CHAPTER - 6

Entrainer Selection Approach for Distillation

Column

Onkar A. Deorukhkar1*, Tamini B. Rahangdale1, Yogesh S. Mahajan1

1-
Dr. Babasaheb Ambedkar Technological University, Lonere-Raigad-402103.
(*corresponding author: [email protected])

Abstract
This chapter represents an overview regarding selection procedure of entrainer,
which is very important in separation processes like azeotropic/extractive
distillation. Screening of entrainer plays an important role in synthesis and design
of these processes. Addition of entrainer is used to break azeotrope of binary
mixture which introducing it into a pure component. This chapter gives an idea
about different types of entrainer, entrainer addition distillation methods,
selection process, and vapour liquid equilibrium and RCM technique. There are
three types of entrainer heavy, intermediate and light entrainer which based on
the boiling point of the entrainer. A selection process of entrainer is different for
different processes and which is dominantly based on the type of entrainer used
for operation and distillation process. Different selection criteria are given to
screen entrainer for all types (i.e. maximum, minimum and close boiling) of
azeotropic binary mixture in both homogenous and heterogeneous distillation
and also in reactive distillation. The feasibility of entrainer is determined by
residue curve map (RCM) technique. To determine feasibility using RCM,
vapour liquid diagram is necessary to understand.
Keywords: Distillation, Entrainer, Vapour Liquid Equilibrium, Residue Curve
Map (RCM)
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1. INTRODUCTION
Entrainer is very important in distillation separation process. It plays a vital role
in making a boiling point difference in the components whereas a criterion for
entrainer selection is dependent on the behaviour of the system. For today’s
importance in separation point of view many researchers are working in
distillation field. Entrainer refers to the separating agent used to enhance the
separation of close boilers or azeotrope by azeotropic or extractive distillation.
Entrainer is added to the azeotropic mixture which is difficult to separate. The
entrainer are specific to the mixture, benzene is used as entrainer for separating
ethanol and water mixture but not for ethanol and ethyl methyl ketone mixture [1].
Distillation of azeotropic close boiling mixture consist of two or more
component, in which entrainer is added, enhances the separation of component.
Application of entrainer is different for different type of distillation. In extractive
distillation, entrainer is added continuously in top section of the column for
enhancing relative volatility of mixture. When entrainer forms azeotrope with
one or more component of the mixture, at this condition entrainer is added batch
wise to the distillation column, this process is called azeotropic batch distillation.
Various types of techniques are currently used to break azeotrope using entrainer.
These techniques are classified as homogenous azeotropic distillation,
heterogeneous azeotropic distillation, reactive distillation and salted distillation
which are discussed below [2, 3].
Depending on the boiling point of entrainer, three types of entrainer are observed
which are described below.
 Heavy entrainer: entrainer which have higher boiling point as compared
to both the component of azeotropic mixture.
 Intermediate entrainer: the boiling point of entrainer is in between
boiling point of both the component of mixture.
 Light entrainer: this type of entrainer have low boiling point with respect
to the both the component of mixture. Application of light entrainer is
more favourable in batch stripper than batch stripper [3].

2. LITERATURE SURVEY
A decade ago, Pham and Doherty (1990) [4] studied rules for entrainer selection
and updated in the books of Fair and Stichlmair [5] and Doherty and Malone [6]. In
1977, Matsuyama and Nishimura [7] first assumed that each binary face has no
Advances in Chemistry and Chemical Engineering 62

more than one azeotrope and that the ternary system possesses at most one
ternary azeotrope. They show that only 113 different and independent residue
curve maps are possible. In 1991, Bernot et. al. [8] describes the feasibility and
separation sequencing in multi-component batch distillation. Dussel et. al. [9]
Investigate the azeotropic separation technique using an entrainer by
homogenous batch distillation. Because their rules do not cover all possible
cases, Rodriguez et. al. [2, 10] established a complete set of rules for entrainer
selection for the separation of azeotropic mixture by both homogenous and
heterogeneous batch distillation. Laroche et al. (1991) [3] discussed comparatively
three types of entrainers (light, intermediate, and heavy) and their feasibility for
the separation of homogenous azeotropic distillation on the basis of equivolatility
curve, isovolatility curve, and local volatility order. By analyzing different
entrainers, Laroche and his coworkers observed that each class of entrainer has
specific strength and weakness. So they concluded that comparison of candidate
entrainer should be takes place in same class of entrainer and from that the best
candidate is selected by designing, costing and optimizing feasible separation
sequences. There are number of research chapter in which entrainer feasibility
was discussed for specific type of separation process for specific system of the
component. Here we will review entrainer criteria for different type distillation
process and determination methods of their feasibility.

3. ENTRAINER ADDITION DISTILLATION METHODS:

Based on the properties and role of the entrainer, distillation is divided in three
main groups which are given below.
a) Homogenous azeotropic distillation:
Entrainer used in distillation which is completely miscible with
component in original mixture. It forms homogenous azeotrope with
component in the original mixture, this carried out in single feed column.
b) Heterogeneous azeotropic distillation
Entrainer forms heterogeneous azeotrope with one or more components
in the original mixture which is carried out distillation column with a
decanter.
c) Extractive distillation
This process is carried out in two feed column in which entrainer is
introduced above the original mixture feed point and largely removed as
63 Advances in Chemistry and Chemical Engineering

bottom product. Entrainer is used to enhance the relative volatility of low

volatility component to precede the separation of mixture. Entrainer has
high boiling point (heavy entrainer) as compared to the original mixture
component. It does not form any type of azeotrope.
Other than above distillation techniques some more are used now a day which
are listed below:
a) Reactive distillation
Entrainer reacts with one or more component from original mixture. The
non-reacting component is produce as a distillate and the entrainer is
recovered from reverse reaction. Jong et. al. investigate the selection
criteria for entrainer based reactive distillation for esterification with iso-
propanol.
b) Salt distillation
It is the one type of extractive distillation in which relative volatility is
altered by addition of salt as an entrainer in the top reflux [2, 3].

4. ENTRAINER SELECTION CRITERIA

Previously, several authors studied the different technique for entrainer selection
for various types of distillation which are discussed above. To break azeotrope to
its pure component; the design of distillation requires two steps. First step is
selection of entrainer and second is synthesizing a separation sequence for
selected entrainer. Suitable entrainer is to be selected which leads to feasible
separation of azeotropic mixture. Small quantity of entrainer is able to enhance
the relative volatility of given component reduces the cost of separation.
Bernot et. al. [8] proposed the criteria depending upon the type of azeotropic
mixture A-B (i.e. maximum, minimum and close boiling) involved in the
process.
Application of feasibility criteria defines the four general conditions to screen
entrainer for separation of minimum, maximum and close-boiling azeotropic
binary mixture for batch distillation [2].
a. No additional azeotrope is introduced.
b. A minimum-temperature binary azeotrope exists between Entrainer
(E) and either A or B component.
Advances in Chemistry and Chemical Engineering 64

c. A maximum-temperature binary azeotrope exists between Entrainer

(E) and either A or B component.
d. There might be a ternary azeotrope.
Above four rules are applied for homogenous batch distillation but for
heterogeneous batch distillation additional two rules are suggested by Rodriguez
et. al.(2001) [10] which are listed below.
a. E is not miscible with one of component of the original mixture
(either A or B).
b. E forms minimum temperature heteroazeotrope with A or B.
The above rules are established by some scheme which is briefly explained by
Rodriguez et. al.(2001) [10].
For esterification reaction in reactive distillation, Jong et. al. [11] concluded that
the entrainer used in the process should fulfil the following criteria,
a. It should increase the relative volatility of water compare to alcohol;
water removed from the top and reaction equilibrium shifts to product
side.
b. It shoud be insoluble with water, then the distillate can easily separated
using decanter in two phases (i.e. as entrainer phase and aqueous phase)
c. It should have low solubility of entrainer in water, such that no further
purification is necessary.
d. It should have low solubility of water in entrainer, such that entrainer can
be used as a recycle.
Above criteria is applied only for specific esterification process but we can also
follow this criteria in which water is used as reactant. Effects of various
entrainers on different polarity can be investigated using above criteria.
65 Advances in Chemistry and Chemical Engineering

Figure 1.1: Entrainer based reactive distillation (Jong et.al. 2006)

5. CONCEPT OF VAPOUR LIQUID EQUILIBRIUM

When entrainer is added to binary mixture, ternary mixture results, for this
vapour liquid equilibrium is necessary to consider for predicting composition of
overhead and bottom product. VLE diagram is used to solve problems related to
separation. VLE is used identify and evaluate thermodynamic state, properties of
mixture and composition of the liquid and vapour in that mixture. The vapour
liquid equilibrium diagrams are constructed at either constant pressure or at
constant temperature [12]. The low boiling component at high temperature forms
superheated vapour and at low temperature it forms sub-cooled liquid. In
between that vapour and liquid both are present which are in equilibrium with
each other. The general vapour liquid equilibrium diagram of binary mixture at
constant pressure is illustrated in below fig 1.2 [12]. Vapour-liquid equilibrium is
also constructed as X-Y diagram. The X-Y diagram of binary mixture which
forms azeotrope is differs from the ideal binary mixture diagram [13].
A liquid can split into two different partially miscible or immiscible phases. Two
separate phases are formed to lower the Gibbs free energy of the system and this
leads to liquid-liquid equilibrium. Vapour liquid-liquid equilibrium occurs when
pressure of the system decreased with both liquid-liquid (LL) equilibrium and
vapour-liquid-liquid (VLL) equilibrium. The VLLE diagram has same properties
as that of LLE diagram.
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Figure 1.2: vapour liquid equilibrium T-x-y phase diagram (koretsky 2004)
67 Advances in Chemistry and Chemical Engineering

Figure 1.3: (a) vapour-liquid x-y diagram for ideal binary mixture (b) vapour-
liquid x-y diagram for binary mixture that forms an azeotrope. (Seader and
Henley 2006)

6. RESIDUE CURVE MAPS

Residue curve map (RCM) analysis is useful for the selection of entrainer for
azeotropic and extractive distillation. RCM is geometric representation of vapour
liquid equilibrium (VLE) phase behaviour of multi-component mixture which
consists of collection of residue curve and trajectories compositions of
components with respect to time. The boiling points of pure components, binary,
ternary or multi-component mixture indicated on the diagram. The composition
trajectories move from lightest component to the heavy component i.e. the
temperature continually increases to as the liquid gets richer in heavier
component. Temperature indicated by arrow on residue curve from lighter
component to heavier component. The nature of RCM changes with extent of
reaction i.e. depending upon the reaction kinetics. These curves can be
determined either experimentally or by mathematical simulation of the
experiment. The rules and construction of residue curve map is already described
[14]

Consider a ternary mixture of component A, B, C forms two binary azeotrope

and no ternary azeotrope. The pure component and their temperature are marked
on vertices; azeotrope (binary or ternary) and their temperature are also marked
on residue curve. The residue curve originates at lightest boiler (azeotrope AB)
which goes in the direction of heavier component B or C creating imaginary
Advances in Chemistry and Chemical Engineering 68

boundary connecting the two binary azeotropes. The dividing curve is called a
distillation boundary [14].
The presence of azeotrope dividing composition space into distillation regions by
distillation boundary such that residue curve in different regions go toward
different components. For multi-component mixture, multiple distillation
boundaries may exit. These distillation boundaries begin at same point but end at
different points (i.e. different regions) and vice versa.
Evolution of Feasibility of entrainer using RCM technique consists of step wise
procedure which is explained briefly. First construct the RCM for given multi-
component mixture consisting of azeotropic component and the given candidate
entrainer. Next, check the phase behaviour of the system, whether it is liquid-
liquid or vapour-liquid phase. The tie-lines indicate the two phase compositions.
Then draw an envelope over the RCM composition space, superimposing the
composition scale rather than temperature scale.
There are some criteria to evaluate the feasibility of entrainer using RCM
techniques which are given below [1].
1. Arrange the list of components and candidate entrainer
2. Prepare an RCM for each candidate entrainer: To construct RCM for the
system of A, B, and the candidate entrainer, requires thermodynamic
physical property.
a. If it is not available then modelled using UNIFAC, provided the
predictions are in agreement with available azeotrope data.
b. If no physical property model is available, then construct RCM using
available azeotropic temperature, composition (approximate), and
solubility (approximate) data.
c. If neither physical property nor azeotropic data available then
required information can be calculated using guessing or calculated
experimentally.
3. Determine the feasibility of candidate entrainer from the structure of the
RCM:-
a) The entrainer does not divide components (A and B) to be
separated into different distillation regions.
b) The entrainer induces liquid-liquid phase separation; there exists
liquid-liquid equilibrium tie line crossing distillation boundary.
69 Advances in Chemistry and Chemical Engineering

4. Evaluate all separation sequences: - number of distillation column with

decanters and also their interconnections from the RCM of system for all
feasible entrainer.
5. Determine the most promising entrainer for given feasibility conditions.
6. Design, stimulate and optimize separation sequences.

It has been mentioned here one example for understanding the RCM plot for
dimethoxyethane /ethanol mixture separation using water as an entrainer.

Figure 1.4: RCM plot for water-ethanol-DEM system [1].

Here, they have assumed 50:50 mol percentages of DEM and ethanol in the
process.
The system consists of three binaries azeotropes and a ternary azeotrope with
three distillation boundaries and multiple liquid phase regions. In this process, a
minimum boiling homogeneous azeotrope is breakdown by means of water.
Ternary azeotrope does not lie in the multiple liquid phase region, because of this
the separation is not that much feasible to that extent of the maximum separation.
Advances in Chemistry and Chemical Engineering 70

So here, RCM gives a significant approach towards separation with water with
more number of distillation sequences [1].

7. CONCLUSION
To understand the behaviour of the separation process of any reaction system, it
is very important to know the VLE and RCM strategy for the screening of
entrainer. In this chapter we focus on the different procedures for selection of
entrainer for different distillation methods. For a good separation, knowledge of
distillation regions, boundaries and tie line plays a vital role. With VLE, VLLE is
also necessary to predict the nature of the curvature of the residue maps. For a
good design of distillation process, a selection criterion of entrainer / solvent is
the main step, which is involved in this review chapter.

REFERENCES:
[1] Julka V., Chiplunkar M., O’Young L., 2009, “Selecting Entrainers for
Azeotropic Distillation”, AICHE, pp. 47-53
[2] Rodriguez-Donis I., Gerbaud V., and Joulia X., 2001, “Entrainer
Selection Rules For the Separation of Azeotropic and Close-Boiling
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[3] Laroche L., Bekiaris N., Andersent W. And Moraris M., 1991
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[6] Doherty M. F. and Malone M. F., 2001 “Conceptual Design of

Distillation System”, Mcgraw-Hill, New York, pp. 568
[7] Matsuyama H. and Nishimura H., 1977, “Topological And
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Journal Of Chemical Engineering of Japan, Vol 10(3) , pp. 181-187
71 Advances in Chemistry and Chemical Engineering

[8] Bernot C., Doherty M., and Malone M., 1992 “Feasibility and Separation
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[11] De Jong M. C., Dimian A. C., Kuipers N. J. M. and De Haan A. B.,
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[12] Koretsky, M.D. 2004, “Engineering and chemical thermodynamics”,
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