Chemical Engineering Science 56 (2001) 4393–4416

www.elsevier.com/locate/ces

Multicomponent homogeneous azeotropic distillation

2. Column design
Dennis Y.-C. Thong, Megan Jobson ∗
Department of Process Integration, UMIST, P.O. Box 88, Manchester M60 1QD, UK

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

Abstract
A new design tool for single-feed, two-product columns separating multicomponent azeotropic mixtures is proposed. Column
parameters are determined numerically, based on geometric principles. Many feasible combinations of design parameters can be
determined rapidly, and can be represented conveniently in a feasibility matrix. This matrix can be used to identify favourable
combinations of design parameters. The new column design method is developed separately for two cases—columns producing
pure components, and columns performing general splits. In the case of columns producing pure components, the accuracy of the
design method can be improved by the application of an iterative convergence procedure. ? 2001 Elsevier Science Ltd. All rights
reserved.

Keywords: Distillation; Azeotropic; Multicomponent; Design; Manifolds; Feasibility matrix

1. Introduction
There exist e7ective design methods for distilla-
tion columns separating ideal liquid mixtures, the most
popular of which are the Fenske–Underwood–Gilliland
methods. The Fenske and Underwood methods for the
calculation of the minimum theoretical number of stages
and minimum re<ux ratio, respectively, are shortcut
methods based on the assumption of constant relative
volatility. Either the operating re<ux ratio or actual num-
ber of stages can then be speci=ed, and the other calcu-
lated using an empirical correlation, e.g., the Gilliland
correlation.
Most design methods for columns separating non-ideal
and azeotropic mixtures have concentrated on the cal-
culation of the minimum energy requirements (Koehler,
Aguirre, & Blass, 1991; Poellmann, Ganz, & Blass, 1994;
Julka & Doherty, 1990; Bausa, von Watzdorf, & Mar-
quardt, 1998) of a proposed split. The traditional route for
non-azeotropic column design does not work for columns
separating azeotropic mixtures as a reliable method for
calculating the theoretical minimum number of stages
∗ Corresponding author. Tel.: +44-161-200-4381;
fax: +44-161-236-7439.
does not exist. Even if there was such a method, the
wide and sometimes unusual array of splits possible in
azeotropic mixtures would complicate the development
of a correlation between the re<ux ratio and the number
of stages.
Several design methods exist for columns separat-
ing azeotropic mixtures. The boundary value procedure
(Levy, Van Dongen, & Doherty, 1985) and stage com-
position line approach (Thong, Castillo, & Towler,
1999) are suited for use in ternary mixtures. While the
stage composition line approach addresses some of the
limitations of the boundary value procedure, both mani-
folds are limited in use to ternary mixtures. A geometric
design method (the !-method) proposed by Julka and
Doherty (1993) can be applied to columns separating
multicomponent azeotropic mixtures. The !-method is,
however, only applicable to splits where one component
is removed, i.e., the equivalent of direct and indirect
splits in non-azeotropic mixtures.
In this work, new column design methods are devel-
oped for use in single-feed, two-product columns sepa-
rating multicomponent azeotropic mixtures. The design
methods are numerical and do not require visual repre-
sentation in order to be applied. These design methods
are therefore applicable to mixtures with any number of

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 6 - 2
4394 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416
components. The design methods apply to columns per-
forming any type of split.
2. Background
2.1. Boundary value method
The boundary value design method is proposed by
Levy et al. (1985) to determine the minimum re<ux ratio
for ideal, non-ideal and homogeneous azeotropic distilla-
tion. Assuming that the feed composition and quality is
=xed, once two product compositions are speci=ed, there
remains one degree of freedom remaining between the
re<ux and boil-up ratio. Once a value of the re<ux (or
boil-up) ratio is speci=ed, rectifying and stripping com-
position pro=les can be calculated from the previously
speci=ed product compositions. The locations of the pro-
=les depend on the values of the re<ux and boil-up ratios.
The minimum re<ux ratio is the value of the re<ux ra-
tio at which the two pro=les just touch—this occurrence
can be veri=ed visually when the pro=les are plotted in a
ternary diagram.
Besides determining minimum re<ux, the boundary
value method can be used to determine feasible design
parameters (number of stages, feed stage location, re-
<ux ratio, boil-up ratio) for a proposed split. The method
is, however, iterative in nature, possibly requiring many
attempts to obtain a solution. If the speci=ed products
turn out to be infeasible, the method will not =nd any
parameters at all. The boundary value method is not prac-
tically applicable to mixtures with four and more com-
ponents as the chances of two curves intersecting in 3-D
and higher-dimensional spaces is very small.
2.2. Stage composition line approach
The stage composition line approach to column design
is proposed by Thong et al. (1999) to address the limita-
tions in the use of composition pro=les in column design.
Like the boundary value method, the calculation of stage
composition lines requires the complete speci=cation of
both product compositions. While a composition pro=le
joins composition points at the same re<ux or boil-up ra-
tio at di7erent stage numbers, the stage composition line
joins points at the same stage for di7erent values of the
re<ux or boil-up ratio. Unlike composition pro=les, ev-
ery point on a stage composition line can be reached by
operating at the appropriate re<ux or boil-up ratio. Rec-
tifying and stripping stage composition lines can be cal-
culated from each product, and every intersection from a
=nite number of intersections represents a feasible com-
bination of operating parameters.
While removing the trial and error aspect from col-
umn design, stage composition lines su7er from the same
limitations as the boundary value method. Because both
product compositions have to be speci=ed completely,
stage composition lines will be lines (one-dimensional
entities) in multicomponent mixtures. Like composition
pro=les, the chances of two lines intersecting in 3-D and
higher space is very small. The stage composition line
approach is therefore only applicable to columns separat-
ing ternary mixtures. Nevertheless, the underlying princi-
ples behind the stage composition line approach are used
in the development of the new column design method in
Sections 3–5.
2.3. Geometric design procedure (!-method)
The !-method (Julka & Doherty, 1993) is an extension
of the zero-volume criterion (Julka & Doherty, 1990) to
determine the minimum re<ux ratio for direct and indirect
splits in multicomponent azeotropic mixtures. Once both
product compositions are speci=ed, a rectifying (direct
split) or stripping (indirect split) plane can be calculated
at a value of the re<ux ratio. This plane is constructed
from the =xed points of the rectifying (direct split) and
stripping (indirect split) section material balances. The
size and position of this plane depend on the value of the
re<ux ratio. The stripping (direct split) and rectifying (in-
direct split) composition pro=les can also be calculated.
The condition for minimum re<ux is the pinching of the
stripping or rectifying pro=le on the rectifying or stripping
plane. Expressed geometrically, minimum re<ux occurs
when the volume formed by the =xed points and pinch
point in the stripping or rectifying pro=le is minimised.
The zero-volume criterion is adapted by Julka and
Doherty (1993) for column design. The plane of =xed
points is calculated at a value of the re<ux ratio that is
above the minimum value. The co-product composition
pro=le then intersects the plane instead of pinching on it,
as shown in the direct split in Fig. 1. The ‘reverse rectify-
ing pro=le’ is then calculated up the column, starting from
di7erent feed stage compositions, and terminates when
the required distillate purity is obtained. The parameter
! is representative of the distance between the feed stage
composition and rectifying plane. As can be observed
from Fig. 1, larger values of ! tend to lower the required
number of rectifying stages at the cost of more stripping
stages. The optimum value of ! is determined by plot-
ting a stage-! graph and selecting a value of ! which
minimises the total number of stages. The entire proce-
dure can be repeated for a di7erent value of the re<ux
ratio.
The !-method is limited to splits where one compo-
nent is recovered, which is analogous to direct or indi-
rect splits in non-azeotropic mixtures. The new design
method which will be presented in Sections 4 and 5 ap-
plies to all types of splits. A ‘tuning algorithm’ for greater
accuracy is incorporated in the new design method. This
algorithm is similar to the calculation of the ‘reverse
 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416
Fig. 1. A direct split with the rectifying plane formed by =xed points
x1r , x2r and x3r . Three ‘reverse rectifying pro=les’ are calculated at
three di7erent values of !.
rectifying pro=le’ in Fig. 1. The new design procedure
also makes use of planes, but the calculation of these
planes is simple and does not require the calculation of
=xed points. Instead of multiple stage-! graphs to identify
favourable combinations of parameters, the new method
represents all information succinctly in a ‘feasibility
matrix’.
3. Theory
It is a widely accepted fact that composition pro=les
are very sensitive to small <uctuations in the product
compositions. Fig. 2 displays several rectifying pro=les
calculated from almost identical distillate compositions at
a re<ux ratio (r) of 5. All the pro=les lie in a ‘rectifying
manifold’ for the product composition d at r = 5. This
Fig. 2. Composition pro=les calculated from d at r = 5 lie inside a rectifying manifold. A–C are pinch points at r = 5.
4395
manifold contains all the possible composition pro=les
leading to d calculated at a re<ux ratio of anything up
to a value of 5. The manifold is constructed from d
and three other points—A–C. Point A is the pinch point
at r = 5, calculated from an equimolar distillate mixture
of tert-butanol and 2-butanol (0.5 tert-butanol and 0.5
2-butanol). Point B is the pinch point at r = 5, calcu-
lated from a distillate composition of tert-butanol and
2-butanol, with a small quantity of isobutanol (0.495
tert-butanol, 0.495 2-butanol, 0.01 isobutanol). Point C is
the pinch point at r = 5, calculated from a distillate com-
position of tert-butanol and 2-butanol, with a small quan-
tity of 1-butanol (0.495 tert-butanol, 0.495 2-butanol,
0.01 1-butanol). These compositions are chosen to re-
<ect the full range of possible composition pro=les for
equimolar mixtures of tert-butanol and 2-butanol con-
taining up to 1% impurities. Other compositions in the
vicinity of d can be speci=ed, but the resulting composi-
tion pro=les will always lie in the manifold. The manifold
does not include any limitations in the number of stages
as it utilises the pinch points in its construction, i.e., the
manifold represents the limit of operation at an in=nite
number of stages. The plane ABC is identical to the rec-
tifying plane of =xed points (Julka & Doherty, 1990) at
r = 5.
A more complete set of manifolds can be constructed
by including the number of stages—this is illustrated
in Fig. 3. The various planes are calculated from the
points on the composition pro=les leading to the repre-
sentative compositions, and represent the possible liquid
composition on various stages at r = 5. The plane ABC
is the manifold of stage compositions at an in=nite
number of stages at r = 5. Similar planes can be cal-
culated at di7erent values of the re<ux ratio. Because
they are calculated from stage-to-stage composition pro-
=les, the mole fractions of the impurities (isobutanol and
1-butanol) have a signi=cant in<uence on the size and
location of the resulting planes. In this example, a value
4396 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416
Fig. 3. Rectifying manifolds for distillate composition d at various stages (r = 5).
of 0.01 was chosen to re<ect the maximum allowable
impurity in distillate. The size of the planes at Nr = ∞
are independent of mole fraction of impurity in the dis-
tillate. This is because the positions of the pinch point
curves are not a7ected by small variations in the distillate
composition.
Fig. 4 shows the stripping manifolds for the strip-
ping section producing a bottoms composition b. In this
case, two representative compositions are required. The
=rst (0.2 2-butanol, 0.3 isobutanol, 0.5 1-butanol) is free
from tert-butanol. The second (0.01 tert-butanol, 0.197
2-butanol, 0.297 isobutanol, 0.496 1-butanol) contains all
four components. Composition pro=les (one ternary, one
quaternary) are calculated from these two compositions.
The manifolds are constructed from the points on these
pro=les. The stripping manifolds are, in this case, lines.
Each line represents the possible liquid composition at
a certain stage for a speci=ed boil-up ratio. These lines
are stripping manifolds, generated from an approximate
product composition, and should not be confused with
stage composition lines, generated from a speci=c prod-
uct composition, which represent the liquid composition
at a stage for any boil-up ratio. When the stripping man-
ifolds are plotted with a set of rectifying manifolds, e.g.,
the manifolds in Fig. 3, every intersection between the
two sets of manifolds corresponds to a certain combina-
tion of the total number of stages, feed stage location,
re<ux and boil-up ratio. This constitutes the basis for the
column design method. The selection of the various rep-
resentative compositions depends on the type of split re-
quired, and is discussed further in the following sections.
Constant molar over<ow is assumed in all examples, but
this assumption can be relaxed, at the expense of consid-
erably longer solution times, if more accurate results are
desired.
4. Design method for columns producing pure
components
4.1. Product regions, composition manifolds and the
feasibility matrix
In a C-component azeotropic mixture a pure compo-
nent can be the product of a distillation column regardless
of its node=saddle characteristics, although in almost all
cases the component will be a node. These are equiva-
lent to direct=indirect splits in non-azeotropic liquid mix-
tures. Because most azeotropes are minimum-boiling, a
pure component will very often be the bottom product
from a column. There will normally be purity require-
ments on the product stream, something in the order of
90 –99.99%.
Once the minimum acceptable purity of the desired
component in the product stream has been speci=ed, a
product region can be de=ned. A product region is the
set of all compositions that meet the speci=ed purity
requirements. Composition manifolds can then be calcu-
lated from this product region. While a point on a compo-
sition pro=le represents the composition at a certain stage
and value of the re<ux ratio leading to a speci=ed prod-
uct composition, a composition manifold represents all
the possible compositions at a certain stage and value of
the re<ux ratio leading to a product region. Fig. 5 shows
a distillate product region of 95% tert-butanol, and two
of many possible rectifying manifolds.
The rectifying manifolds are formed from com-
position pro=les calculated from three representative
compositions, d 1; d 2 and d 3 in Fig. 5. The manifold
corresponding to Nr = 5 and r = 1 is formed by join-
ing the composition points or the three binary compo-
sition pro=les at Nr = 5 and r = 1. The representative
 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416 4397

Fig. 4. Stripping manifolds for bottoms composition b at various stages (s = 5).

Fig. 5. A 95% tert-butanol distillate product region and two rectifying manifolds calculated from three representative compositions d 1; d2 and
d 3. The dashed lines represent the binary composition pro=les.

compositions for a high-purity product region are all the
possible binary combinations of components with the
component to be recovered. These points are chosen to
re<ect the full range of composition pro=les originating
from all possible product compositions on the d1-d 2-d 3
face of the product region.
Once the manifolds have been calculated, a co-product
composition is speci=ed completely, i.e., the mole frac-
tions of all independent components are speci=ed. Stage
composition lines are calculated from this co-product
composition. The intersection between a stage composi-
tion line and a composition manifold indicates feasible
parameters. Fig. 6 displays the stage composition lines
and several rectifying manifolds at Nr = 5. Every inter-
section between the set of stripping stage composition
lines and rectifying manifolds represents a feasible com-
bination of parameters, i.e., operating the column with
these parameters will allow the production of a bottoms
composition b and a distillate composition with a pu-
rity of 95% tert-butanol. There will always be (C −
1) binary representative compositions regardless of the
number of azeotropes and distillation boundaries. Conse-
quently, composition manifolds are always formed from
(C − 1) points on (C − 1) binary composition pro=les and
will always be hyperplanes in the (C − 1)-dimensional
composition space. As a result, the manifolds and stage
composition lines will always intersect. This occurrence
is explained further in Thong (2000). A numerical pro-
cedure for calculating the intersection between a line and
hyperplane can also be found in Thong (2000).
4398 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416

Fig. 6. Several rectifying manifolds at Nr = 5; and stripping stage composition lines for a bottoms composition b.

The design procedure for columns producing pure

products is as follows:
1. Select the component to be recovered and the purity
required.
2. Find the representative compositions by identifying all
possible binary product combinations with the com-
ponent to be recovered, at the desired purity. These
compositions de=ne the product region. Construct the
composition manifolds from the composition pro=les
calculated from the representative compositions.
3. Specify an exact co-product composition. Calculate
the stage composition lines for the co-product compo-
sition.
4. Identify intersections between the stage composition Fig. 7. A feasibility matrix consisting of an outer (Nr × Ns ) matrix,
lines and the composition manifolds. Each intersec- each element of which is an (r × s) matrix.
tion will correspond to a certain total number of
stages, feed stage location and re<ux and boil-up
ratio. a value of 100% (of the desired component) can be used
Once a feasible combination of Nr ; Ns ; r and s has been for the product composition in Eq. (1).
identi=ed, there is one degree of freedom remaining be- There will be, in general, many intersections, corre-
tween the feed composition and feed quality. The feed sponding to many di7erent feasible combinations of Nr ;
and product compositions, re<ux and boil-up ratios, and Ns , r and s. A matrix of feasible con=gurations and oper-
feed quality are related by (Thong, 2000): ating parameters can, if desired, be set up. Because there
1−q+s q+r are four independent parameters, Nr ; Ns , r and s, the ma-
fi = di + bi for i = 1; : : : ; C − 1: trix will be an Nr × Ns matrix, with each element being
s+r+1 s+r+1
(1) an r × s matrix, as illustrated in Fig. 7.
Fig. 8 shows four of these matrices from the example
One additional equation represents the overall material in Figs. 5 and 6. A value of 1 indicates that the rectifying
balance around the feed and product streams. When one and stripping manifolds at that particular combination
of the product compositions from a column is not com- of Nr , Ns , r and s intersect. Conversely, a value of 0
pletely speci=ed, as is the case for the distillate product indicates that the manifolds do not intersect. Discrete
in Fig. 6, there is one additional degree of freedom in the values of the re<ux and boil-up ratios, with intervals of
product composition subject to the purity constraint. Be- unity are chosen in this example. Larger intervals would
cause the constraint on purity is usually tight (¿99%), expedite the calculation of the matrix while smaller
 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416
Fig. 8. Four elements of the (Nr × Ns ) matrix for the example in Figs. 5 and 6.
intervals would provide more information at the expense
of longer computational times. The feasibility matrix
tends to be sparse (more 0’s) at lower total stage counts,
i.e., at the top and left of the (Nr × Ns matrix). The
minimum number of stages can be identi=ed simply by
searching for the non-zero matrix, or matrices, with the
lowest total stage count. Minimum re<ux, however, is
not easily established because the feed composition and
condition are not speci=ed beforehand, i.e., the re<ux
and boil-up ratios are varied independently.
Once the feed composition or feed condition has been
speci=ed, the feasibility matrix can be transformed into
a matrix of relative costs. As an example, Eqs. (2) and
(3) (Thong, 2000) can be applied to the entire feasibility
matrix to calculate a matrix of vapour loads


di − fi
Vs = sF for i = 1; : : : ; C − 1; (2)
di − bi
Vr = Vs + (1 − q)F: (3)
The matrix of limiting vapour loads can also be used to
select column modi=cations to increase throughout, as
described by Thong et al. (1999). Fig. 9 shows two of
the four (r × s) matrices in Fig. 8, now transformed into
four matrices with related limiting vapour loads. The feed
and product compositions used in Eqs. (1) – (3), are also
listed. The feed quality, q; is the calculated parameter.
4399
If a more accurate indicator of column cost is re-
quired, detailed cost models can be applied (e.g., Miller
& Kapella, 1977; Douglas, 1988) as information on
<owrates, temperatures and compositions is available
at each intersection. Hydraulic performance at each in-
tersection can also be determined by applying more
rigorous methods (Liu & Jobson, 1999), if required, for
column debottlenecking.
4.2. Tuning method to correct the feasibility matrix
Because the composition manifolds are approximated
by linear hyperplanes although they are actually surfaces,
the feasibility matrix will be inexact, especially in mix-
tures exhibiting highly non-ideal VLE. If the actual man-
ifolds curve toward the bottoms composition the design
procedure underestimates the range of feasible operating
parameters, i.e., the feasibility matrix does not have as
many 1’s as it should. If the manifolds curve away from
the bottoms composition the procedure overestimates the
range of feasible operating parameters. The matrix of fea-
sible parameters can be corrected using a tuning method,
which is described below. The proposed algorithm is
one way of facilitating convergence, and more elegant
or computationally ePcient methods may well exist. The
method was tested on a number of cases and was found
to be reliable and robust.
4400 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416
Fig. 9. Two matrices of limiting vapour loads, calculated from two
of the four matrices in Fig. 8. All values are normalised relative to
the value at Nr = 10; Ns = 10; r = 3; s = 4.
Step 3 in the design procedure requires the speci=ca-
tion of an exact co-product composition, and not a prod-
uct region as in Fig. 6. This speci=cation is to allow the
range of feasible parameters to be corrected using a tun-
ing method. Instead of calculating the composition pro-
=les from both product compositions and working to-
wards the feed stage composition, as has been the case
thus far, the tuning method starts from either the distil-
late or bottoms composition and calculates the complete
composition pro=le up to the other product composition.
Similar calculations have been reported by Van Don-
gen and Doherty (1985), Poellmann and Blass (1994),
and Julka and Doherty (1993). The method is described
in detail in Appendix A, but the outline is described
here.
The method requires the speci=cation of two product
compositions—one =xed, and one estimated, the number
of stages and feed stage location, re<ux and boil-up ra-
tios. The composition pro=le is calculated all the way up
(or down) the column from the =xed product composi-
tion, at the speci=ed re<ux and boil-up ratios until the to-
tal number of speci=ed stages is reached. The estimated
co-product composition is necessary for the computation
of the full composition pro=le. The calculated co-product
composition at the other end of the column will, in most
cases, not be the same as the estimated co-product com-
position. This calculated co-product composition is, to-
gether with the estimated co-product composition, used
to derive a new estimate for the co-product composi-
tion, to be used in the next iteration. The method will
=nally converge on a co-product composition, which is
the actual co-product composition for that set of operat-
ing parameters, i.e., plotting rectifying and stripping pro-
=les in the usual manner from both product compositions
will result in the pro=les intersecting at the feed stage
composition.
Fig. 10 presents a <owchart of the tuning algo-
rithm, as applied to the example in Figs. 5 and 6.
In this case, the bottoms composition is speci=ed,
while d est ; is used as the =rst estimate of the distillate
composition.
The parameters shown in Fig. 10 (Nr = 10; Ns = 10;
r = 4; s = 3) are obtained from the feasibility matrix in
Fig. 8. A graphical depiction of the tuning algorithm is
shown in Fig. 11. A =rst estimate of the distillate com-
position, d 0 ; is provided. In Fig. 11, the dotted line is the
composition pro=le calculated from this =rst estimate. d 1
is the calculated distillate composition, obtained from the
composition pro=le in the =rst iteration. Because the dif-
ferences between the individual mole fractions of d 0 and
d 1 are greater than the accepted tolerance, a second esti-
mate of the distillate composition is required. This esti-
mate is derived from d 0 and d 1 (see Appendix A), and
is used to calculate the complete composition pro=le in
the second iteration. The iterative procedure is continued
until it converges on a distillate composition. This dis-
tillate composition, d f in Fig. 11, exceeds the required
tert-butanol purity and implies that the rectifying mani-
folds curve towards the bottoms composition. The com-
position pro=le corresponding to d f is plotted in Fig. 11
as a solid line. The composition pro=les calculated us-
ing d 0 and d f are similar because the initial guess of the
distillate composition is a good one. The tuning method
does not require a good initial guess to converge. In Fig.
11, a poor initial guess of the distillate composition, d ∗ ; is
provided. The composition pro=le corresponding to this
distillate composition is plotted in Fig. 11 as a dashed
line. This composition pro=le strays outside the compo-
sition space, but the iterative procedure rounds up all
negative numbers to a value of zero, and all mole frac-
tions greater than one are assigned a value of one. The
iterative procedure converges on the same =nal distillate
composition, d f .
 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416 4401

Fig. 10. A <owchart of the tuning algorithm in the case of a completely speci=ed bottoms composition.

Fig. 11. Composition pro=les calculated from b at Nr = 10; Ns = 10; r = 4; s = 3. d 0 is the =rst estimate of the distillate composition. d 1 is
the calculated distillate composition with d 0 as the estimate. d ∗ is a di7erent (=rst) estimate of the distillate composition. Both estimates
converge to the =nal distillate composition d f . The solid, dashed and dotted lines are the composition pro=les calculated using d f , d ∗ and d 0 ,
respectively.

Further application of the tuning method using various
combinations of Nr ; Ns ; r and s from Fig. 8, produces
the corrected matrix of feasible parameters, as shown in
Fig. 12. The numbers in bold indicate the feasible com-
binations that were previously undetected. A comparison
of the two sets of matrices suggests that the rectifying
manifolds curve towards the bottoms composition. Al-
though the tuning algorithm can be applied using every
combination of parameters, it is usually suPcient to use
the parameters on the periphery of feasibility, i.e., feasi-
ble parameters with adjacent infeasible parameters, and
vice versa.
This corrected feasibility matrix can now be trans-
formed into a matrix of relative costs or vapour loads,
and is more accurate than the matrices in Fig. 9.
4.3. Eight-component example
In this example an eight-component azeotropic mix-
ture comprising acetone, methyl acetate, chloroform,
methanol, ethyl acetate, ethanol, benzene and toluene,
is examined. The pure component and mixture proper-
ties are obtained from the HYSYS v.1.2.9 simulation
4402 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416
Fig. 12. Four elements of the corrected feasibility matrix in Fig. 8. The numbers in bold indicate the corrected elements (cf. Fig. 8).
package. The Wilson activity coePcient model and an
ideal vapour phase model are used. The Wilson param-
eters are not available for the methyl acetate–toluene
binary pair, so the UNIFAC method is applied to esti-
mate the missing parameters. By applying the methods
outlined by Rooks, Julka, Doherty, and Malone (1998),
the mixture is found to form 18 azeotropes and =ve
distillation regions. An indirect split to recover toluene
is proposed. The distillate composition (mole fractions:
0.16 acetone, 0.14 methyl acetate, 0.14 chloroform,
0.14 methanol, 0.14 ethyl acetate, 0.14 ethanol, 0.14
benzene, 1E−4 toluene) is speci=ed, while the toluene
purity in the bottoms is required to be at least 99.9%.
The feasibility test described in Thong and Jobson
(2001) will con=rm the feasibility of this pair of product
compositions.
The design procedure identi=es a matrix of feasible
parameters, which is corrected by applying the tuning
algorithm. Fig. 13 shows two of the (r × s) matrices
before and after correction. The corrected matrices dis-
play a greater range of feasible parameters—this implies
that the stripping manifolds curve towards the distillate
composition.
The intersection corresponding to Nr = 11; Ns = 11,
r = 2, s = 3 (Fig. 13) is then selected arbitrarily, with
q = 1 and the feed composition calculated using Eq. (1).
The calculated feed composition and product speci=-
cations are listed in Table 1. These values, with the
speci=ed parameters, are used to initialise a rigorous
simulation, the results of which are also listed in Table
1. The discrepancies between the design speci=cations
and simulation results are highlighted in bold. The dis-
tillate composition from the simulation is similar to the
speci=ed composition. The bottoms composition, at 98%
toluene, does not meet the required purity. This di7er-
ence is primarily due to an increase in the vapour and
liquid <owrates in the top half of the stripping section,
an occurrence that is not accounted for in the design
method. In this case, the purity speci=cation on the
bottom product can be met either by partially vapor-
ising the feed (q = 0:94) or by increasing the boil-up
ratio (s = 3:1). These changes are small, which sug-
gests that the assumption of constant molar over<ow is
reasonable.
A design method for single-feed columns producing
a pure component is proposed. The method requires the
speci=cation of a product region for the component to be
recovered, and a co-product composition. Every intersec-
tion between the composition manifolds, from the product
region, and stage composition lines, from the co-product
composition, represents a feasible combination of pa-
rameters. The multiple intersections represent di7erent
 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416 4403

Fig. 13. Two elements of the feasibility matrix, before and after correction, for the proposed indirect split in an eight-component mixture.

Table 1
Comparison between design speci=cations and simulation results for an indirect split in an eight-component azeotropic mixture

Components Feed Distillate Bottoms

Design method Rigorous simulation Design method Rigorous simulation

Acetone 0.08 0.16 0.16

Methyl acetate 0.07 0.14 0.14
Chloroform 0.07 0.14 0.14
Methanol 0.07 0.14 0.14 99.9% 98%
Ethyl acetate 0.07 0.14 0.14 toluene toluene
Ethanol 0.07 0.14 0.14
Benzene 0.07 0.14 0.13
Toluene 0.50 1E − 4 7E − 5

feasible combinations of parameters, all of which, if re-
quired, can be incorporated in an (Nr × Ns ) feasibility
matrix, each element of which is an (r × s) matrix. An
iterative tuning algorithm can correct errors in the feasi-
bility matrix, caused by the linear approximation of the
composition manifolds.
5. Design method for columns performing general splits
5.1. Combined composition manifolds and the
feasibility matrix
Fig. 3 in Section 3 shows several rectifying mani-
folds for a distillate composition d. These manifolds
are calculated from the composition pro=les generated
from three representative compositions, d1; d2 and d 3;
as shown in Fig. 14. The indices 1, 2, 3 and 4 repre-
sent tert-butanol, 2-butanol, isobutanol and 1-butanol,
respectively.
The representative compositions are obtained by
analysing the reachability matrix (Knight & Doherty,
1990). The full algorithm for a rectifying manifold is as
follows:
1. Specify the mole fraction of the principal components
in the distillate composition and set the value of all
others to zero. In the case of a distillate composition
on a composition boundary, obtain a composition on
the boundary and not on a linear approximation of
the boundary. This generates the =rst representative
composition, d 1.
2. Identify the distillation or composition boundary on
which the distillate composition lies (Rooks et al.,
1998). Identify the highest-boiling singular point
on the boundary. From this point identify, using
the reachability matrix, all reachable higher-boiling
points.
3. From d 1; move a short linear distance towards one of
the reachable higher-boiling points identi=ed in Step 2.
4404 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416
Fig. 14. Rectifying manifolds for a distillate composition d, calculated from three representative compositions.
This generates the second representative composition,
d2.
4. Repeat Step 3 for all reachable points. This generates
the remaining representative compositions d 3; : : : ; d n.
The representative compositions for a bottoms composi-
tion are generated in an analogous manner, the only dif-
ference being the identi=cation of lower-boiling points
instead of higher-boiling points. It can be deduced from
the algorithm that the design method assumes splits with
both products on either distillation or composition bound-
aries, i.e., the design method does not apply to splits with
one or both products in the interior of the composition
space.
When applied to the mixture in Fig. 14, the three
representative compositions d 1; d2 and d 3 lie on the
1-2, 1-2-3 and 1-2-4 edge=faces of the quaternary dia-
gram. Step 3 in the algorithm for identifying represen-
tative compositions requires a small shift in composi-
tion. When a product composition is on a composition
boundary, as is the case of the distillate composition in
Fig. 15, this small shift can be interpreted as a purity
requirement, i.e., the maximum tolerable mole fractions
of singular points 3 and 4 in the distillate are both 0.01.
When a product composition lies on a distillation bound-
ary, this composition shift can be interpreted as a recovery
requirement.
The size and position of the composition manifolds
depend on the magnitude of the composition shifts.
Fig. 15 displays two rectifying manifolds calculated at
the same stage number, re<ux ratio and approximate
product composition. The di7erence between the two
manifolds is caused by the di7erence in magnitude of
the composition shifts, or, in this case, the mole fraction
of impurities in the distillate. The smaller composition
shift (0:1 mol% impurities) results in a smaller rectify-
ing manifold, which is closer to d than the manifold
calculated with the larger composition shift (1:0 mol%
impurities). This simply means that a purer product will
require more stages and re<ux.
Although the amount of impurities has an in<uence
on the size and position of the manifolds, the relative
amounts of the impurities do not. As an example, the
rectifying manifolds in Fig. 14 are valid at any pro-
portion of 3 and 4 in the distillate. This o7ers signi=-
cant advantages in column design for n-component mix-
tures as only the total amount of each impurity has to
be speci=ed and not the individual mole fractions of the
impurities.
At this point, the stripping manifolds could be calcu-
lated, and the intersections between the rectifying and
stripping manifolds evaluated. A problem that is likely to
arise is the failure to detect intersections that correspond
to feasible parameters. As the manifolds are evaluated at
discrete values of the re<ux and boil-up ratios, there will
be gaps between every manifold. As a result, some fea-
sible combinations of parameters will not be identi=ed.
Instead, manifolds for di7erent values of re<ux or boil-up
ratios can be combined. Fig. 16 illustrates the combined
manifolds for 10 rectifying stages and re<ux ratios of 2–
4. Because the rectifying manifolds are planes, the com-
bined manifold will be a convex volume. This combined
manifold is the locus of compositions at 10 rectifying
stages and a re<ux ratio between 2 and 4, leading to a
distillate composition d .
 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416
Fig. 15. Two rectifying manifolds at the same stage number and re<ux ratio. The manifolds are calculated at two di7erent levels of impurities
in the distillate composition.
Fig. 16. A combined rectifying manifold for a distillate composition
d , at 10 rectifying stages and a re<ux ratio of 2– 4.
Combinations of manifolds at a certain stage number,
at successive values of the re<ux ratio, will lead to the
generation of a ‘stage composition manifold’, which con-
tains all the compositions at a certain stage at any re<ux
or boil-up ratio in the speci=ed range leading to an in-
completely speci=ed product composition. For the exam-
ple in Fig. 16, the stage composition manifold will be a
volume. This stage composition manifold is equivalent to
a stage composition line, which contains all components
leading to a completely speci=ed product composition.
Combined manifolds can also be plotted for a strip-
ping section in the same way. Fig. 17 shows two com-
bined stripping manifolds, generated from three regular
manifolds, leading to a bottoms composition b. The reg-
4405
ular manifolds in Fig. 17 are linear while the combined
manifolds are volumes, since four points make up each
manifold. These volumes are really approximations of the
combined manifolds, which should be surfaces. Smaller
boil-up ratio intervals will result in more accurate strip-
ping manifolds.
An intersection between a combined rectifying and
combined stripping manifold indicates feasible pa-
rameters, as shown in Fig. 18. For clarity, only two
combined manifolds are plotted. One of the intersec-
tions corresponds to a set of feasible parameters, as
indicated by the column on the right. Unlike the design
method in Section 4.1, the design method for general
splits identi=es feasible ranges of the re<ux and boil-up
ratios instead of precise values. Once a pair of values
for the re<ux and boil-up ratios have been speci=ed,
the feed composition or feed condition can be speci=ed.
Eq. (1) can then be applied to calculate the dependent
variable.
The design method for columns performing general
splits can therefore be de=ned as follows:
1. Specify the principal mole fractions of the distillate
composition if it lies on a composition boundary. If it
lies on a distillation boundary, obtain a composition
on the boundary. This generates the =rst representative
composition.
2. Repeat Step 1 for a bottoms composition.
3. Specify a fractional distance . The composition shift
is calculated as follows:
Composition shift = (Wi − x1i ) for i = 1; : : : ; C − 1
(4)
4406 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416

Fig. 17. Two combined stripping manifolds for a bottoms composition b, at 10 stripping stages and boil-up ratio intervals of 1–2 and 2–3.

Fig. 18. The intersection of a pair of combined rectifying and stripping manifolds indicates feasible parameters.

where Wi is the composition of reachable singular

point and x1i the =rst representative composition.
4. Calculate the remaining representative compositions
using the algorithm presented earlier.
5. Form the combined rectifying and stripping mani-
folds by calculating composition pro=les from the
representative compositions and grouping points
with the same stage number and re<ux or boil-up
ratios.
6. Identify intersections between the manifolds. Every Fig. 19. Two of the elements in the feasibility matrix for the proposed
intersection represents a feasible set of parameters. split in Fig. 18.

Although Fig. 18 shows only one intersection, there

will be many intersections between both sets of mani- tion 4.1, the feasibility matrix for general splits displays
folds, re<ecting the many di7erent feasible combinations feasible intervals of the re<ux and boil-up ratios and not
of parameters. These combinations can be represented in exact values. Fig. 19 shows two of the many (r × s) ma-
a feasibility matrix, as before. Unlike the matrices in Sec- trices for the example in Fig. 18.
 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416
These matrices, unlike the ones in Section 5:3, can-
not be corrected. This is because the tuning algorithm re-
quires one completely speci=ed product composition for
the calculation of the complete composition pro=le. Be-
cause neither product composition is speci=ed completely
in a general split, the tuning algorithm cannot be applied
to the feasibility matrix.
5.2. Comments
A comparison of the design method for pure compo-
nents (Section 4.1) and the design method for general
splits will show that the design method for pure com-
ponents is in fact a special case of the broader design
method for general splits. Although it is not strictly re-
quired, a (C − 1)-dimensional split performed in a sim-
ple column with a pure component as one product will
always mean that the component in question is a node.
This, in turn, indicates that all singular points in the same
region as the pure component will be reachable from the
pure component, if it is an unstable node, or the com-
ponent will be reachable from all the singular points
in the region, if the component is a stable node. The
manifolds generated using both methods will be qual-
itatively similar, although the manifolds generated us-
ing the design method for general splits will be more
accurate.
This similarity is demonstrated in Fig. 20, where an in-
direct split to recover chlorobenzene is proposed. Because
point 4 (chlorobenzene) is reachable from all the singu-
lar points, application of the design method for general
splits will identify three representative compositions—
two on the binary axes 1– 4 and 2– 4, and one on the
Fig. 20. Stripping manifolds for a pure chlorobenzene bottoms product using (a) the design method for general splits and (b) the design method
for pure components.
4407
(3– 4) distillation boundary. The resulting stripping man-
ifolds will be a set of angular lines, which will be ap-
proximated by a set of 2-D volumes (areas), as shown in
Fig. 20a. In Fig. 20a the composition shift, , is speci=ed
as 0.001, which is equivalent to specifying a chloroben-
zene purity of 99.9% in the design method for pure com-
ponents (Fig. 20b). Only two representative composi-
tions are required in this case. The manifolds in Figs. 20a
and b are in fact qualitatively identical. The application
of the design method for pure components is, however,
more ePcient in this case as the manifolds are easier to
describe.
Every stripping manifold in Fig. 20a is generated from
three points—two on the binary composition boundaries,
and one that should be on the distillation boundary. The
points, labelled x; y and z in Fig. 20a, are calculated
from composition pro=les from a representative compo-
sition on the (3– 4) boundary. The algorithm for calculat-
ing this representative composition, described in Section
5.1, assumes linear composition and distillation bound-
aries. Since the distillation boundary in Fig. 20a is not
completely straight, the calculated representative compo-
sition will not be on the boundary. As a result, the compo-
sition pro=les calculated from this composition will stray
from the distillation boundary, as do the points x; y and
z in Fig. 20a. This will a7ect the accuracy of the design
method. The accuracy can be improved by calculating
representative compositions, when required, on the dis-
tillation boundary (and not on a linear approximation of
the boundary) using the method described by Thong and
Jobson (2001).
In the design method for general splits, neither prod-
uct composition is speci=ed completely. This is in
4408 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416
Fig. 21. Stage composition lines, calculated from a completely speci=ed distillate composition, and stripping manifolds, calculated from an
incompletely speci=ed bottoms composition, do not intersect as the distillate composition is too constrained.
contrast to the design method for columns producing pure
components, where the co-product composition is spec-
i=ed completely to enable the application of the tuning
algorithm for the correction of the feasibility matrix. In-
stead of specifying completely the co-product composi-
tion, the mole fractions of the principal components can
be speci=ed, as is the case in the design method for gen-
eral splits. This type of speci=cation will result in the
generation of composition manifolds, or combined man-
ifolds, from the co-product composition. The end results
in both cases will be similar, but the range of feasible
parameters identi=ed is likely to be greater in the case of
the incomplete product speci=cations as there will be ad-
ditional degrees of freedom in the unspeci=ed mole frac-
tions. In not specifying completely the co-product compo-
sition, however, errors in the feasibility matrix cannot be
corrected.
Similarly, instead of specifying two incomplete prod-
uct compositions for a general split, one product compo-
sition can be speci=ed completely. As before, composi-
tion manifolds can be calculated from the incompletely
speci=ed product while the completely speci=ed product
composition results in the generation of stage composi-
tion lines. Intersections are evaluated in the usual manner,
and the feasibility matrix can be constructed. Because
one product composition is speci=ed completely, the tun-
ing algorithm can be applied to correct the feasibility
matrix.
The obvious drawback to completely specifying one
product composition is the speci=cation of the amounts
of impurities. In the worst case, an improper product
speci=cation will result in no intersections being de-
tected. This problem does not arise when the co-product
is a pure component as there will always be intersections
between the stage composition lines and composition
manifolds as long as both product compositions are in
the same distillation region. This is not the case with
other, more general splits. An example is illustrated in
Fig. 21. The distillate composition is speci=ed com-
pletely, leading to the generation of rectifying stage
composition lines. These lines, which remain largely on
the 1-2-4 composition boundary, and the stripping man-
ifolds, do not intersect, which implies that these product
compositions are infeasible although Fig. 18 in Section
5.1 shows that these product compositions are in fact
feasible.
6. Four-component example
The design method is applied to a quaternary
azeotropic mixture of methyl acetate, methanol, ethyl
acetate and ethanol at atmospheric pressure. The pure
component and mixture properties are obtained from the
HYSYS v.1.2.9 simulation package. The Wilson liquid
activity model and an ideal vapour phase model are used
in this example. The mixture forms three azeotropes and
the composition space displays two distillation regions.
Using the feasibility test for classes of splits described
in Thong and Jobson (2001), a sharp split between
methanol and ethyl acetate is identi=ed. This is a type
A split, so a pair of distillate and bottoms compositions
are arbitrarily speci=ed, with  = 0:001 for both product
compositions, representing, in this case, a maximum tol-
erable impurity of 0:1 mol%. Table 2 lists the product
compositions used in the design method, as well as the
representative compositions for both products, which
are used to calculate the feasibility matrix. One of the
 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416 4409

Table 2
Product compositions and representative compositions used in the design method for a proposed split in a quaternary azeotropic mixture

Components Distillate Bottoms

Product Representative Product Representative

composition compositions composition compositions
d d1 d2 d3 d4 b b1 b2 b3 b4

Methyl acetate 0:750 0.75 0.75 0.75 0.75 ¡0:001 0 0 1E−3 7E−4
Methanol 0:250 0.25 0.25 0.25 0.25 ¡0:001 0 7E−4 0 3E−4
Ethyl acetate ¡0:001 0 5E−4 1E−3 0 0:800 0.80 0.80 0.80 0.80
ethanol ¡0:001 0 5E−4 0 1E−3 0:200 0.20 0.20 0.20 0.20

Table 3
Comparison between design speci=cations and simulation results for a general split in a quaternary azeotropic mixture

Components Feed Distillate Bottoms

Design method Rigorous simulation Design method Rigorous simulation

Methyl acetate 0.328 0:750 0.72 ¡0:001 ¡0:001

Methanol 0.109 0:250 0.24 ¡0:001 ¡0:001
Ethyl acetate 0.450 ¡0:001 0.017 0:800 0:804
Ethanol 0.113 ¡0:001 0.019 0:200 0:196

elements of this matrix is shown below
Nr = 20
r ratios will also vary along the length of the column. As
12345
1   lated using Eq. (1), the size of this range depending on
0000
2 0 0 0 0
Ns = 20 s 3  
0 0 1 1
4
0111
5
One of the elements of the (r × s) matrix, highlighted
in bold, is used to initialise a rigorous simulation. Be-
cause ranges of re<ux and boil-up ratios are identi=ed,
mid-point values of r = 3:5 and s = 3:5 are chosen. The
feed composition is calculated using Eq. (1) after a feed
quality (q = 1) is speci=ed. Table 3 lists the results from
the simulation, in comparison to the design speci=cations.
The bottoms speci=cations are largely met, while the
distillate speci=cations are not. This is primarily due to
the non-constant vapour and liquid <ows through the col-
umn, a condition that is not accounted for in the design
method. Heat e7ects can be accommodated in the design
method by introducing energy balances in the calculation
of the composition pro=les (Knight & Doherty, 1986).
Including energy balances will increase the accuracy of
the design method at the expense of computational ef-
fort. However, the principal purpose of the design method
is to provide initial values for rigorous simulations. The
examples presented here indicate that the assumption of
constant molar over<ow is suPcient for this purpose. An
additional source of errors is the calculation of the feed
composition using Eq. (1), which is exact for uniform
vapour and liquid <ows only. When the vapour and liquid
<ows in the column vary, the external re<ux and boil-up
a result, a range of feasible feed qualities can be calcu-
the extent of the heat e7ects on the internal <ows.
7. Conclusions
A new distillation column design method is presented.
The design method overcomes the limitations of existing
design tools by eliminating the requirement of specify-
ing completely both product compositions. Composition
manifolds, analogous to points on a composition pro=le,
can be calculated from incompletely speci=ed product
compositions. The intersection of a pair of rectifying and
stripping manifolds indicates feasible parameters. The de-
sign method is developed for two scenarios—a column
producing a pure component, and a column performing a
general split. The design method is applied here assum-
ing constant molar over<ow, although this assumption is
easily relaxed at the cost of additional computational
e7ort.
In the case of a column producing a pure component,
composition manifolds are calculated from the pure com-
ponent product region. The composition of the co-product
is speci=ed completely, leading to the generation of stage
composition lines. Every intersection between the stage
composition lines and composition manifolds represents
di7erent combinations of column parameters. This infor-
mation can be conveniently represented in a feasibility
4410 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416

matrix, which can, if so desired, be transformed into a

matrix of appropriate economic indicators, from which
favourable parameters can be identi=ed. Errors in the fea-
sibility matrix due to the assumption of linear composi-
tion manifolds can be corrected by applying a numerical
tuning algorithm.
For columns performing general splits, both product
compositions are incompletely speci=ed. This generates
rectifying and stripping manifolds, from which combined
rectifying and combined stripping manifolds are formed.
The size and position of these combined manifolds de-
pend on the amount of impurities in the product compo-
sitions, a value of which can be speci=ed prior to design.
A feasibility matrix represents the feasible and infeasible
combinations of parameters, calculated from the inter-
sections between the combined rectifying and combined
stripping manifolds. The design method for general splits
is applicable in cases where both products are on distil-
lation or composition boundaries, and is limited by the
Fig. 22. Flowchart displaying the overall strategy employed in the
assumption of linear manifolds. tuning algorithm.

Notation

b bottoms mole fraction volving a pure component product. In a broader sense, the
C number of components tuning algorithm is used to calculate one product com-
 fractional distance position given the co-product composition, number of
d distillate mole fraction stages and feed stage location, and values of the re<ux
f feed mole fraction and boil-up ratios. Fig. 22 illustrates the overall strategy
F feed molar <owrate employed. The terms i and i represent the completely
N number of stages and incompletely speci=ed product compositions, respec-
q feed quality (0 = saturated tively. The actions in Fig. 22 are labelled 1–5, and are
vapour, 1 = saturated liquid) described in detail below.
r external re<ux ratio
s external boil-up ratio
V vapour molar <owrate (mol=s) A.1.1. Specifying invariant parameters
W mole fraction of singular point The =rst step in the algorithm is the speci=cation of i
x liquid phase mole fraction (i = 1; : : : ; C − 1), Nr , Ns , r and s. This is straightforward
as the values of these parameters can be obtained from
Subscripts the results of the column design method. The values of
these parameters remain constant throughout the duration
i component i in a multicomponent mixture of the calculations.
r rectifying section
s stripping section
A.1.2. Specifying an estimate of i
This step is necessary for the calculation of the com-
Acknowledgements plete composition pro=le in the next step. A value of iest
The authors would like to acknowledge the support of (i = 1; : : : ; C − 1) can be obtained from the results of the
the UMIST Process Integration Research Consortium. design method. For columns producing pure components,
the value of i could be the mole fraction of the compo-
nent to be recovered (e.g., 0.99 tert-butanol) and equimo-
Appendix A. Tuning algorithm for the correction of the
lar amounts of the remaining components. For a general
feasibility matrix
split, i can be any of the representative compositions.
A.1. Overall strategy Although it is not necessary to provide a good initial es-
timate of i , as is demonstrated in Fig. 11 in Section 4.2,
The tuning algorithm is described brie<y in Section 4.2 poor estimates will usually result in longer convergence
as a means to correct the feasibility matrix for a split in- times.
 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416
Fig. 23. Column model for a speci=ed bottoms composition and an
estimated distillate composition.
A.1.3. Calculation of the complete composition pro9le
The complete composition pro=le is the merger of the
rectifying and stripping pro=les. The complete composi-
tion pro=le is calculated starting from the speci=ed prod-
uct composition i . The composition pro=le in the col-
umn section producing this product is calculated in the
usual manner, up to the feed stage. The remaining com-
position pro=le is calculated in the same direction up (or
down) the remainder of the column to the top (or bottom)
stage using bubble point (or dew point) calculations and
material balances over i .
An example is illustrated in Fig. 23. The bottoms com-
position is speci=ed completely and the stripping pro=le
is calculated by alternating between a material balance
over the bottom half of the column, represented by the
lower control volume, and bubble point calculation, rep-
resented by thick curved arrows. This calculation con-
tinues until x n has been computed. The value of yn is
then obtained using a bubble point calculation, i.e., yn
is assumed to be in equilibrium with x n as there is per-
fect mixing on the feed stage. The value of x n+1 is then
calculated by a material balance over the top half of the
column. The bubble point and material balance calcula-
tions continue up the rectifying section until the speci=ed
top stage is reached. The liquid (or vapour, depending
on the type of condenser) composition is the calculated
distillate composition icalc . The feed composition and
condition are not required in the calculations. The equa-
tions describing both material balances in Fig. 23 are as
follows:
4411
Stripping section
syn−1 + i
xn = for i = 1; : : : ; C − 1: (A.1)
s+1
Rectifying section
(r + 1)yn − i
x n+1 = for i = 1; : : : ; C − 1: (A.2)
r
Eqs. (A.1) and (A.2) are applied when the composition
pro=le is calculated up the column. If the distillate com-
position is speci=ed and the composition pro=le is to be
calculated down the column, both material balances are
the same but the calculated variables are now yn−1 and
yn in the stripping and rectifying sections, respectively.
The calculation procedure is similar in the case where the
distillate is speci=ed completely. In this case, however,
dew point calculations are used instead of bubble point
calculations.
A.1.4. Criterion for convergence
This step simply requires the discrepancy between the
mole fractions of the estimated and calculated values of
i to be smaller than a speci=ed tolerance. This toler-
ance can be an absolute value, e.g., 0.001, or a fractional
change, e.g., a 0.1% change from the last iteration. In the
boundary value method for column design (Van Dongen
& Doherty, 1985), two product compositions are feasible
if there is a composition pro=le linking the two products.
The composition pro=les are usually calculated starting
from both product compositions—if the pro=les intersect
at a point, the product compositions and design parame-
ters are feasible. A converged value of i has the same
physical meaning as the aforementioned approach as the
convergence means that the material balances and VLE
relations are satis=ed at all column stages.
A.1.5. Obtaining a new estimate for i
Once icalc is obtained from an initial guess of iest and
the discrepancy between icalc and iest is not small enough
for convergence, a new value of iest is necessary for the
next iteration. This is achieved by combining icalc and
iest , the full procedure for which is described below.
1. Rationalise icalc , i.e., round o7 to unity mole fractions
that are greater than one, and set to zero any negative
mole fractions. This generates icalc; rat .
2. Calculate the intermediate composition iest; int using
the following equation:
(icalc; rat − iest )
iest; int = iest + for i = 1; : : : ; C − 1;
FCONi
where FCONi is the convergence factor
3. Normalise iest; int . This generates iest for the next iter-
ation.
Step 2 in the algorithm represents a linear combination of
the mole fraction of each component in iest and icalc; rat .
4412 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416

Table 4 Table 5
Typical values of FCONi in use in various cycles Distillate composition (speci=ed) and bottoms compositions (initial
guess and converged) in an indirect split
Cycle 1 2 3 4
Distillate Bottoms Bottoms
FCON1 20 60 1000 2500 (speci=ed) (initial guess) (converged)
FCON2 5 20 500 1000
FCON3 2.5 5 10 100 Acetone 0.16 0.01 6E−11
FCON4 2 2.5 10 25 Methyl acetate 0.14 0.02 1E−8
FCON5 1.5 2 5 25 Chloroform 0.14 0.03 6E−6
Methanol 0.14 0.04 9E−8
Ethyl acetate 0.14 0.05 6E−5
Ethanol 0.14 0.06 8E−7
Interpreted in a di7erent way, it represents a linear com- Benzene 0.14 0.07 8E−4
Toluene 1E−4 0.72 0.9991
position shift from iest to icalc; rat , the magnitude of this
shift being determined by the convergence factor FCONi .
The larger the value of FCONi , the smaller the composi-
tion shift. Notice that Step 2 is carried out for all C com- the tuning algorithm converges ‘naturally’ on i , i.e., the
ponents. This necessitates a normalisation of the mole algorithm does not need large values of FCONi to con-
fractions in Step 3. verge. This situation does not arise in the case of a gen-
The value of FCONi depends on the di7erence between eral split, although in this work the tuning algorithm is
icalc and iest and is, in general, di7erent for each compo- applied only to the pure-component case. The algorithm
nent. This di7erence, Qi , is calculated using does not mathematically guarantee convergence on an
Qi = icalc − iest for i = 1; : : : ; C − 1: exact value of i although convergence was achieved in
all cases studied. Even if non-convergence occurs, iest at
The value of FCONi also depends on the iteration count. the end of the iteration will be close enough to the ac-
The procedure is divided into various cycles, each cy- tual value of i , as will be demonstrated in the following
cle containing a certain number of iterations during section.
which FCONi is held constant. FCONi is calculated for
each component by comparing the value of Qi against A.2. Examples
Qi; min , which is a benchmark and does not necessarily
have to be the same as the minimum tolerance de=ned Application of the tuning algorithm to two examples
in Section A.1.4. As an example, FCONi is calculated is now presented. In both cases four cycles are used,
as follows (Qi; min = 0:0001) during the =rst cycle. the =rst two cycles having 10 iterations each, and the
Table 4 lists some values of FCONi during di7erent last two having 20 iterations each. The convergence fac-
cycles. tors used in these examples are shown in Table 4 in
If Section A.1.5.
Qi ¿1000Qi; min ; FCONi; 1 = 20 In the =rst example, the indirect split to recover a 99.9%
Qi ¿100Qi; min ; FCONi; 1 = 5 toluene bottoms product, presented in Section 4.3, is anal-
Qi ¿10Qi; min ; FCONi; 1 = 2:5 ysed. The parameters used are Nr = 11, Ns = 11, r = 2,
Qi ¿1Qi; min ; FCONi; 1 = 2 s = 3. Table 5 displays the speci=ed distillate composi-
Qi ¡Qi; min ; FCONi; 1 = 1:5 tion, the initial guess of the bottoms composition, and the
=nal converged value. The calculation took 10 s to com-
As mentioned before, the size of FCONi is inversely pro- plete on a computer with a Pentium III processor. Com-
portional to the size of the composition shift from iest to parison of the two bottoms compositions in Table 5 will
icalc; rat . Table 4 shows that the algorithm ‘forces’ con- reveal that the initial guess of the bottoms composition is
vergence as the iteration count increases. The purpose of a poor one. Nevertheless, the algorithm converges on a
the low FCONi values in the =rst cycle is to allow poor =nal value. Fig. 24 shows the mole fraction of the various
estimates of i to be accounted for. The values of FCONi components plotted against the iteration count.
become progressively larger as the cycle count increases. The tuning algorithm should converge on the exact bot-
FCONi in the =nal cycle can be set to a large enough toms composition, i.e., composition pro=les calculated
value to arti=cially induce convergence, i.e., FCONi is from both product compositions should meet exactly at
so large that the change in i is smaller than the mini- the feed stage when calculated at the speci=ed parame-
mum speci=ed tolerance. This approach can potentially ters. Table 6 shows the calculated rectifying and strip-
lead to convergence on an incorrect value of i . Such ping pro=les from the speci=ed distillate composition
situations are avoided by allowing a suPcient number and converged bottoms composition, respectively. The
of iterations in the previous cycles. It should be noted pro=les do not meet exactly at the feed stage, as high-
that in the case of a split involving pure components, lighted in bold. This is because the mole fractions of the
 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416 4413

Fig. 24. Mole fraction of the various components plotted against the iteration count in an indirect split.

impurities in the bottoms, which exert a major in<uence
on the stripping pro=le, are not completely converged.
Table 7 shows the pro=les for a di7erent converged bot-
toms composition, this time with large values of FCONi
and after many iterations. The pro=les intersect exactly
at the feed stage in this case. The calculation took 2 min
to complete on a Pentium III computer. The converged
bottoms compositions in Tables 6 and 7 are almost identi-
cal although the feed stage compositions, calculated from
both product compositions, are di7erent. This similarity
shows that for a preliminary study, the tuning algorithm
can be applied with an acceptable degree of accuracy in
a reasonable number of iterations. The discrepancy be-
tween feed stage compositions also highlights the e7ect
of small di7erences in the product compositions on the
resulting composition pro=les. The 0’s in both tables rep-
resent mole fractions that are less than 10−8 .
The next example is the general split from Section 6.
The distillate composition is speci=ed arbitrarily, and the
initial estimates and =nal converged bottoms composi-
tion are shown in Table 8. Also shown in Table 8 is the
actual converged bottoms composition using large values
4414 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416

Table 6
Rectifying and stripping pro=les calculated from the (speci=ed) distillate and (converged) bottoms compositions, respectivelya

Acetone Methyl acetate Chloroform Methanol Ethyl acetate Ethanol Benzene Toluene

Distillate 0.1599 0.14 0.14 0.14 0.14 0.14 0.14 0.0001

1 0.1271 0.1096 0.1697 0.0649 0.2269 0.1368 0.1647 0.0003
2 0.1007 0.0875 0.1888 0.0327 0.2991 0.1071 0.1832 0.0008
3 0.0819 0.0723 0.1987 0.0208 0.3508 0.0780 0.1954 0.0020
4 0.0697 0.0626 0.2021 0.0165 0.3833 0.0588 0.2027 0.0044
5 0.0622 0.0566 0.2013 0.0146 0.4012 0.0479 0.2066 0.0095
6 0.0573 0.0529 0.1978 0.0136 0.4077 0.0418 0.2088 0.0202
7 0.0534 0.0502 0.1913 0.0126 0.4029 0.0373 0.2100 0.0423
8 0.0488 0.0475 0.1797 0.0113 0.3835 0.0325 0.2103 0.0864
9 0.0423 0.0437 0.1600 0.0094 0.3430 0.0261 0.2074 0.1682
10 0.0338 0.0382 0.1304 0.0070 0.2778 0.0184 0.1950 0.2995
11 0.0250 0.0316 0.0954 0.0048 0.1975 0.0115 0.1674 0.4668

Bottoms 6E−11 1E−8 6E−6 9E−8 6E−5 8E−7 8E−4 0.9991

1 0 0 0 0 0.0001 0 0.0016 0.9982
2 0 0 0 0.0001 0.0004 0.0003 0.0031 0.9961
3 0 0 0.0001 0.0021 0.0008 0.0073 0.0057 0.9839
4 0 0 0.0003 0.0503 0.0015 0.1202 0.0083 0.8194
5 0 0 0.0003 0.2200 0.0010 0.2937 0.0061 0.4790
6 0 0 0.0003 0.3353 0.0007 0.2353 0.0056 0.4228
7 0 0 0.0004 0.4308 0.0005 0.1571 0.0053 0.4059
8 0 0 0.0004 0.5043 0.0003 0.0945 0.0049 0.3955
9 0 0 0.0005 0.5533 0.0002 0.0528 0.0044 0.3887
10 0 0 0.0005 0.5824 0.0002 0.0282 0.0010 0.3847
11 0 0 0.0006 0.5985 0.0001 0.0146 0.0036 0.3825
12 0 0 0.0007 0.6071 0.0001 0.0075 0.0033 0.3814

a Values highlighted in bold indicate the feed stage compositions as calculated from the distillate and bottoms compositions.

Table 7
Rectifying and stripping pro=les calculated from the (speci=ed) distillate and (converged, accurate) bottoms compositions, respectively

Acetone Methyl acetate Chloroform Methanol Ethyl acetate Ethanol Benzene Toluene

Distillate 0.1599 0.14 0.14 0.14 0.14 0.14 0.14 0.0001

1 0.1271 0.1096 0.1697 0.0649 0.2269 0.1368 0.1647 0.0003
2 0.1007 0.0875 0.1888 0.0327 0.2991 0.1071 0.1832 0.0008
3 0.0819 0.0723 0.1987 0.0208 0.3508 0.0780 0.1954 0.0020
4 0.0697 0.0626 0.2021 0.0165 0.3833 0.0588 0.2027 0.0044
5 0.0622 0.0566 0.2013 0.0146 0.4012 0.0479 0.2066 0.0095
6 0.0573 0.0529 0.1978 0.0136 0.4077 0.0418 0.2088 0.0202
7 0.0534 0.0502 0.1913 0.0126 0.4029 0.0373 0.2100 0.0423
8 0.0488 0.0475 0.1797 0.0113 0.3835 0.0325 0.2103 0.0864
9 0.0423 0.0437 0.1600 0.0094 0.3430 0.0261 0.2074 0.1682
10 0.0338 0.0382 0.1304 0.0070 0.2778 0.0184 0.1950 0.2995
11 0.0250 0.0316 0.0954 0.0048 0.1975 0.0115 0.1674 0.4668

Bottoms 3E−11 1E−8 6E−6 2E−18 6E−5 3E−17 8E−4 0.9991

1 0 0 0 0 0.0001 0 0.0016 0.9982
2 0 0 0 0 0.0004 0 0.0031 0.9965
3 0 0 0.0001 0 0.0008 0 0.0058 0.9932
4 0 0 0.0003 0 0.0020 0 0.0104 0.9872
5 0 0 0.0009 0 0.0046 0 0.0185 0.9760
6 0 0 0.0022 0 0.0104 0 0.0322 0.9551
7 0 0.0002 0.0055 0 0.0226 0 0.0540 0.9177
8 0.0001 0.0006 0.0125 0 0.0459 0 0.0856 0.8553
9 0.0005 0.0020 0.0261 0 0.0835 0 0.1236 0.7642
10 0.0022 0.0058 0.0472 0 0.1316 0.0002 0.1577 0.6553
11 0.0081 0.0147 0.0731 0 0.1761 0.0019 0.1749 0.5512
12 0.0252 0.0318 0.0960 0 0.1988 0.0116 0.1684 0.4682
 D. Y.-C. Thong, M. Jobson / Chemical Engineering Science 56 (2001) 4393–4416 4415

Table 8
Distillate composition (speci=ed) and bottoms compositions (initial guess, converged and accurately converged) in an general split

Distillate Bottoms Bottoms Bottoms

(speci=ed) (initial guess) (converged) (accurate-conv.)
Methyl acetate 0.750 0 0.166 0.236
Methanol 0.249 0 4E−7 5E−7
Ethyl acetate 9.9E−4 0.8 0.736 0.764
Ethanol 1E−5 0.2 0.098 1E−4

Fig. 25. Mole fraction of the various components plotted against the iteration count in an general split.

of FCON and many iterations. The parameters used in
this example are Nr = 20, Ns = 20, r = 2, s = 2.
Table 8 shows that the parameters used in this example
will result in some errors in the =nal converged bottoms
composition, although the errors are not substantial. Un-
like the previous example, the bottoms composition in this
general split does not converge naturally. This can be ob-
served from the oscillations in the composition–iteration
graphs in Fig. 25. The mole fractions are ‘forced’ to con-
verge by increasing the value of FCONi in each succes-
sive cycle. Careful observation of the values in Table 8
will reveal that the initial guess and converged distillate
compositions are in di7erent distillation regions. Thus, it
can be seen that the tuning algorithm does not require
good estimates of i in order to converge.
The oscillations in Fig. 25 point out inePciencies in
the algorithm, i.e., iterations within a cycle continue al-
though an improvement in the solution is not forthcom-
ing. These inePciencies can be recti=ed by taking into
account these oscillations, e.g., moving on to the next
cycle when oscillations are detected. Such steps will im-
prove the ePciency of the algorithm but will not a7ect
the accuracy of the results obtained.
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