Computerx chem. Engng Vol. 20, Suppl., pp.

$55-$60, 1996
Copyright 1996 Elsevier Science Ltd
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Pergamon

MINIMUM

ENERGY DEMAND FOR NONIDEAL MULTICOMPONENT

D I S T I L L A T I O N S IN C O M P L E X C O L U M N S
J. BAUSA, R. v. WATZDORF and W. MARQUARDT

Lehrstuhl fiir Prozei~technik, RWTH Aachen, Turmstrat3e 46, D-52056 Aachen, Germany
e-maih (bansa, watzdorf, marquardt}@lfpt.rwth-aachen.de
A b s t r a c t - The minimum energy demand of a specified separation is a key parameter in process
design. However, a simple and fast short-cut method applicable to all types of splits and
mixtures in both simple and complex columns is not yet available. In this paper a new general
method for calculating the minimum energy demand for distillation columns is presented. It
stems from a geometric analysis of the plate-to-plate profiles and uses all pinch points of both
column sections. No a-priori choice of relevant solution branches of the pinch equations is
required. The computational effort is low since no rigorous plate-to-plate calculations are
necessary. The method can be applied to nonideal multicomponent mixtures of an arbitrary
number of species and is not restricted to any type of split. Its extension to complex columns
with sidecolumns or sidestreams is outlined.
INTRODUCTION
The design of multicomponent separations by distillation gives rise to a large number of possible column
sequences, especially when complex columns with sidestreams, -strippers and -enrichers are taken into consideration. To determine and exclude unfavourable sequences in an early phase simple and fast short-cut
methods are needed, which allow a quick evaluation of the separation. The minimum energy demand of a
specified separation is a purely thermodynamically fixed value and depends only on the specification of the
feed, the desired products and the column pressure. Thus it can be evaluated in an early stage of process
design, when detailed information is not yet available. It can serve as a first estimate for the actual energy
demand of the column and will constitute an effective means for rapid evaluation of alternatives.
For ideal mixtures characterized by constant relative volatilities and negligible heat effects recent generalizations of the classical Underwood method (Underwood, 1948) have provided a comprehensive suite of
short-cut procedures applicable to all kinds of separations in simple and complex columns. For nonideal
mixtures, however, corresponding general techniques are still missing. Even for simple columns, a short-cut
procedure, which accounts for nonideal mixtures and which can be applied to all types of splits, is not yet
available. Instead conventional simulation programs are used in industrial practice allowing to determine
the minimum energy demand only in a time consuming process with many manual iterations.
In the first part of this paper the fundamentals of the geometric analysis of nonideal separations are
briefly outlined. An illustrative example is provided highlighting the drawbacks of the different available
techniques. Subsequently a new general technique for minimum reflux calculation is exposed and applied to
nonideai separations both in simple and complex columns.
COLUMN PROFILES AND PINCH POINTS
The considerations which lead to the new minimum reflux method presented here are based on a geometric
analysis of the rigorous plate-to-plate profiles. Using component balance, energy balance and thermodynamic properties of the mixture the following set of equations can be derived for the rectifying section:
Y*(~+I)
y
QD
h n + l + L,~ +----D

L~
D
L~ + --'~Xn,i "~ ~

L,~
L
D
Ln + D h~ + L--~+D hD

XD, i ; n = 1 ... n I

; n = 1 ... n I

; i = 1 ... C

(1)

(2)

If the product composition, the product flowrate and an arbitrary condenser duty are given, the profile of
the rectifying section can be calculated step by step starting from the distillate. For given flowrate and
composition of both products the corresponding reboiler energy can be determined using an energy balance
for the whole column and the profile of the stripping section can be calculated from a set of equations
analogous to eqs. (1) and (2). Since the condenser duty was chosen arbitrarily, the calculated profiles do
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European Symposiumon Computer Aided Process Engineering---6. Part A

not need to correspond to a feasible separation. They correspond to a feasible separation only if they
intersect in composition state space. The so-called point of intersection represents the liquid on the feed
tray. Calculating the minimum reflux ratio with the boundary value method (BVM) means searching for
the smallest reflux ratio that makes intersection of both profiles possible (Levy et al., 1985).
Equations (1) and (2) can be seen as an implicit recurrence. If all variables on plate n are given, the
composition on plate n + 1 can be calculated. This recurrence has fixed points where n = ',~+1, which
correspond to the pinch points of the separation and can be calculated in the rectifying section from
Y*(:~P)

Lp
L p + D "xP'i

fp

Lp + D

D
L p q- D xD'i
Lv

-ShD

(3)

i = 1 ... C ,

(4)

Lp + D

For a given product Eqs. (3) and (4) have one degree of freedom. Thus the solution manifold is one
dimensional and can be interpreted geometrically by a curve in the composition state space parametrized
by the energy demand. If the condenser duty is also fixed, pinch points can be determined. Since the pinch
equations have in most cases more than one solution branch (Fig. 2, left), multiple pinch points for a specified
reflux ratio can be calculated in each column section. Thus, continuation methods and bifurcation analysis
are required in order to reliably determine all solutions. There are two types of pinch points: End pinches
are stationary points, thus the column profile must end in these pinches; in contrast a profile will go to a
saddle but will leave it afterwards. The type of a pinch point can be determined by means of the eigenvalues
of the linearized plate-to-plate recurrence, as shown by Julka et al. (1990) and PSllmann et al. (1994).
The solutions of the algebraic pinch equation do not necessarily have to occur in the column profile.
Some of them can never be reached by the column profile of a simple separation. Thus, it is not a simple
task to determine which of the calculated pinch points will actually occur in the column profile.
ILLUSTRATIVE
SEPARATION PROBLEM
Let us consider a split of the type ABC/CD of an azeotropic quaternary mixture, where the distillate contains
negligible amounts of the heaviest component D and the bottom product contains negligible quantities of
components A and B. In order to apply the boundary value method we have to estimate the mole fraction
of component D in the distillate and of components A and B in the bottom product since at least traces
of all components have to be in both products. The great sensitivity of the plate-to-plate profiles requires
two nested iterations. Firstly, a reflux ratio has to be estimated. Subsequently, the exact amount of the
trace impurities minimizing the distance between both profiles has to be determined. If intersection is not
possible: the reflux ratio has to be increased and the amount of the impurities has to be recalculated.
AN

profiles of the stripping section

profile of the rectifying section

A saddle pinch BD//~oluene

c h l o r o f o r m [ ] ~ ~I

///~uene

column profile
~ l u e n e

I ~,

chloroform ~

__chloroform

etone
Fig. 1:

Plate-to-plate profiles at QB,mi,~ (:gD = (0.45/0.45/0.1/0), 2B

(0/0/0.125/0.875), 2"F = (0.18/0.18/0.115/0.525), D / F = 0.4, p = 1.013 bar).

acetone
=

Fig. 1 shows profiles of both column sections at minimum reflux determined by the boundary value
method. Since the bottom product lacks two of the feed components, the plate-to-plate calculation leads
to a manifold of profiles if the amount of the trace components is varied (between 10 -25 and 10 -6 in the
example). In the distillate only one component is absent; thus there is no sensitivity of the column section
profile. O11 the right side of Fig. 1 the profile of the whole column is shown which consists of the intersecting
stripping and rectifying profiles. The dashed parts of the rectifying and stripping profiles are not part of
the column profile. It is clear that the effort to determine minimum reflux with this method will drastically
increase if mixtures with more components are taken into consideration.

European Symposiumon Computer Aided Process Engineering---& Part A

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This problem is well known. However, Julka and Doherty (1990) have proved that the plate-to-plate
profiles of ideal separations will always be embedded in the rectifying plane spanned by the appertaining
pinch points irrespective to the exact concentration of impurities. Consequently they advocated to search
for the reflux ratio for which the end pinch of the one column section is situated on the rectifying plane
spanned by the pinch points of the other section. For certain separation problems, however, no end pinch
point is present in the column composition profile (s. Fig. 1, right) and the method cannot be applied.
In order to remedy this problem KShier et al. (1991) have proposed to employ the angle spanned by
the vectors pointing from the feed state to the adjacent two pinch points as a criterion for minimum reflux.
They claimed that the minimum reflux condition is uniquely defined by the particular set of pinch points for
which this angle is minimal. While this criterion reduces to that of Julka and Doherty and has a physical
explanation in the ternary case, it lacks a corresponding foundation for multicomponent separations. In
addition, the proper choice of the pair of pinch points is not obvious for certain separations as indicated by
Fig. 1. Either the saddle pinch point of the rectifying and the end pinch point of the stripping profile or the
corresponding, alternative pinch point pair are feasible candidates for the minimum angle criterion.
P611mann et al. (1994) substitute the minimum angle criterion by a physical explainable one. However,
their procedure also uses only one pinch point in each column section without giving a reliable criterion to
determine the right solution branch. Even for ternary systems the occurrence of pinch points in the column
profile can often not be stated a-priori and for more than three components this problem gets even more
involved. In order to tackle the problem of minimum reflux calculation in a general way, a new criterion has
to be devised, which is applicable to any kind of split irrespective of the mixture's nonideality and which
requires no a-priori selection of pinch points.
A NEW CRITERION TO DETERMINE MINIMUM ENERGY DEMAND
An analysis of the geometric behavior of the profiles shows that their trajectories in the composition state
space can be predicted based upon the knowledge of the corresponding pinch points, since they must end in
an end pinch and will change their direction in a saddle pinch. In the stripping section in Fig. 1 the three
pinch points and the composition of the bottom product form a tetrahedron which approximates all possible
stripping profiles regardless the specification of the trace components. Although the rectifying profile is
curved it can be approximated by a triangle which is formed by the two pinch points and the distillate state.
The geometric approximation of the manifold of the stripping profiles and the rectifying profile can be used
to determine if intersecting profiles of both column sections exist: If the tetrahedron of the stripping section
and the triangle of the rectifying section intersect, there must also be intersecting profiles of both column
sections, thus the separation is feasible. To determine minimum reflux with the new method means to find
the smallest reflux ratio which makes intersection of the two simplexes possible. If the triangle penetrates
the tetrahedron, the separation is possible but at higher than minimum reflux. If there is no intersection at
all, the profiles of the column sections cannot intersect and the separation is not feasible. Thus the reflux
ratio which allows the triangle just to touch the tetrahedron must be found (see Fig. 2).
pinch point curves
Bc~Oluene

\ \
//',,t.

endpi=hbraches
\

=
at = = m

rectification bodies
B
toluene

saddle pinch branches

2'~0 ~

reO,,x

chloroform

v azeotrope

/ ~ D

chloroform

Fig. 2: Pinch point loci and rectification bodies corresponding to Fig. 1.

For noaideal mixtures this linear approximation of the plate-to-plate profiles is not exact. The column
profiles can either be concave or convex so that they do not touch at the predicted minimum reflux ratio
(concave case) or touch at a lower reflux ratio (convex case). A comparison for the column in Fig. 1
of the results obtained by the new method ( Q B , m i , ~ / F = 26.2 MJ/kmol), the boundary value method
( Q B , , n i n / F = 25.5 MJ/kmol), and the rigorous simulation tool ASPEN PLUS ( Q s , m i , , / F = 26.1 MJ/kmol)

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European Symposium on Computer Aided Process Engineering--6. Part A

shows that it is still a good approximation. For highly nonideal mixtures or when higher accuracy is needed,
the column profile must be approximated by a body with a curved surface. In this case the tangents of the
rectification body's surface in a pinch point are given by the eigenvectors of the jacobian of the plate-to-plate
recurrence. Investigations along those lines are projected for future work.
The only information needed to determine minimum reflux with the new procedure is the specification
of the products, the column pressure and thermodynamic data of the mixture. In the first step all pinch
point curves of both column sections are calculated and stored. Next a lower bound for the energy demand
has to be estimated and corresponding pinch points axe selected from the stored pinch point curves. Now
the geometric rectification bodies which are formed by the product composition and the pinch points of
the respective column section can be checked for intersection. Since simple polyhedrons can be checked for
intersection in a much more general and easy way than manifolds of plate-to-plate profiles, this task can
be done by a very simple algorithm that is valid for any dimension. Thus the procedure can be applied
irrespective of the number of components. If the bodies do not intersect, the reflux ratio is increased and
corresponding pinch points and bodies axe determined. Using a bisection algorithm the smallest reflux ratio
which allows an intersection can be calculated. Since no computation of column profiles is required, the
procedure is very fast 1.
When applied to ideal mixtures, the new method is equivalent to the geometrical interpretation of
Underwood's method, with the difference, that only pinch points with positive mole fractions are used. The
criterion incorporates certain formulations of the criteria proposed by Julka et al. (1990).

rectification bodies
saddle pinch
B~
toluene

p l a t e - t o - p l a t e profiles
/&toluene

13 end pinch

point of
contact

/1\

/
~

~'~

/ feed tray/

benzene ,

acetone

chloroform acetone

chloroform

Fig. 3: Separation with a pinch at the feed tray (For product composition see
Fig. 1, ~'F =(0.27/0.27/0.11/0.35), D / F = 0.6, p = 1.013 bar).

An important advantage of the new method is that in general no choice of relevant pinch points is
required, since all solutions are used when no tangent pinch occurs. This feature is very important for
separations where the occurrence of a certain pinch point in the column profile cannot be stated a-priori.
Fig. 3 shows a separation where the product composition is the same as in Fig. 1, only the flowrates and
the feed composition differ. Thus, the rule introduced by PSllmann et al. (1994) to predict the occurrence
of pinch points will make no difference between both cuts since it is based on the product composition only.
However, Fig. 1 and 3 show that under minimum reflux different pinch points occur in the column profile. In
Fig. 1, the ternary pinch chloroform/benzene/toluene appears in the column profile whereas a pinch on this
solution branch can never be reached by the column profile in Fig. 3. The end pinch of the rectifying section
that is not reached in Fig. 1 occurs under minimum reflux in the column profile of Fig. 3. The qualitative
difference of these cuts is indicated by the type of intersection between the rectification bodies: In Fig. 2
the triangle touches one edge of the tetrahedron with one of its sides whereas in Fig. 3 the triangle touches
the lower surface of the tetrahedron with its vertex. The minimum energy demand for the separation was
determined with the BVM (QB,m~n/F = 29.7 MJ/kmol), the new method (QB,,u,JF = 29.5 MJ/kmol) and
ASPEN PLUS (QS,mi,~/F = 30.2 MJ/kmol).
Another advantage of the new method is that no special treatment of separations with a tangent pinch is
required, where three pinch solutions occur for a specified reflux ratio on the same branch of the pinch loci.
In this case only the solution that is nearest to the product composition needs to be considered, since all
solutions lying behind this pinch can never be reached by the column profile. When the reflux ratio is higher
than the reflux ratio at the inflection point, there will be again only one solution of the pinch equation on
the solution branch. Thus the pinch point makes a jump when the reflux ratio exceeds the reflux ratio at the
1The calculation of thc separation in Fig. 1 took 11 CPU scconds on a SPARCstation 10.

European Symposium on Computer Aided Process Engineering--6. Part A

$59

inflection point. If the rectification bodies intersect after this jump, minimum reflux is controlled only by
the tangent pinch. In this special case the rectification bodies will not only touch, but cut into each other.
COMPLEX COLUMNS
As columns with sidecolumns can be transformed into a sequence of simple columns as shown by Carlberg et
al. (1989), the minimum reflux procedure can easily be extended to this type of complex column. Separations
in sideproduct columns, however, are qualitatively different. Using the analogous sequence as depicted in
Fig. 4 on the left and specifying feed and distillate streams, bottom product composition as well as the
thermal state of the sideproduct, the net stream leaving the primary separation can be calculated. The
energy demand of the primary separation is obtained by applying the minimum reflux criterion for simple
columns.
D

J"

~)

s
:

toluene

~primary
%separation

liquid state on

~ e a m

tray

ii
~

secondary
; eparation
~

~i!:iii!~ii
aceto

vapour state on
sidestream tray
~deproduet)

: -

column profile

chloroform

Fig. 4: Minimum reflux calculation for a sidestream column.

The secondary separation, however, needs some special considerations, which have not been covered by
the previous work (K6hler et al., 1994). In terms of the BVM the liquid phase on the sidestream tray being
in thermodynamic equilibrium with the sidestream must be reached by a plate-to-plate profile calculated
from the bottom. When the plate-to-plate profile is approximated by the rectification body of the stripping
section, the new criterion requires the composition on the sidestream tray to be within this body. At
minimum reflux the composition on the sidestream tray will lie on the surface of the body (s. Fig. 4, right).
Two different design cases are conceivable: In the first case, a certain bottom product flowrate is chosen
and the corresponding sidestream composition can be calculated by mass balances. Calculating the pinch
points for a fixed bottom product flowrate and variable reboiler duty and testing for the surface criterion
provides the energy demand of the secondary separation which is required to meet the sidestrearn composition
implicitly specified by the particular choice of bottom product flowrate. Subsequent to the calculation of the
minimum energy demand for both separations, the minimum energy demand of the whole column is set to
the higher one of the two values. Thus, in general either the primary or the secondary column will operate
above minimum reflux. Alternatively, intermediate heat exchange can be provided.
0
90 I

QB,min
F

0.2

tTB, toluene

0.4

0.6

0.8

70
60
50 !-

columnwith

main

---~

secondary

separation

separation

40 ~
30 I ~ - - ~
20 0

......
J"
0.1

.2

0.3 B
F-D

0.4

0.5

columnwith
side enricher

().6

Fig. 5: Minimum energy demand for a separation of the type A/BCD/D.

In the second case, the purity of the sideproduct is determined, which is obtained when both separations
axe operated under minimum reflux. The calculation involves the determination of the pinch points of the
secondary separation for a fixed reboiler duty as given by the overall energy balance and a variable bottom

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European Symposiumon Computer Aided Process Engineering--6. Part A

product flowrate. The application of the surface criterion yields the optimal choice of bottom product flowrate
and the limiting sidestream purity for a thermodynamically optimal separation (Meiers et al., 1995),
Fig. 5 shows the minimum energy demand for a separation of the type A / B C D / D in a column with a
sidestream in the stripping section for a varied bottom/sidestream flowrate for the system acetone/chloroform/benzene/toluene (xF = (0.4/0.1/0.1/0.4), 2"B = (0/0/0/1), ZD = (1/0/0/0), D / F = 0.4, qs = O,
p = 1.013 bar). The limiting sideproduct purity is obtained at the bottom flowrate, where the minimum
energy demand of the primary and the secondary separation intersect. Fig. 5 shows that in the considered
case a column with a side enricher has advantages compared to a column with a sidestream only for a high
recovery of component toluene in the bottom product.
CONCLUSIONS AND SIGNIFICANCE
The described method to determine minimum reflux can be applied to any type of split of a nonideal
mixture of any number of components. An important feature is the use of all pinch points. Thus, no a-priori
selection of relevant solutions of the pinch equation is needed. When extended to complex columns, not only
stand-alone distillation columns, but also sequences of both simple and complex columns can be evaluated.
The procedure is fast and easy to use, allowing the evaluation of a large number of variants at an early
phase of process design. Based on the minimum reflux an economic optimal reflux ratio for the actual column
can be estimated. When target compositions and separation pressure are not fixed, it is possible to explore
the influence of these parameters on the minimum reflux ratio. Another application is to initialize rigorous
MINLP optimizations, which need good initial values in order to achieve convergence within reasonable
computational time.
NOTATION

Symbols

Subscripts

B
C
D
F
h
L
N
p
Q

bottom product flow rate, [kmol/s]

number of components
distillate flow rate, [kmol/s]
feed flow rate, [kmol/s]
molar enthalpy, [kJ/kmol]
liquid flow rate, [kmol/s]
net product flow rate, [kmol/s]
pressure, [bar]
energy, [W]

B
D
F
f
i
n
P

S
T
V
x, y

sideproduct flowrate, [kmol/s]

temperature, [K]
vapour flow rate, [kmol/s]
phase composition, [kmol/kmol]
recovery, [kmol/kmol]

L
V
*

bottom
distillate
feed
feedtray
component
tray
pinch point

Superscripts
liquid phase
vapour phase
equilibrium state

REFERENCES

Carlberg, N.A. and Westerberg, A.W., 1989, Temperature-heat diagrams for complex columns. 2. Underwood's method for side strippers and enrichers. Ind. Eng. Chem. Res. 28, No. 9, 1379-1386.
Julka, V. and Doherty, M.F., 1990, Geometric behavior and minimum flows for nonideal multicomponent
distillation. Chem. Eng. Sci. 45, 1801-1822.
KShler, J., Aguirre, P. and Blat], E., 1991, Minimum reflux calculations for nonideal mixtures using the reversible distillation model. Chem. Eng. Sci. 46, 3007-3021.
KShler, J., Kuen, T. and Blab, E., 1994, Minimum energy demand for distillations with distributed components and sideproduct withdrawals. Chem. Eng. Sci. 49, 3325-3330.
Levy, G.S., Van Dongen, D.B. and Doherty, M.F., 1985, Design and synthesis of homogeneous azeotropic
distillations. 2. Minimum reflux calculations for nonideal and azeotropic columns. Ind. Eng. Chem. ,~andam. 24, No. 4, 463-474.
Meiers, R., v. Watzdorf, R. and Marquardt, W., 1995, Nherungsverfahren zur Auslegung yon Seitenstromkolonnen. Chem.-Ing.-Tech. 67, No. 5, 612-615.
PSllmann, P., Glanz, S. and BlaB, E., 1994, Calculating minimum reflux of nonideal multicomponent distillation using eigenvalue theory. Computers chem. Engng 18, Suppl., $49-$53.
Underwood, A. J., 1948, Fractional distillation of multicomponent mixtures. Chem. Eng. Prog. 44, 603-614.