large differences in re­
ported viscosities are observed as depicted in Fig. 12. Gilmore
et al. (2019) attributed this observation to samples being not
fully dried, which results in lower viscosities.
A final remark concluding viscosities of DES in extractive
distillation is, that despite rather high viscosities especially
at room temperature, the decrease with rising temperatures
is significant. For thermally sensitive processes this may be a
problem, in distillation, however, higher temperatures are
common anyway and thus mitigate the viscosity issue of DES
somewhat. Still, the viscosity issue should be kept in mind,
in view of mass transfer but also design of column internals.
3.4. Comparison with other solvent types
From an engineering perspective, another essential question
is: How do DES in extractive distillation compare to other
entrainers like ILs or conventional solvents with regard to
price and amounts needed for a specific separation task?
414 Chemical Engineering Research and Design 184 (2022) 402–418
Fig. 12 – Viscosity of CC – Ur (1:2); Abbott et al. ( ) (Abbott
et al., 2003), Yadav et al. ( ) (Yadav and Pandey, 2014),
Gilmore et al. ( ) (Gilmore et al., 2019), Xie et al. ( ) (Xie
et al., 2014).
3.4.1. Minimum amounts
The amounts needed can be compared on the basis of direct
results from VLE measurements and thermodynamic models
on a “standalone” basis, where the minimum amount of
entrainer needed for breaking the azeotrope is calculated
with a mole fraction of unity (entrainer free basis) and the
condition AB = 1, which corresponds to the intersection
point of the uni-volatility curve with the triangle edge in the
ternary diagram. For the case of ethanol – water, which re­
presents the most investigated system, a comparison of en­
trainers in regard to minimum amounts needed to break the
azeotrope is provided in Fig. 13.
As can be seen, the investigated DES outperform con­
ventional solvents with regard to minimum amounts and are
comparable or even better than ILs. Also for the IPA – water
system, DES show remarkable entrainer performance as
shown in Fig. 14. However, the minimum amount of en­
trainer deduced from the isovolatility criterion does not ne­
cessarily correlate with the effectiveness of the entrainer.
The influence of increasing entrainer amounts on the re­
lative volatility also needs to be taken into account. A vi­
sualization of this phenomenon can be done with equi-
Fig. 13 – Minimum entrainer amount (weight fractions)
needed for breaking the ethanol – water azeotrope, a
(Orchillés et al., 2010), b (Ge et al., 2008), c (Tsanas et al.,
2014), d (Zhang et al., 2016), e (Zhang et al., 2015), f (Gjineci
et al., 2016), g (Li et al., 2021), h (Zhang et al., 2019); ▨ ILs, ■
conventional solvents, □ DES.
Fig. 14 – Minimum entrainer amount (weight fractions)
needed for breaking the IPA – water azeotrope, a (Zhang
et al., 2007), b (Zhang et al., 2018), c (Zhang et al., 2014),
d (Zhang et al., 2018), e (Zhang et al., 2017); ▨ ILs, ■
conventional solvents, □ DES.
volatility curves in ternary diagrams (Luyben and Chien,
2010). Further, information from uni-and equi-volatility
curves is mainly relevant for the separation column and not
the entrainer regeneration/recycle column, which also con­
tributes to the total cost of the process.
Therefore, the most conclusive results regarding en­
trainer performance are achieved by process simulation.
However, until now, few process simulations with DES as
entrainers are available, which is also followed by scarcity in
direct comparison between different solvents. For the se­
paration of the ethanol – water azeotrope with GA – CC (3:1),
Ma et al. (2017) reported a reduction in specific energy con­
sumption (MJ/kgEthanol) of 28.2% and 15.9% compared to the
conventional entrainer ethylene glycol respectively the ionic
liquid [EMIM][BF4]. Han and Chen (2018) studied the separa­
tion of ethanol – water with Ur – CC (2:1) and found a re­
duction in TAC of 14.6% compared to the conventional
solvent ethylene glycol. The same system was studied by
Fontana et al. (2021) with a rate-based setup, with savings of
27 – 43% in specific energy consumption reported. Con­
cerning the IPA – water azeotrope, De et al. (2019) reported a
reduction in TAC by 21.4% for the entrainer G – CC (2:1)
compared to glycerol. Cui et al. (2020) also investigated the
IPA – water azeotrope, comparing the conventional solvent
ethylene glycol with EG – CC (2:1) and G – CC (2:1), with
savings in TAC by 30.9% respectively 30.3% for the DES-based
process. The findings of the process simulation investiga­
tions concur with the deductions from the calculated
minimum amounts. Compared to conventional solvents, DES
seem to show a better entrainer performance based on TAC
and specific energy demand. Only one process simulation
study directly compared a DES with an IL, where the DES
showed a better performance. However, since this is the only
direct comparison available until now, no reliable deduction
can be drawn from this.
3.4.2. Price
In Table 3, prices of common ILs and DES components are
listed. For the sake of comparison, the cost on a small scale
basis from a single vendor (MilliporeSigma, 2021) is com­
pared, under the assumption that economics of scale is valid
for all components.
Although this list is comprised of a limited selection of
solvents, it can be deduced that the price of DES is
 Chemical Engineering Research and Design 184 (2022) 402–418
Table 3 – Prices of common ILs, conventional solvents and DES constituents, prices retrieved from86.
IL CAS number Price [$]
[Emim][OTf] > 98% (1 kg) 145022–44–2 2440
[Emim][BF4] > 98% (1 kg) 143314–16–3 1480
[Bmim][OTf] > 97% (1 kg) 174899–66–2 1440
[Bmim][OAc] > 95% (1 kg) 284049–75–8 1280
[Emim][OAc] > 95% (1 kg) 143314–17–4 1150
[Bmim][BF4] > 98% (1 kg) 174501–65–6 1000
[Emim][Cl] > 95% (1 kg) 65039–09–0 473
[EMpy][EtSO4] > 95% (1 kg) 872672–50–9 418
considerably lower than that of ILs and lies in the range of
conventional solvents, since for preparation of the DES only a
simple mixing of the starting materials is required.
4. Conclusion and future prospects
In this first review of its kind, the current state of research
regarding DES as entrainers in extractive distillation was
summarized and evaluated. Most research up to now has
been focusing on experimental VLE data procurement and
subsequent modelling of the obtained data. Most DES in­
vestigated up to now are based on choline chloride as HBA,
with the focus on azeotropic alcohol – water systems. For
modelling of the VLE data, gE-models are exclusively used,
with the NRTL model being the most used. As DES are a
special class of solvents the standard procedure for para­
meter regression, where model parameters obtained from
binary subsystems are used to calculate ternary VLE, does
not yield satisfying results. Therefore, two approaches are
found in literature: Direct correlation of pseudo-ternary
systems for fixed entrainer fractions and the individual
constituent approach, where model parameters are re­
gressed for the quarternary systems treating the DES as two
separate components. Regardless of the modelling approach
used, DES show a higher separation performance than con­
ventional solvents, comparable to ILs. These findings are also
supported by process simulations, with savings in TAC up to
30% reported. However, direct comparisons with ionic liquids
are scarce, so no reliable conclusion can be drawn yet.
Concerning general entrainer feasibility, DES behave like
conventional heavy boiling entrainers, and the same con­
siderations regarding properties like miscibility, viscosities or
thermal stability are valid. Even though the decrease of
viscosity with rising temperature is significant, in general
viscosities of DES are rather high, similar to ionic liquids,
which may affect mass transfer in columns. Information
about miscibility with azeotropic systems over the full
composition range is mostly lacking. Concerning thermal
stability, there is also lack on consistent data, with sig­
nificant differences reported by different research groups.
There is great potential for future research on this topic.
The number of azeotropic systems investigated is still lim­
ited and may be expanded. Especially non-polar systems in
combination with hydrophobic DES are hardly covered until
now. Concerning the DES themselves, the vast majority used
in extractive distillation research is based on choline chloride
as HBA, however, many different HBA are possible. However,
before advancing towards new systems and component
combinations, the existing data should be validated and ex­
panded over larger concentration ranges. Especially in view
of model parameter validity, in order to get more robust
415
DES component CAS number Price [$]
choline chloride > 98% (1 kg) 67–48–1 111
ethylene glycol > 99% (1 l) 107–21–1 95
glycerol > 99% (1 l) 56–81–5 65
urea > 99.5% (1 kg) 57–13–6 53
triethylene glycol 99% (1 kg) 112–27–6 50
parameters which then can be used for simulations yielding
more reliable results. The development of predictive models
for DES similar to ILs is also an open topic, which would not
only contribute greatly to entrainer screening procedures,
but also to the field of DES in general. Furthermore, the
generation and validation of fundamental thermodynamic
and transport data is needed, especially in view of entrainer
miscibility with azeotropic systems over the whole compo­
sition range and long term thermal stability of the DES en­
trainers. For conclusive comparisons of DES with
conventional solvents or ILs, process simulations are needed
which still are limited in number, especially those directly
comparing economics of DES and ILs. Finally, actual lab scale
extractive distillation experiments are encouraged, with only
one reported experiment up to date, offering room for pio­
neering work in a novel research field.
Deep eutectic solvents as entrainers in extractive dis­
tillation are a promising new technology, combining high
separation capability and low volatility similar to the related
class of ionic liquids, with possible advantages concerning
price and toxicity issues over the latter. However, substantial
research has still to be made for their use in an industrial
setting.
Declaration of Competing Interest
The authors declare that they have no known competing fi­
nancial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgement
Financial support by the Austrian Research Promotion
Agency (FFG) is gratefully acknowledged (FFG project
number: 879587).
Appendix A. Supporting information
Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.cherd.2022.06.019.
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