Theoretical Foundations of Chemical Engineering, Vol. 39, No. 1, 2005, pp. 16–23.

Translated from Teoreticheskie Osnovy Khimicheskoi Tekhnologii, Vol. 39, No. 1, 2005, pp. 19–26.
Original Russian Text Copyright © 2005 by Ivanova, Timoshenko, Timofeev.

Synthesis of Flowsheets for Extractive Distillation

of Azeotropic Mixtures
L. V. Ivanova, A. V. Timoshenko, and V. S. Timofeev
Lomonosov State Academy of Fine Chemical Technology, pr. Vernadskogo 86, Moscow, 117571 Russia
E-mail: ilv79@mail.ru
Received April 23, 2004

Abstract—An algorithm for synthesizing extractive distillation flowsheets for separation of complex ternary
azeotropic mixtures with different vapor–liquid equilibrium patterns is proposed.

Separation of end fractions of given compositions
from azeotropic mixtures is complicated by thermody-
namic and topological constraints, which can be sur-
mounted using the principle of redistribution of con-
centration fields between separation regions [1–3]. This
principle can be implemented using homogeneous and
heterogeneous (involving extraction, adsorption,
absorption, and chemical and other separation tech-
niques) separation systems. In homogeneous systems,
distillation can be designed so that, at one of the steps,
an azeotropic fraction is isolated, which is then sepa-
rated by special methods. If this fraction contains two
or more components, one can use extractive distillation
or separation of the azeotropic mixture at different
pressures. If the fraction contains more than two com-
ponents, separation can be performed by methods using
the curvature of the separating manifold [3, 4]. Previ-
ously [2, 5], a general approach to synthesizing flow-
sheets for distillation of multicomponent nonideal
(including azeotropic) mixtures was put forward, which
is based on the concept of a distillation region. Later
[6–8], some approaches to synthesizing flowsheets for
distillation of multicomponent mixtures containing a
single binary azeotrope were proposed, which use sep-
aration of an azeotropic mixture at different pressures.
Note that, in practice, thermodynamic and topolog-
ical constraints on separation of end fractions of given
compositions are most often surmounted by using
extractive distillation. However, conventional extrac-
tive distillation methods are highly energy-intensive.
Therefore, it is topical to develop and use optimal
energy-saving technologies. This problem is solved in
several steps:
structural optimization of a flowsheet,
optimization of the operating parameters of distilla-
tion columns,
design optimization of flowsheet elements.
Since distillation is irreversible, its thermodynamic
efficiency depends on the process path—a set of flow-
sheets or distillation trajectories. To date, approaches to
synthesizing extractive distillation flowsheets have
been developed obviously insufficiently. This question
was considered only in few works. For example, a num-
ber of systems of different structures for separation of
multicomponent azeotropic mixtures were proposed
[9]. Certain technological solutions for distillation of an

(‡) (b)
A B A
F F

S
S B
(c) (d) (e) (f) (j)
A B C A B
A B A A C
F F
F F F
S C B B S
S S C
S C

Fig. 1. Flowsheets for separation of (a, b) ternary and (c–g) quaternary zeotropic mixtures: A, B, C are components of a mixture; S
is a low-volatile extractant; F is feed (a, b) ABS and (c–g) ABCS.

0040-5795/05/3901-0016 © 2005 MAIK “Nauka /Interperiodica”

 SYNTHESIS OF FLOWSHEETS FOR EXTRACTIVE DISTILLATION
A B C A
F S
S
Fig. 2. Representation of the distillation flowsheet in Fig. 1c
as the orgraph L. The nodes represent columns (empty cir-
cles) and fractions (filled circles).
(‡) (b)
A B C A
Fn Fn
S S
Fig. 4. Graph U obtained by merging two nodes S (repre-
senting fractions) of the graph M.
ethanol–water mixture were presented [10]. However,
thermodynamic and topological constraints on the
compositions of the products were not always taken
into account and the proposed solutions are inoperable.
Thus, structural optimization of extractive distillation
currently remains virtually beyond the scope of consid-
eration. Solving this problem is expediently begun
from developing general algorithms for synthesizing
flowsheets of this class. Within such a problem formu-
lation, one can analyze not only distillation systems
involving columns from which the products are with-
drawn from two points, but also more complex struc-
tures with partially coupled heat and material flows.
However, early in our consideration, we restrict our-
selves to synthesizing a flowsheet for distillation of ter-
nary azeotropic mixtures in systems of two-point with-
drawal columns.
By now, extractive distillation flowsheets have been
classified. All the possible variants of separation can be
divided into two large classes [9]. The first class
includes flowsheets in which an extractant is used as far
upstream as the first column of a distillation system
and, consequently, thermodynamic and topological
constraints on the compositions of the product fractions
are lifted. In flowsheets of the second class, the initial
multicomponent mixture is predistilled until a fraction
of azeotrope-forming components is isolated, which is
then separated by extractive distillation. Taken
together, the two classes encompass all the possible
variants of separation. Flowsheets of the first class for
distillation of mixtures with low dimensionality of the
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
17
B C
Fn
S
Fig. 3. Graph M obtained by splitting the node F of the
graph L.
(‡) (b)
B C
A B A
Fn Fn
S
S B
Fig. 5. Graphs corresponding to flowsheets for extractive
distillation of an A–B binary azeotropic mixture.
concentration space can be used as elements of separa-
tion of mixtures in the second class of flowsheets for
mixtures of higher dimensionality.
Let us consider an algorithm for synthesizing flow-
sheets of the first class. Introduction of an extractant
lifts the thermodynamic and topological constraints on
the compositions of the product flows; therefore, as
prototypes for synthesis, we use sets of flowsheets for
distillation of zeotropic mixtures in simple two-section
columns. Let the object of separation be an (n + 1)-
component mixture consisting of an n-component ini-
tial azeotropic mixture and an extractant. Let us assume
that the extractant is the least volatile component of the
mixture.
Figure 1 presents the flowsheets for distillation of
ternary and quaternary zeotropic mixtures. For further
analysis, we represent them as oriented graphs in which
nodes characterize columns and fractions, and edges
describe flow relationships between them. Let the
nodes that characterize the fractions be labeled with the
corresponding letters. For example, the flowsheet in
Fig. 1c is represented by the graph in Fig. 2. The graph
in Fig. 2 describes the separation sequence. The next
step of the synthesis is to split the flow F of the (n + 1)-
component mixture into two individual flows: the
n-component mixture Fn and the extractant S. Formally,
if we start from the graph L in Fig. 2, we will obtain the
graph M in Fig. 3. This structure already almost fully
represents the extractive distillation flowsheet. It is only
necessary to create a cycle for the extractant S by merg-
Vol. 39 No. 1 2005
18 IVANOVA et al.

(a) (b) (c) (d) (e)

A B C A S C S A B S C A A

F F F F F C

S B C B S

(f) (j) (h) (i) (g)

A B C A S C S A B S C A A

F F F F F C

S B C B S

(k) (l) (m) (n) (o)

A B C A S C S A B S C A A

B
Fn C
Fn Fn Fn Fn

S B C B S

Fig. 6. Synthesis of graphs corresponding to extractive distillation flowsheets.

ing two nodes (characterizing the fractions) labeled
with S. We will obtain the graph U in Fig. 4.
Note that, depending on the vapor–liquid equilib-
rium pattern, more than one edge may leave the node S
(the extractant may also be necessary for separating the
mixture in the second column of the system) (Fig. 4b).
The extractant S is assumed to ensure separation of the
entire n-component mixture into pure components.
Since the extractive distillation system has a closed
(without taking into account losses) cycle for the
extractant, one of the conditions of operability of flow-
sheets synthesized using the proposed algorithm is the
presence of a cycle in the orgraph. By a cycle, we mean
the possibility of passing through a number of graph
nodes and returning to the starting node with allowance
for the orientation of edges. A cycle must include at
least two nodes representing columns. A second condi-
tion of operability of the proposed flowsheets is the
introduction of the extractant into the column in which
an azeotropic pair of components is separated.
Let us consider the simplest example, namely, sepa-
ration of an A–B binary azeotropic mixture. Obviously,
for the given type of flowsheets, the extractant must be
introduced into the first separation column; therefore,
Fig. 5 presents only such variants. It is seen that the first
operability condition is satisfied only by the graph in
Fig. 5a. The structure of this graph fully corresponds to
the classical flowsheet for extractive distillation of a
binary azeotropic mixture with a low-volatile extract-
ant.
The example considered is trivial. Therefore, let us
present our algorithm and illustrate it by the example of
separation of a ternary azeotropic mixture.
(1) Choose a vapor–liquid equilibrium pattern
according to Serafimov’s classification (Table 1) [11].
As an example, we consider a pattern of type 3.1.1 t1a
with direct orientation of distillation lines.
(2) Synthesize flowsheets for distillation of a quater-
nary zeotropic mixture (Figs. 1c–1g) and represent
them as orgraphs of the L type (Figs. 6a–6e).
(3) In flowsheets of the set obtained (Figs. 6a–6e),
select and label nodes to which an edge from the node
S (representing the extraction column) should be
directed. For the selected type of extractive distillation
flowsheets, these nodes describe the columns that are
the first in the separation sequence (filled circles).

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 39 No. 1 2005

 SYNTHESIS OF FLOWSHEETS FOR EXTRACTIVE DISTILLATION 19

Table 1. Types of phase diagrams of ternary azeotropic mixtures with direct and reverse orientation of distillation lines
Diagram type Direct Reverse Diagram type Direct Reverse
A C A

3.1.0 t1a 3.2.1 t3a

B C B A B C
A C A C

3.1.0 t1b 3.2.1 t3b

B C B A B C B A
C A C A

3.1.0 t2 3.3.0 t1a

B A B C B A B C
A C A A

3.1.1 t1a 3.3.0 t1b

B C B A B C B C
C A C A

3.1.1 t1b 3.3.0 t2

B A B C B A B C
A A A

3.2.0 t1 3.3.1 t1b

B C B C B C
A C A A

3.2.0 t2a 3.3.1 t1c

B C B A B C B C
A C A A

3.2.0 t2b 3.3.1 t2

B C B A B C B C

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 39 No. 1 2005

20 IVANOVA et al.

Table 1. (Contd.)
Diagram type Direct Reverse Diagram type Direct Reverse
A C A A

3.2.0 t2c 3.3.1 t3a

B C B A B C B C
C A A A

3.2.1 t1 3.3.1 t3b

B A B C B C B C
A C A A

3.2.1 t2a 3.3.1 t4

B C B A B C B C
A C

3.2.1 t2b

B C B A

(4) Split the node F into nodes Fn and S and remove
the node S incident to the incoming edge. This opera-
tion is equivalent to replacement of the node F by Fn.
(5) Connect the node S to the labeled node (repre-
senting the extraction column) with an oriented edge
leaving the node S and check the obtained structures
(Figs. 6k–6o) for operability.
Of five graphs obtained, only two (Figs. 6k, 6l) meet
the operability conditions. They correspond to quite
trivial flowsheets in Fig. 7.
Analyzing the graphs in Fig. 6, one can reveal a cer-
tain set of flowsheets whose operability depends only
on the phase portraits of the corresponding distillation
systems. These are the graphs in Figs. 6k, 6l, and 6o. In
A B C A
ABC ABC
S S
Fig. 7. Operable flowsheets for the vapor–liquid equilib-
rium pattern of type 3.1.1 t1a.
the corresponding flowsheets, there is extractant recir-
culation, and their applicability is determined by the
vapor–liquid equilibrium pattern. Therefore, when ana-
lyzing structures for phase diagrams of different types,
we further consider only these variants. In the flow-
sheets corresponding to the graphs in Figs. 6m and 6n,
there is no extractant recirculation, and these flowsheets
do not meet the operability conditions.
Let us consider an algorithm for synthesizing
extractive distillation flowsheets of the second class. In
this case, the first step is the distillation of the initial
mixture; therefore, for all the flowsheets of this class,
the extractant is used at any separation step other than
the first. Below are the main steps of the algorithm.
(1) Determine the type of the phase diagram. As an
example, we will consider the same vapor–liquid equi-
librium pattern of type 3.1.1 t1a with direct orientation
B of distillation lines.
(2) Synthesize flowsheets for distillation of a quater-
nary zeotropic mixture. When determining the
C sequence of separation of components, it is necessary
to consider the possibility of distilling the initial mix-
ture into an azeotropic constituent and a zeotropic con-
stituent. It is seen that the component C can also be iso-
lated without using extractive distillation. Of the five

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 SYNTHESIS OF FLOWSHEETS FOR EXTRACTIVE DISTILLATION 21

(‡) (b) (c) (d)

F1 A B F1n A B F1 A B

A B

ABC

F F
F S
S
C S
C S C S C

Fig. 8. (a–c) Graphs and (d) flowsheet for extractive distillation.

possible separation variants proposed, only one flow-
sheet (Fig. 8) meets this condition.
(3) Determine and label graph nodes to which an
edge from the node S (representing the extraction col-
umn) should be directed. For the selected type of
extractive distillation flowsheets, these nodes describe
the columns where azeotrope-forming components are
separated.
(4) Design extractant recirculation. In this case, add
a node corresponding to the introduction of the extrac-
tant into the column of separation of an azeotropic pair
of components. In Fig. 8b, such a node is labeled by S.
(5) Check the obtained structures for operability.
Among extractive distillation flowsheets of the sec-
ond class, some variants of process design can also be
a priori discarded. These are the flowsheets in Figs. 1d,
1f, and 1g. In the flowsheets in Figs. 1d and 1f, with
allowance for the separation of the zeotropic constitu-
ent of the mixture in the first column, the extractant is
withdrawn upstream of the point of separation of the
azeotropic pair of components. To implement the flow-
sheet in Fig. 1g, in the case of precise distillation, the
initial mixture must contain at least four components.
Thus, using the algorithm proposed, for separation
of the ternary mixture described by the vapor–liquid
equilibrium pattern of type 3.1.1 t1a with direct orien-
tation of distillation lines, we synthesized three opera-
ble extractive distillation flowsheets (Fig. 7, Fig. 8d).
(‡)
Two of them belong to the first class of flowsheets, in
which azeotrope-forming components are separated in
the first column and extractive distillation is used start-
ing with the first column; the third flowsheet belongs to
the second class of flowsheets, in which the initial mix-
ture is predistilled.
Let us consider the same vapor–liquid equilibrium
pattern of type 3.1.1 t1a but with reverse orientation of
distillation lines. We will not dwell on algorithm steps
in detail but will consider its results. It is seen that, in
this case, the algorithm leads to other operable flow-
sheets (Fig. 9). The flowsheet in Fig. 9a belongs to the
first class of extractive distillation flowsheets and has
quite an unconventional structure, and the flowsheet in
Fig. 9b belongs to the second class of flowsheets, in
which the zeotropic constituent is preseparated.
Thus, the selection of flowsheets for separation of
azeotropic mixtures is a complex problem, which
involves the investigation of the vapor–liquid equilib-
rium pattern and the analysis of all the possible variants
of flowsheets. Therefore, we further consider the possi-
bility of applying some flowsheets or others by the
example of known types of phase diagrams of ternary
(‡) (b) (c)
A B C A B
A C
F F F
B S
(b) S S
C

A ë A B ë (d) (e)
A B C A B
ABC ABC

B F F
S S
S C S

Fig. 9. Flowsheets for the vapor–liquid equilibrium pattern

of type 3.1.1 t1a with reverse orientation of distillation Fig. 10. Flowsheets of the (a–c) first and (d, e) second class
lines. of extractive distillation flowsheets.

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 39 No. 1 2005

22 IVANOVA et al.

A B C A B C

ABC ABC

S S S

Fig. 11. Separation flowsheets for complex vapor–liquid equilibrium patterns.

mixtures. Earlier, we determined the flowsheets that out using an extractant. These are types 3.1.2 t1b and
can be implemented, depending on the type of phase 3.1.1 t1b. Within the concentration simplexes corre-
diagram of a mixture being separated (Fig. 10). The sponding to these types, a single bundle of distillation
results of analyzing these variants are presented in lines develops. This makes possible the separation of
Table 2. In addition, there are two types of phase dia- the pure components A, B, and C in a sequence of two
grams for which separation can also be performed with- distillation columns.
Note that, in each particular case, it is necessary to
carefully study the applicability of a separation variant.
Table 2. Operability of flowsheets in Figs. 10a–10e for var- For example, for a number of vapor–liquid equilibrium
ious types of phase diagrams with direct/reverse orientation patterns (3.2.0 t2b, 3.2.0 t2c, 3.2.1 t2b, 3.2.1 t3b,
of distillation lines when, in the first column, (I) an extractant
is used and (II) the initial mixture is distilled 3.3.0 t2, 3.3.1 t3b), flowsheets of the second class are
implementable only when the initial feed composition
I II belongs to a certain distillation region of the concentra-
Diagram
type tion simplex. For example, for the system characterized
10a 10b 10c 10d 10e by the vapor–liquid equilibrium pattern of type
3.1.0 t1a +/+ +/– –/+ –/+ +/– 3.2.0 t2b with direct orientation of distillation lines,
distillation of the initial mixture (isolation of the com-
3.1.0 t1b +/+ +/+ +/+ –/+ +/– ponent C) is possible if the initial feed composition
3.1.0 t2 +/+ +/– –/+ –/+ +/– belongs to the region AzÄÇ–B–C–AzÄë and the compo-
3.1.1 t1a +/+ +/– –/+ –/+ +/– sition of the distillate of this column corresponds to the
3.1.1 t1b +/+ +/+ +/+ +/– –/+
segment B–AzÄÇ.
3.1.1 t2 +/+ +/– –/+ –/– –/– As noted above, the operability of a flowsheet is
3.2.0 t1 + + – – – determined by the presence of a cycle in the corre-
sponding orgraph. The direction of the edge represent-
3.2.0 t2a +/+ +/– –/+ –/+ +/– ing the extractant recirculation is determined by the
3.2.0 t2b +/+ +/+ –/– –/+ +/– vapor–liquid equilibrium pattern of the initial mixture.
3.2.0 t2c +/+ +/+ –/– –/+ +/– The extractant must be directed only to the column
3.2.1 t1 +/+ –/+ +/– –/– –/–
(columns) in which the extractant is necessary for sep-
aration of the mixture. In the case of a complex vapor–
3.2.1 t2a +/+ +/– –/+ –/+ +/– liquid equilibrium pattern (3.1.1 t2, 3.2.1 t1, 3.2.1 t2b,
3.2.1 t2b +/+ +/– –/+ –/+ +/– 3.3.0 t1a, 3.3.0 t1b, 3.3.0 t2, and also all the subtypes of
3.2.1 t3a + + – – – 3.3.1), the extractant must be introduced simulta-
neously into two columns of the distillation system.
3.2.1 t3b +/+ +/+ –/– –/– +/– Therefore, such process design should always be com-
3.3.0 t1a +/+ –/– –/– –/+ +/– pared with two consecutive extractive distillation sys-
3.3.0 t1b +/+ –/– –/– –/– –/– tems for revealing the most efficient solution (Fig. 11).
3.3.0 t2 +/+ –/– –/– –/+ +/– Thus, we have developed a universal algorithm for
3.3.1 t1a +/+ –/– –/– –/+ +/– synthesizing flowsheets for extractive distillation of
3.3.1 t1b +/+ –/– –/– –/– –/– multicomponent azeotropic mixtures, which is based
on the use of flowsheets for distillation of zeotropic
3.3.1 t1c +/+ –/– –/– –/– –/– mixtures in simple two-section columns as prototypes
3.3.1 t2 +/+ –/– –/– –/– –/– of extractive distillation flowsheets. This algorithm
3.3.1 t3a +/+ –/– –/– –/– –/– should be applied at the step of structural optimization
of distillation flowsheets for reducing the energy con-
3.3.1 t3b +/+ –/– –/– –/– +/–
sumption for separation. It was noted that the operable
3.3.1 t4 +/+ –/– –/– –/– –/– flowsheets thus obtained should be subjected to further

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 39 No. 1 2005

 SYNTHESIS OF FLOWSHEETS FOR EXTRACTIVE DISTILLATION
analysis and discrimination for applicability to a partic-
ular separation problem.
ACKNOWLEDGMENTS
This work was supported by the Russian Foundation
for Basic Research, project no. 04-03-32987.
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