Chemical Engineering Science 56 (2001) 4417– 4432

www.elsevier.com/locate/ces

Multicomponent homogeneous azeotropic distillation

3. Column sequence synthesis
Dennis Y.-C. Thong ∗ , Megan Jobson
Department of Process Integration, UMIST, PO Box 88, Manchester M60 1QD, UK

Received 27 April 2000; received in revised form 2 February 2001; accepted 19 February 2001

Abstract
An algorithmic distillation column sequence synthesis procedure for multicomponent azeotropic mixtures is proposed. The
synthesis procedure is divided into several stages, and makes use of the feasibility test for classes of splits, as de6ned by Thong
and Jobson (Chem. Eng. Sci. (2001a) submitted), to systematically generate a range of feasible and potentially feasible column
sequences for a speci6ed separation requirement. A set of rules is applied to generate a recycle superstructure for every identi6ed
sequence. Stream compositions and recycles are then 6nalised. Column design methods presented in Thong and Jobson (Chem.
Eng. Sci. (2001b) submitted) are then applied to every column in the sequence. ? 2001 Elsevier Science Ltd. All rights reserved.

Keywords: Distillation; Azeotropic; Multicomponent; Sequence synthesis; Recycles; Boundary crossing

1. Introduction A variety of column sequencing methods (Wahn-

All distillation sequencing techniques for non-
azeotropic mixtures are sequential in nature, i.e., all splits
are identi6ed for a given feed composition and quality.
All further splits are then identi6ed for every product
stream from all the possible 6rst splits. The process
continues until no further splits are possible. This se-
quential approach is a comprehensive way of identifying
all feasible column sequences that do not have internal
recycles. The presence of recycle streams in the column
sequence breaks down the ordered procession of splits
and changes the nature of the problem from sequential to
iterative.
Ternary and quaternary diagrams allow the mixing
and splitting material balances to be represented graphi-
cally, thereby facilitating an intuitive solution to complex
sequencing problems with three or four component
mixtures. While being a useful tool for three and four
component mixtures, graphical representation of higher
dimensional composition spaces is not possible. The lack
of visual aids therefore complicates column sequencing
in mixtures with more than four components.
∗ Corresponding author. Tel.: +44-161-200-4381; fax: +44-161-
236-7439.
scha=t, Le Rudulier, & Westerberg, 1993; Bauer &
Stichlmair, 1998; Rooks, Julka, Doherty, & Malone,
1998) have been proposed for the separation of multi-
component azeotropic mixtures. None of these methods
require visual aids and are, in theory, applicable to mix-
tures with any number of components. All these methods
are sequential, with stream compositions determined at
each successive step. This approach limits the number of
sequences that can be generated as there are restrictions
on feasible products from a column with a completely
speci6ed feed stream (Wahnscha=t, Koehler, Blass,
& Westerberg, 1992; Fidkowski, Doherty, & Malone,
1993).
In this work a column sequence synthesis procedure is
developed for application to multicomponent azeotropic
mixtures. The synthesis procedure uses feasible and po-
tentially feasible classes of splits, de6ned in Thong and
Jobson (2001a) as splits producing product regions, or
sets of product compositions. Synthesis is carried out se-
quentially, with each product region being the feed to
the next split. Because precise stream compositions do
not have to be speci6ed, the feed regions (product re-
gions from the previous split) only serve to constrain the
split to lie in certain zones in the composition space, in
which many di=erent splits are possible. This approach

0009-2509/01/$ - see front matter ? 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 1 ) 0 0 0 5 7 - 4
4418 D.Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4417– 4432
also makes full use of the potential bene6ts from recy-
cling for the manipulation of feed compositions.
2. Background
Wahnscha=t et al. (1993) present a general synthesis
methodology for the separation of multicomponent mix-
tures. The methodology is sequential in nature, and makes
use of process simulations to determine product compo-
sition ranges for a speci6ed feed composition. Recovery
and purity speci6cations are represented by pseudobinary
‘separation tasks’, one for every binary pair in the mix-
ture. The methodology starts by sequentially identifying,
by repeated process simulations, all the possible column
sequences for a given feed composition. Some splits are
then combined, and recycles are assigned. Because recy-
cles alter the feed compositions and Fow rates to process
units, the relevant units will normally have to be simu-
lated again, until the Fowsheet simulation converges. The
synthesis methodology is applicable to processes involv-
ing any type of unit operation, and is, in principle, applica-
ble to the separation of n-component mixtures, although
its implementation su=ers when there are more than three
components in the mixture as obtaining the appropriate
recycle compositions becomes diGcult. The methodol-
ogy can miss interesting sequences because of the use of
the pseudobinary representation of stream compositions
and splits which, in azeotropic mixtures, does not convey
the full extent of the limits imposed by non-ideal VLE
on the unit operations. This limitation is compounded
by the use of process simulations to determine product
compositions—some feasible splits will not be identi6ed
as the (distillation) simulations are carried out at large
reFux ratios.
Bauer and Stichlmair (1998) develop a superstruc-
ture of columns, each of which performs a ‘preferred
separation’, which is a thermodynamically ideal separa-
tion. A ternary example is illustrated in Fig. 1. A preferred
separation is performed in an adiabatic column, which is
not the same as a reversible separation. Starting with a
speci6ed feed composition, a series of preferred separa-
tions is identi6ed. This series forms the superstructure,
which is then optimised using mixed integer non-linear
programming routines, the objective being the minimi-
sation of the total annualised cost. Recycle streams are
determined prior to the optimisation step (Fig. 1). This
necessarily requires the user to specify mixing operations
and therefore necessitates some understanding of the lim-
its imposed by the non-ideal VLE. Ternary and quater-
nary residue curve maps are used to aid the selection of
suitable recycling options for three and four-component
mixture. The application of the method to mixtures con-
taining more than four components is therefore depen-
dent on the existence of an appropriate recycling scheme,
which they do not attempt to develop. The application
of computationally intensive MINLP routines to complex
superstructures separating n-component mixtures, where
the size of the superstructure is potentially overwhelm-
ing, is a further limitation of the method. To overcome
this limitation, the authors simplify the superstructures
by combining some splits in the complex superstructure.
Although this simpli6cation reduces the size of the prob-
lem, there is no guarantee of the solution quality as clear
guidelines for combining splits do not exist.
The ‘common saddle test’ (Rooks et al., 1998) for col-
umn feasibility requires the composition pro6les from
both speci6ed product compositions to approach the same
saddle at total reFux. This behaviour is inferred from
the reachability matrix (Knight & Doherty, 1990). Re-
peated application of the common saddle test to a speci-
6ed feed composition yields a variety of feasible column
sequences within the distillation region that contains the
feed composition. Recycling is not accommodated, al-
though an algorithm to determine feed compositions that
allow complete recovery of a component is presented in
Rooks et al. (1998). The sequencing procedure does not
incorporate any information on optimality since column
design is not performed. The common saddle criterion is
a suGcient condition for split feasibility. Thus, the cri-
terion precludes other feasible splits (Thong & Jobson,
2001a), resulting in the procedure missing some poten-
tially promising feasible column sequences.
3. Distillation column sequence synthesis procedure
3.1. Problem speci5cation
The 6rst step in any sequencing procedure is the spec-
i6cation of the problem. After the feed composition has
been identi6ed, the adjacency and reachability matrices
can be calculated using methods outlined in Knight and
Doherty (1990). The distillation regions and boundaries
can then be identi6ed (Rooks et al., 1998). The desired
products are then speci6ed. A simple check will reveal if
the feed and products are in di=erent distillation regions.
Section 3.5 describes a variation of the sequence synthesis
procedure that includes columns that straddle boundaries.
Other boundary crossing techniques, e.g., phase split-
ting, liquid–liquid extraction, and boundary shifting by
changing the operating pressure or mass transfer regime
(Castillo & Towler, 1998) are not accounted for here, al-
though they can be incorporated in the general synthesis
framework. The procedure continues at the next stage in
the absence of a distillation boundary between the feed
and product compositions. The problem speci6cation is
summarised in the following algorithm:
1. Identify the mixture and feed composition.
2. Calculate all azeotropes in the mixture (Fidkowski
et al., 1993).
 D.Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4417– 4432
Fig. 1. A complex superstructure of preferred splits, as represented on a ternary diagram. A preferred split is formed by extending the vector
joining a liquid composition x, with the vapour composition in equilibrium with it, y∗ (Bauer and Stichlmair, 1998).
3. Calculate the adjacency and reachability matrices
(Knight & Doherty, 1990).
4. Identify all distillation regions and boundaries (Rooks
et al., 1998).
5. Identify all distillation compartments (Thong & Job-
son, 2001a).
6. Determine which distillation region the feed lies in
by calculating a residue curve from the feed com-
position. Assuming linear compartmental boundaries,
determine geometrically the compartment which con-
tains the feed composition (Thong, 2000).
7. Specify the desired products or components to be re-
covered.
8. See Section 3.5 if a distillation boundary separates the
feed from one or more of the desired products. If not,
proceed to Section 3.2.
An equimolar mixture of methyl acetate, methanol,
ethanol and isopropanol is to be separated into its con-
stituent components. Fig. 2 shows the quaternary dia-
gram, adjacency and reachability matrices, and lists the
distillation regions, boundaries and compartments. One
binary minimum-boiling azeotrope exists. All four com-
ponents are to be recovered, and because no distillation
boundary exists in the mixture, no boundary crossing
is required. The feed composition lies in the (1-3-4-5)
compartment.
3.2. Preliminary screening of column sequences
The sequence synthesis procedure exploits the fact that
internal recycle streams allow the manipulation of the
feed compositions to any column in the sequence. Pre-
vious approaches to the synthesis problem (Wahnscha=t
et al., 1993; Bauer & Stichlmair, 1998; Rooks et al.,
1998) only considered exact feed compositions to the
4419
various splits. Because the feed composition constrains
the range of feasible product compositions (Wahnscha=t
et al., 1992; Fidkowski et al., 1993), many feasible splits
will be overlooked. Instead of specifying splits sequen-
tially from 6xed feed compositions, the synthesis proce-
dure generates sequences of columns, each performing a
class of split (Thong & Jobson, 2001a). Precise composi-
tions are not speci6ed, and the feeds to the various splits
only serve to constrain the product regions from these
classes of splits to certain distillation regions or compart-
ments, and not to limited ranges of product compositions,
as do precise feed compositions.
Once all the feasible and potentially feasible classes of
splits for an n-component mixture have been identi6ed,
all possible column sequences are generated by recur-
sive searching, starting with (C-1)-dimensional splits
and ending with binary splits. The column sequences
that recover the desired components are accepted while
the others are rejected. A promising column sequence
can then be selected for further study. All stream com-
positions in all column sequences, except the overall
feed composition, do not have to be speci6ed at this
point. No recycling exists at this stage. The full al-
gorithm for screening feasible column sequences is as
follows:
1. Identify all (C-1)-dimensional and lower-dimensional
classes of splits using the algorithms in Thong and
Jobson (2001a).
2. Select either a (C-1)-dimensional split in the compart-
ment which contains the feed, or a cross-compartmental
split involving the feed compartment and an adjacent
compartment.
3. For the selected (C-1)-dimensional split identify the
sub-region (compartment) that the product regions lie
in.
4420 D.Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4417– 4432

Fig. 2. A quaternary diagram representing the composition space of a four-component azeotropic mixture. Also shown are the adjacency and
reachability matrices. The mixture displays one distillation region and two compartments.

4. For both product streams from the 6rst split, identify

all possible splits in the compartments in which these
products lie, as well as any cross-compartmental splits
involving adjacent compartments.
5. Repeat Step 4 for all further product streams. Stop
when no further splits are possible.
6. Combine any identical splits in di=erent parts of the
same sequence, i.e., combine feed streams to columns
performing the same class of split.
7. An intermediate stream that does not contain any de-
sired components can either be fed to any column or
left unseparated.
8. Repeat steps 2–5 for all (C-1)-dimensional splits in the Fig. 3. Separation tree for a 1=3-4-5 6rst split. In all cases the
feed compartment and cross-compartmental splits in- methyl acetate-methanol azeotrope (1), methanol (3), ethanol (4) and
volving adjacent compartments. This generates many isopropanol (5) are recovered. Superscripts denote the split type.
column sequences.
9. For each column sequence, determine if all desired partment, as well as the Type C splits between compart-
components are recovered. Accept the sequence if they ments can be selected to be the 6rst split. Enumeration of
are. Reject it otherwise. all these splits leads to a total of 46 di=erent potentially
Table 1 lists the feasible and potentially feasible classes feasible sequences, i.e., sequences where all four compo-
of splits identi6ed for the quaternary azeotropic mixture nents are recovered. Fig. 4 lists these potentially feasi-
presented in Section 3.1. All quaternary, ternary and bi- ble sequences. The asterisks indicate identical splits that
nary splits are listed and labelled according to split type. can be combined. All the sequences listed in Fig. 4 are
Type D splits are omitted in this example. potentially feasible as they all involve Type C splits—
To illustrate the screening algorithm, a 1=3-4-5 split is if the particular Type C split is infeasible, the sequence
arbitrarily selected (Step 2). The distillate composition becomes infeasible too.
is that of the azeotrope, so no further splits are possible
with this stream. The bottoms product lies in the (3-4-5) 3.3. Generating recycle options for a sequence of
compartment, in which three Type A splits are possible columns
(Table 1). Fig. 3 shows the separation tree corresponding
to the 1=3-4-5 split as the 6rst split. Once all potentially feasible sequences have been iden-
None of the options in Fig. 3 lead to the recovery ti6ed, suitable recycling options can be identi6ed using
of methyl acetate (2), which is a desired product. As a a simple procedure. First, a superstructure of recycling
result, this sequence is rejected. Instead of the 1=3-4-5 options is constructed. Every end product from a col-
split, any of the other quaternary splits in the feed com- umn (component, azeotrope or a stream with no desired
 D.Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4417– 4432 4421

Table 1
Feasible and potentially feasible classes of splits for the quaternary mixture in Fig. 2. Superscripts denote the split type

4-distillation 1-2-3-4-5
regions

Compartments C#1 C#2

(1-2-4-5) (1-3-4-5)

1=4-5A 1=4-5A
1=2-4-5A 1=3-4-5A
Quaternary 1-2=4-5A 1-3=4-5A
splits 1-2=2-4-5A 1-3=3-4-5A
(Types A & B) 1-2-4=5A 1-3-4=5A
1-2-4=4-5A 1-3-4=4-5A
1-2-4=2-4-5B 1-3-4=3-4-5B
C#1xC#2
Quaternary 1-2=3-4-5
splits 1-3=2-4-5
(Type C) 1-2-4=3-4-5
1-3-4=2-4-5

3-distillation 1-2-3-4 1-2-3-5 2-4-5 3-4-5

regions

Compartments C#1 C#2 C#3 C#4 C#5 C#6

(1-2-4) (1-3-4) (1-2-5) (1-3-5) (2-4-5) (3-4-5)

Ternary 1=4A 1=4A 1=5A 1=5A 2=4-5A 3=4-5A

splits 1=2-4A 1=3-4A 1=2-5A 1=3-5A 2-4=4-5A 3-4=4-5A
1-2=4A 1-3=4A 1-2=5A 1-3=5A 2-4=5A 3-4=5A
(Types A & B) 1-2=2-4A 1-3=3-4A 1-2=2-5A 1-3=3-5A

Ternary C#1xC#2 C#3xC#4

splits 1-2=3-4 1-2=3-5
(Type C) 1-3=2-4 1-3=2-5

Binary splits 1=2A 1=3A 2=4A 2=5A 3=4A 3=5A 4=5A

components) is a potential recycle stream. Every feed to a
column is a potential destination for every recycle stream.
The size of this superstructure is then reduced using a set
of rules, which are as follows:
1. Azeotropes can either be recovered, partially recov-
ered, or recycled completely.
2. Never recycle a stream to the column that produces it.
3. Never mix a recycle stream with a feed to a column
performing a split where the recycle stream contains
one or more components that are not present in either
product stream.
4. Never mix streams with compositions in di=erent com-
partments. The exception to this are recycle streams
to columns performing Type C splits, which can lie in
either compartment that the split traverses.
The 6rst rule accounts for di=erent requirements, e.g., the
azeotrope might be recycled to the reactor, or might be
recycled internally in the separation scheme. The second
rule is rigorous for one-feed, two-product columns as
the recycling of a product stream to the parent column
will result in the material balance over the column being
violated. The third rule is a consequence of the synthesis
procedure, which generates splits in a backward direction,
i.e., products from a column are selected 6rst, then the
required feed to the column is calculated. If a feed stream
to a column performing a pre-speci6ed split has more
components than both product streams from the column,
the split will be infeasible.
The fourth rule is based on the observation that cross-
ing boundaries by recycling always leads to infeasible
sequences (Doherty & Caldarola, 1985). This rule is con-
servative, as there are cases where mixing across the
boundary is possible. An example is presented in Fig. 5.
Here, streams b1 and d 1 are mixed although they exist
in di=erent distillation regions. The column sequence in
Fig. 5 can be seen to be feasible since all the internal
material balances are satis6ed. This sequence is feasi-
ble because of the curvature of the distillation boundary,
which allows the material balance over the second and
4422 D.Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4417– 4432

third columns to be satis6ed, i.e., composition b1 lies in

the triangle formed by b2, b3 and d 3. Furthermore, even
straight boundaries can be crossed by mixing as the po-
sition of the boundary can be manipulated by changing
the operating pressure or mass transfer regime.
The recycling options are generated for one of the po-
tentially feasible sequences in Fig. 4. Fig. 6 shows a
four-column sequence with potential recycles indicated
by dashed lines. In Fig. 6 the type of splits that the
columns perform are indicated by letter. As the azeotrope
(1) is recycled internally in this example, the only pos-
sible location for this stream, identi6ed by elimination
using the recycling rules, is the feed stream to the 6rst
column. The feed stream to the 6rst column can accept
all recycle streams as there are no distillation boundaries
in the mixture, and the column performs a Type C split
that traverses both compartments. Similar recycling su-
perstructures can be generated for the other 45 sequences
listed in Fig. 4.

3.4. Determining stream compositions and 5nalising

recycle streams in a column sequence

Only product regions have been determined thus far

in the synthesis procedure. The recycle streams enable
a split to be performed, but the appropriate recycle op-
tions can only be 6nalised after the stream compositions
have been determined. Determining stream compositions
is an iterative procedure and starts with specifying prod-
uct compositions for a particular split. An appropriate
test for feasibility (Thong & Jobson, 2001a; Bausa, von
Watzdorf, & Marquardt, 1998) is applied to test for prod-
uct feasibility. If the selected product compositions are
infeasible, another pair of compositions can be speci6ed.
The process of searching for feasible product composi-
tions continues until a pair of feasible compositions is
found. This process is carried out for every column in the
sequence as follows:
1. For all columns performing a Type B, C or D split,
identify feasible product compositions by arbitrarily
specifying product compositions and checking for fea-
sibility using an appropriate feasibility test. Feasible
product compositions are identi6ed independently for
each column performing a Type B, C or D split.
2. For all columns performing Type A splits that do not
have a speci6ed feed composition (a product stream
from a column performing a Type B, C or D split), ar-
bitrarily specify a pair of product compositions. There
is no need for a feasibility test as any product compo-
sitions in the product regions will be feasible (Thong
Fig. 4. Potentially feasible sequences for the recovery of all constituent
components in the quaternary mixture in Fig. 2. & Jobson, 2001a).
3. If a column performing a Type A split has a speci6ed
feed composition, specify either a distillate or bottoms
composition and calculate the co-product composi-
tion using a material balance. If the co-product
 D.Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4417– 4432
Fig. 5. A feasible three-column sequence to recover acetone and chloroform using toluene as the entrainer. The sequence includes a
boundary-crossing operation using mixing. Solid lines indicate separations and dashed lines indicate mixing operations.
Fig. 6. The recycle superstructure for a potentially feasible
four-column sequence to recover all constituent components in a
quaternary mixture (Fig. 2). Solid lines represent de6nite recycles.
Dashed lines indicate potential recycles.
composition is in the appropriate product region, the
product compositions will be feasible. If not, specify
arbitrarily both product compositions.
This process is illustrated using the column sequence
in Fig. 7, which is identical to the sequence in Fig. 6.
Feasible product compositions are identi6ed for the 6rst
column, which performs a Type C split. The bottoms
product stream from the 6rst column is fed to a column
which performs a direct (Type A) split. As methanol
(3) is to be recovered as the distillate from this column,
4423
a material balance determines the bottoms composition,
which is on the (4-5) composition boundary. These prod-
uct compositions are therefore feasible. The columns per-
forming binary splits do not have to be checked for fea-
sibility as they will always be feasible.
It was stated in Thong and Jobson (2001a) that any
product composition in the appropriate product regions
will be feasible if the split is a Type A split. This does
not mean that any feed composition in the appropriate
compartment will enable a Type A split to be realised.
Consider the quaternary mixture in Fig. 8. A feasible
Type A split is the 1=5-6 class of split. Geometrically,
this split requires a feed composition to lie in a plane
formed by the points 1, 5 and 6 in Fig. 8. This feed
composition to this column will be either the overall feed
to the column sequence or a product from a previous
split, and is unlikely to lie in the (1-5-6) plane. As a
consequence, the column performing the 1=5-6 split is
likely to require one or more recycle streams to enable the
split to be executed. Some Type A splits therefore require
recycles, an occurrence which is accounted for in Step 3
of the algorithm to determine stream compositions.
Once all stream compositions have been identi6ed, ap-
propriate recycle options are determined using a mate-
rial balance across every column. This material balance
can be formulated as a geometrical problem, as shown in
a hypothetical four-component mixture in Fig. 9. There
are always only two products from a column, d and b,
which results in the line db. The overall feed to this col-
umn must lie somewhere on the line db. In Fig. 9 there
are three possible recycle streams with compositions ji ,
ki and li . The stream fi has to be fed to this column as it
is the product stream from a preceding column. For the
4424 D.Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4417– 4432

Fig. 7. Stream compositions for the four-column sequence presented in Fig. 6.

Fig. 8. A quaternary azeotropic mixture at 1 atm. The shading indicates the distillation boundary.

split to work, the geometrical entity formed by mixing

Fig. 9. A geometrical representation of a quaternary split and recycle
options. ji and ki are feasible recycle options as the plane ji ki fi
intersects the line db.
any of ji , ki and li with fi , must intersect the line db.
As the composition space is three dimensional, a mini-
mum of three streams, which form a 2-D plane, will be
necessary to ensure a mathematical chance of feasibil-
ity (Thong, 2000). In Fig. 9 the mixing of streams ji , ki
and fi result in a 2-D plane that intersects the line db.
The mixture of streams ji , ki and fi therefore constitutes
a feasible recycle option. There are, in general, multiple
recycle options when there are more than (C-2) potential
recycle streams in a (C-1)-dimensional split.
When the recycling rules are applied to the sequence
in Fig. 7, with the recycle superstructure shown in Fig.
6, one feasible recycle option is shown in Fig. 10. In
this example, the azeotrope (1), methyl acetate (2) and
isopropanol (5) are recycled to the 6rst column. When
 D.Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4417– 4432 4425

Fig. 10. One of several recycle options for the sequence and stream compositions in Fig. 7. The material balance over the two-column subsystem
(dashed line) is not satis6ed—this requires a composition change in the stream (3-4-5).

internal recycles are present, however, material balances

overcolumnsubsystemswithintheoverallsequencehaveto
be satis6ed. The control volume over the 6rst two columns,
represented by the polygon in Fig. 10, shows one mate-
rial balance that is not satis6ed for this particular choice
of stream compositions. The recycle structure is in itself
feasible as the manifold formed by joining points F and
5, and the manifold formed by joining points 2 and points
3, 4 and 5 (representing product region (3-4-5), inter-
sect. This intersection implies that there should be stream
compositions that enable this particular material balance
to be satis6ed. The columns in the material balance es-
sentially perform a direct split to recover methyl acetate
(2). Geometrically, the material balance requires the in- Fig. 11. Geometrical representation of the material balance in Fig.
10. The lines (F-5) and [2-(3-4-5)1 ] do not intersect but the lines
tersection of the line (F-5), which indicates the inputs, (F-5) and [2-(3-4-5)2 ] intersect.
with the line [2-(3-4-5)], which indicates the outputs.
The material balance in Fig. 10 can also be inter-
preted in terms of component Fow rates. There is no All the information discussed in the preceding para-
problem with the methyl acetate and isopropanol bal- graph can be represented succinctly in geometrical form,
ances as methyl acetate is completely removed in stream which is shown in Fig. 11. The line (F-5) does not inter-
(2). The relative amount of the isopropanol recycle (5) sect the line [2-(3-4-5)]. Because the compositions of all
can be varied, allowing any mole fraction of methyl ac- other streams are 6xed, the composition of stream (3-4-5)
etate in the (3-4-5) stream. Because the feed is equimo- has to be modi6ed. This is achieved by selecting a point
lar in all components, however, the mole fractions of on the line (F-5), point X in Fig. 11, and extending the
methanol and ethanol in stream (3-4-5) have to be iden- line from this point to the point (2) till a composition in
tical, as stream (3-4-5) is the only outlet for methanol the (3-4-5) product region is reached. This is equivalent
and ethanol. The current composition of stream (3-4-5) to selecting a recycle-to-feed ratio for the isopropanol
does not allow the material balance to be satis6ed. Vary- (5) recycle and forcing the closure of the material bal-
ing the amount of the isopropanol recycle (5) does not ance. There are two conditions that have to be satis6ed
help. Because the compositions of streams F, 2 and 5 are concurrently—the material balance and the split feasibil-
invariant, the composition of stream (3-4-5) has to be ity. A new composition for the stream (3-4-5), indicated
changed. in Fig. 10 and calculated using the method described here,
4426 D.Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4417– 4432
Fig. 12. A four-column sequence with modi6ed stream compositions and new recycles. Feasible column parameters for all non-binary splits are
listed. The feed is equimolar in all components.
is feasible, i.e., the Type C split performed by the 6rst
column is feasible.
When a stream composition changes, downstream
columns will naturally be a=ected. New downstream
compositions can be determined using the algorithm de-
scribed earlier in this Section. As stream compositions
change, new recycle options must be identi6ed. This is
illustrated in Fig. 12, which displays the new stream
compositions and recycles after the stream composition
changes in Fig. 10. All the material balances are satis6ed
in this sequence, and the methyl acetate (2) recycle is
no longer required. Fig. 12 also shows feasible column
parameters for every non-binary split, calculated using
the column design method presented in Thong and Job-
son (2001b). The recycle-to-feed (R=F) ratios in Fig. 12
are determined from the positions of the intersections
between the various geometrical entities.
3.5. Boundary crossing by exploiting boundary
curvature
Synthesising column sequences that include a bound-
ary crossing operation is identical to the algorithms pre-
sented previously, except for the column that straddles the
boundary. The type of boundary crossing implied here is
the split with a feed in one region and products in an ad-
jacent region. The other type of boundary crossing which
involves open leaves are not accounted for here. Thong
and Jobson (2001a) introduce a simple test to estimate the
direction of curvature of a distillation boundary. Bound-
ary crossing is possible if the feed composition is in the
concave segment of the distillation boundary.
As indicated in Section 3.1, boundary crossing is re-
quired if a distillation boundary separates the feed from
one or more desired products. The sequence synthesis
procedure is carried out as described in Sections 3.1
and 3.2, until a compartment on a distillation boundary
is produced as a product region. At this point, a sim-
ple check is applied to determine if the product region
contains any of the components that are to be recov-
ered. This check is necessary since not only boundaries
but their lower-dimensional constituents can be crossed.
This check is illustrated using the quaternary mixture in
Fig. 8. If the feed composition is in the (1-2-3-5-6) re-
gion and the boundary curves towards the other region,
a boundary crossing operation is feasible. If, say, pure
methanol (4) is a desired product, the boundaries of in-
terest are then (1-3) and (1-2-3-5). Product regions on
the (2-5) and (3-5) boundaries do not contain methanol
(4) and are therefore not worth crossing as there is
no possibility of recovering methanol in subsequent
columns.
At the boundary, splits in the adjacent region are then
carried out and the synthesis procedure is applied nor-
mally. Splits with one of the product regions on the dis-
tillation boundary are not considered. A ternary example
is shown in Fig. 13. The product from the 6rst split lies
on the distillation boundary (3-4) and is in the (1-3-4)
region. This product is, therefore, a candidate feed com-
position for a column that straddles the boundary. Three
splits are identi6ed for the (2-3-4) region, two of which
 D.Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4417– 4432 4427

Fig. 13. An example of a boundary crossing operation in a ternary mixture. The 1=3-4 split exists in region II while the 2-3=4 split is e=ectively
in region I.

Fig. 14. A quaternary diagram representing the composition space of a four-component azeotropic mixture. Also shown are the adjacency and
reachability matrices. The mixture displays two distillation regions.

have product regions on the distillation boundary. These
two splits are therefore eliminated, leaving the 2-3=4 split
as the remaining possible class of split for the column
that crosses the boundary. The 2-3=4 split is, in this case,
a feasible split for the boundary crossing operation (Fig.
13). It can be observed from Fig. 13 that a 2-3=3-4 split is
a feasible boundary crossing operation although the bot-
tom product region is the distillation boundary. The range
of feasible product compositions for this class of split
is, however, limited. Although conservative, the rule for
eliminating these types of splits allows the identi6cation
of splits that maximise the use of boundary curvature, e.g.,
the 2-3=4 split in Fig. 13. Note that the splits identi6ed
here are equivalent to sharp splits in non-azeotropic mix-
tures as only product regions on the composition or dis-
tillation boundaries are considered. This procedure does
not identify products in the interior of the composition
space, which might be feasible products from a column
that straddles a distillation boundary.
Fig. 13 shows the product compositions for the various
splits only to illustrate the procedure. At the preliminary
screening stage (Section 3.2), only product regions will
be known. At the next stage (determining stream com-
positions), appropriate product compositions have to be
identi6ed for the column that straddles the boundary. This
is accomplished by trial and error.
4428 D.Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4417– 4432

Table 2
Feasible classes of splits for the quaternary mixture in Fig. 14
4-distillation 1-3-4-5 2-3-4-5
regions

Compartments C#1 C#2

(1-3-4-5) (2-3-4-5)

1=3-4-5A 2=3-4-5A
1-3=4-5A 2-3=4-5A
Quaternary
1-3=3-4-5A 2-3=3-4-5A
splits
1-3-4=5A 2-3-4=5A
(Types A & B)
1-3-4=4-5A 2-3-4=4-5A
1-3-4=3-4-5B 2-3-4=3-4-5B
3-distillation 1-3-4 1-3-5 1-4-5 2-3-4 2-3-5 2-4-5
regions

Compartments C#1 C#2 C#3 C#4 C#5 C#6

1-3-4 1-3-5 1-4-5 2-3-4 2-3-5 2-4-5

Ternary 1=3-4A 1=3-5A 1=4-5A 2=3-4A 2=3-5A 2=4-5A

splits 1-3=3-4A 1-3=3-5A 1-4=4-5A 2-3=3-4A 2-3=3-5A 2-4=4-5A
(Types A & B) 1-3=4A 1-3=5A 1-4=5A 2-3=4A 2-3=5A 2-4=5A

Binary splits 1=3A 1=4A 1=5A 2=3A 2=4A 2=5A 4=5A

Table 3 of appropriate product compositions is found. The other

Feasible classes of splits on the distillation boundary (3-4-5) of the stream compositions are determined as described in Sec-
quaternary mixture in Fig. 14
tion 3.4. The full algorithm for synthesising column se-
4-distillation 3-4-5 quences that include boundary crossing operations is as
boundaries follows:
Compartments C#1
1. Specify the problem as in Section 3.1.
(3-4-5)
2a. Apply the methods described in Section 3.2 to gen-
Quaternary splits 3-4=5 erate column sequences. When a product region is
(Type A) 3-4=4-5 a compartment on a distillation boundary and the
3-distillation 3-4 3-5 product region contains the desired component(s),
boundary perform all splits in the adjacent region (compart-
Compartments C#1 C#1
ment) that do not have the boundary as a product
(3-4) (3-5) region.
2b. A split on the boundary is possible only if the feed
Ternary splits 3=4 3=5
to the split is on the concave side of the bound-
(Type A)
ary. Boundary curvature can be estimated using the
method presented in Thong and Jobson (2001a).
3. Generate recycle options as in Section 3.3. The feed
As an example, after the 2-3=4 split in Fig. 13 has been stream to the column that straddles the boundary can-
identi6ed as a potential boundary crossing operation, a not be mixed with any recycle streams as the only
distillate composition can be speci6ed on the (2-3) edge recycles that are likely to be of use will be in an ad-
and a straight line plotted from the distillate to the bot- jacent distillation region, and these recycles are pro-
toms composition (benzene, 4). Residue curves are then hibited by rule 4 in Section 3.3.
calculated from initial points on this straight line to de- 4. Determine stream compositions and 6nalise recycle
termine if any point on the line lies in the (1-3-4) region. options as in Section 3.4. Always determine prod-
If so, these point(s) are potential feed compositions to uct compositions for the column that straddles the
the column that straddles the boundary. This also deter- boundary 6rst.
mines one of the product compositions for the preceding
column. If none of the points lie in the (1-3-4) region, Step 2b accounts for the fact that in some cases a split
new product compositions must be found and the residue on the boundary is not possible. As an example, a 3-4
curves recalculated. The process continues until a pair split is possible if the (3-4) product region is a result of
 D.Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4417– 4432 4429

Fig. 15. Potentially feasible sequences for the recovery of all constituent components in the quaternary mixture in Fig. 6:12. Boundary-crossing
operations are highlighted in bold. The asterisks and plus signs indicate splits that can be combined.

a 1=3-4 split (Fig. 13). In this case the feed to the (3-4)
split will not be on the boundary, but inside the (1-3-4)
region. If the (3-4) product region is a result of a 2=3-4
split, a 3-4 split is not possible.
Application of the algorithm is demonstrated on a
quaternary mixture of acetone, chloroform, benzene and
toluene, which forms a binary azeotrope between acetone
and chloroform. The quaternary diagram, adjacency and
reachability matrices are shown in Fig. 14. The boundary
in Fig. 14, represented by the shaded region, is not the
actual boundary but a representation of the fact that the
boundary curves towards the (2-3-4-5) region. The feed
to the column sequence is equimolar in all components.
Table 2 lists the feasible splits for the mixture in ques-
tion. Type D splits are omitted and there are no Type C
splits, since there is no further division of either distilla-
tion region into compartments. Table 3 lists the feasible
splits on the boundary and its lower-dimensional con-
stituents.
Fig. 15 lists the sequences that enable the recovery of
all the components. In six of the options (3A, 3B, 4A, 4B,
5A, 5C), the boundary can be crossed in the toluene-free
ternary composition space. In several options (5A, 5B,
5F-L) the boundary can be crossed twice, once in the
quaternary composition space and again in the ternary
composition space. Although possible, this sequence is
4430 D.Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4417– 4432
Fig. 16. The recycle superstructure for a potentially feasible
four-column sequence to recover all constituent components in a qua-
ternary mixture (Fig. 14). The second column straddles the distillation
boundary.
not preferable, as boundary crossing should generally be
kept to a minimum. Several sequences in Fig. 15 have
the (3-4) product region as an end product. A further
separation between 3 and 4 cannot be performed as the
(3-4) product region is the product of a split on the convex
side of the boundary.
One of the sequences in Fig. 15 is selected for further
study. Fig. 16 shows this sequence and its associated
recycle superstructure. The sequencing algorithm does
not allow the recycling of material to the feed of a column
that straddles the boundary. As a result, streams 2, 3,
4 and 5 cannot be recycled to the feed of the second
column in the sequence. The binary azeotrope (3) has to
be mixed with the feed to the 6rst column as there is no
other suitable recycling option for this stream. Fig. 17
shows the 6nal sequence, which satis6es all the internal
material balances. Only the azeotrope is recycled for this
particular choice of stream compositions. All end product
streams are 99.9% pure.
4. Comments and future work
Although mixing across distillation boundaries is not
accounted for in the sequencing procedure, column se-
quences that exploit this occurrence, e.g., the sequence in
Fig. 5, can be synthesised using the tools that have been
developed. In some cases the mixing of streams might
not be so much a viable option but a necessary opera-
tion to enable a split in a distillation region that does not
contain the feed composition. As the feasible classes of
splits will be the same regardless of mixing strategies,
the sequence-screening step will have to be modi6ed to
allow splits in adjacent distillation regions. One or more
recycling rules will also have to be added to the present
list to accommodate mixing across the boundary.
When determining appropriate recycle streams, a situ-
ation might arise where both product streams from a col-
umn are recycled to the same point. Unless both products
are desired components, the degree of separation can be
reduced and one recycle stream eliminated. An example
of this is shown in Fig. 18, where the bottoms stream from
a 1=3-4 split provides the feed to a 3=4 split on the bound-
ary. The desired products of the three-component feed are
pure benzene, pure acetone and the acetone-chloroform
azeotrope. Th azeotrope (3) could, for example, be recy-
cled to a reactor or fed to another separation process, e.g.,
a membrane separation unit. A recycle of acetone (1) is
necessary to enable a 3=4 split to take place. In this case
both product streams from the 1=3-4 split are fed to the
next split. A reduction in the degree of separation sim-
ply translates as producing a bottoms product from the
1=3-4 split that lies on the straight line joining 3 and 4,
and not on the distillation boundary. This eliminates the
need for an acetone (1) recycle. This particular example
is possible because the (3-4) stream is not a desired end
product and does not therefore have any composition re-
strictions placed on it. This step eliminates unnecessary
recycle streams and can, as in Fig. 18, reduce the degree
of separation in a column, reducing the separation cost.
The problem speci6cation, sequence-screening and re-
cycle generation steps are easily automated. The deter-
mination of the stream compositions and 6nalisation of
recycle streams are carried out manually in this work.
These last two steps can, in principle, be automated as
feasible compositions can be found using an appropriate
feasibility test for product compositions, e.g., Bausa et
al. (1998). Determining appropriate recycle options can
be automated, as the geometric test described in Section
3.3 is numerical and can be formulated mathematically
(Thong, 2000). Any algorithm for automating this step
will have to modify stream compositions to simultane-
ously address the internal material balances as well as
split feasibility.
Although quaternary mixtures have been examined, the
feasibility and column design methods are general and
the sequence synthesis procedure applies to mixtures with
more than four components. A limitation of the procedure
is the use of the recycles, which can become cumbersome
in mixtures with many components. Consider a split in a
quaternary mixture with a feed and both product compo-
sitions speci6ed. Because the product compositions are
speci6ed independently from the feed composition, the
material balance around the column will not necessar-
ily be satis6ed. A minimum of two recycle streams are
required to satisfy the material balance, as three points
are the minimum required to form a 2-D plane. A similar
split in a six-component mixture will require a minimum
of four recycle streams. Although feasible, this might not
 D.Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4417– 4432 4431

Fig. 17. A four-column sequence with stream compositions and recycles. Feasible column parameters for all non-binary splits are listed.

Fig. 18. An example of eliminating a recycle stream by reducing the degree of separation in a split. The dashed line indicates a mixing operation
between streams B1 and acetone (1).

be a practical option. Selection of appropriate product
compositions, as in the example in Fig. 17, can facilitate
a reduction in the number of required recycle streams.
This can be achieved by automating the search for feasi-
ble product compositions to allow the e=ect of di=erent
product compositions on the recycle structure to be ex-
plored.
A potential drawback of the column synthesis proce-
dure in its current form is the generation of a large num-
ber of column sequences. The algorithm is formulated
with the purpose of generating as many column sequences
as possible, so as not to miss promising Fowsheets. As
in non-azeotropic mixtures, the number of potential se-
quences will increase dramatically with multicomponent
mixtures. Shah (1999) has developed a distillation col-
umn synthesis and optimisation method that mathemati-
cally guarantees the global optimum in the separation of
non-azeotropic mixtures. Such an approach is not directly
applicable in the separation of azeotropic mixtures due
to its sequential nature.
4432 D.Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4417– 4432
An interesting topic for future research would be the
optimisation of the sequences generated here.
The column sequencing procedure can be applied
within a larger separation framework that includes phase
splitting, extraction, pressure-swing and mass transfer
e=ects. In the case of phase splitting and extraction, all
that is required is an accurate liquid–liquid equilibrium
model to detect instances of two-phase behaviour. This
model should be able to accurately predict the e=ect of
temperature on the size of the liquid–liquid region as
temperature is an important design variable in decanting
and extraction. Pressure and mass transfer e=ects can
be employed in tandem to shift distillation boundaries.
When applying these techniques, the position of the
boundary would have to be determined at di=erent pres-
sures and mass transfer regimes. Once this is done, the
sequencing procedure can be applied normally as the fea-
sible classes of splits will remain the same under all con-
ditions. It is, however, diGcult to calculate component
stage eGciencies, which are required in the calculation
of mass transfer rates, in mixtures with more than three
components (Castillo & Towler, 1998). The develop-
ment of accurate mass transfer models for n-component
mixtures will facilitate the development of novel column
sequences using the synthesis procedure presented here.
5. Conclusions
An algorithmic synthesis procedure for column se-
quences separating n-component azeotropic mixtures has
been developed. Although the synthesis procedure gen-
erates the splits sequentially, precise stream composi-
tions are not required. The procedure therefore avoids
the restriction on feasible product compositions from a
completely speci6ed feed stream. This approach allows a
more extensive use of recycles to address the issue of ma-
terial balances around the various columns and column
subsystems in the sequence.
The procedure is divided into four distinct stages—
problem speci6cation, preliminary sequence screening,
generation of recycle options and 6nally, the determina-
tion of stream compositions and 6nalisation of the recycle
structure. The problem speci6cation stage involves the
speci6cation of the product requirements as well as the
description of the composition space of the mixture to be
separated. The feasibility test for classes of splits is used
to generate feasible and potentially feasible sequences of
columns in the preliminary sequencing stage. A set of
rules is applied to generate a recycle superstructure for ev-
ery one of the sequences identi6ed in the previous stage.
Thus, many di=erent column sequences can be generated
with minimal computational e=ort as design calculations
are not required. In the 6nal stage, stream compositions
and recycle structures are determined. This stage requires
some trial and error and there exist many possible solu-
tions corresponding to di=erent stream compositions and
consequently, di=erent recycle structures. Column design
can then be carried out using the column design meth-
ods presented earlier in this work. The sequence synthe-
sis procedure is developed to identify feasible sequences
within a distillation region as well as sequences that ex-
ploit boundary crossing. Examples of both situations are
presented.
Acknowledgements
The authors would like to acknowledge the support of
the UMIST Process Integration Research Consortium.
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