Chemical Engineering Science, 1973, Vol. 28, pp. 1967- 1974. Pergmon Press.

Printed in Great Britain

A rigorous calculation method for the minimum stages

in multicomponent distillation
HENRY H. Y. CHIEN
Monsanto Company, 800 N. Lindbergh Blvd., St. Louis, MO. 63 166, U.S.A.

(Received 30 October 1972; in revisedform 20 December 1972)

Abstract-A computer method is presented using stage by stage component material balances and
nonideal vapor liquid equilibria to calculate the minimum stages for a given key component split in a
multicomponent distillation. The calculated results also include an overall material balance and the
distillate to feed ratio. These results are useful for optimal distillation column design.

INTRODUCTION of stages and the reflux ratio generally are the

IN THE design calculation of a distillation column
with a single feed and no side draw, a set of six
design variables must be specified such that it
gives the desired key component split for a given
feed. The variables are: number of stages above
and below the feed, reflux ratio, distillate to feed
ratio, pressure of the column and vapor fraction
of the feed. Once these variables are specified,
the complete column material balance along with
the temperature, internal vapor and liquid flows
and composition profiles of the column can be
calculated provided that models for the vapor
liquid equilibrium and the enthalpy are already
available.
Most of the available rigorous computer pro-
grams for multicomponent distillation calculation
require that the user specify the six variables and
the feed composition. These programs then com-
pute the complete column material and energy
balance. These are so-called simulation or rating
programs based generally on the algorithm of
Thiele and Geddes [l] with contributions of
others [2-41. Using rating programs in design, the
engineer must search for the values of the design
variables over a wide range to find the economic
optimum. The procedure is tedious but necessary
because of a lack of “design programs.” A “de-
sign program” finds automatically the optimum
design for a given split and a desired economic
return definition.
Among the design variables the total number
1967
most difficult ones to estimate. Many useful rules
of thumb have been developed to help the
engineer in choosing the total stages and the
reflux ratio. The success of these rules is attri-
butable to the flatness of the economic return
function near the optimum; it is not too critical
to get the exact optimum.
These rules are generally stated in relative
quantities; e.g. the ratio of the optimum total
stages to the minimum stages is approximately
two and the optimum ratio of the actual reflux to
the minimum reflux is about 1.25. Thus it is
important to be able to calculate the minimum
reflux ratio and/or the minimum stages for the
system.
For ideal binary separation systems, it is not
difficult to obtain the minimum reflux ratio or the
minimum number of stages. However if the sys-
tem is multicomponent and nonideal, the problem
is difficult. There are several methods published
for calculating the minimum reflux ratio of a
multicomponent system. Most are shortcuts [5,7]
but some are rigorous to a certain degree [6,9].
In the area of minimum stages calculation,
Fenske and Winns methods[ 10,111 have been
known for a number of years. Holland[2] dis-
cussed a method for total reflux simulation. Fair
and Bolles [ 121 used a graphical extrapolation
method to find the minimum reflux and minimum
stages using results from a rigorous simulation
program. No rigorous method for a minimum
 HENRY H. Y. CHIEN

stage calculation for multicomponent systems In the Lewis and Matheson [ 131 algorithm one
has been published to the author’s knowledge. A estimates first the bottoms composition and then
conventional distillation rating program could be calculates compositions up the column with the
used for computing the minimum stages, if the bubble point method. Their method is not used
user could overcome the following difficulties: in this work because estimating the feed stage
composition is easier as well as better in reducing
(1) Truncation error increases as the reflux
the truncation error than estimating the bottoms
ratio increases;
composition. (See Ref. [4] for a discussion of
(2) The number of stages and the distillate to
error buildup in a Lewis-Matheson approach.)
feed ratio must be searched to obtain the desired
(4) Find the fractional number of stages to
separation.
match the desired split.
In this paper an algorithm is presented. It is (5) Calculate D/F to satisfy the overall com-
designed to calculate rigorously the minimum ponent material balances.
number of stages for multicomponent, nonideal (6) Use the 0 method to reduce the deviations
systems. For a given key separation, the pro- from the specified key component splits.
gram calculates the minimum number of stages (7) Revise feed stage composition.
(which may be fractional) above and below the (8) Speed up convergence.
feed, the distillate to feed ratio, the distillate and The problem is defined as follows:
the bottoms compositions. The solution is Given
equivalent to an asymptotic solution of a column zi;i= l,... ,n; x z.i= 1
with a finite feed as the reflux approaches infinity.
The result of the calculation with the appro- and
priate rule of thumb can then be used as an initial - N - -M
%f ,XL 7
estimate of the overall optimization study. In the
number of cases investigated in this work, the it is to find
rule of thumb predicted excellent estimates, so
Q;i= l,...,n,
that the subsequent optimization work was con-
siderably reduced. Xi-M;i= I,...,& (1)

ALGORITHM AND THE EQUATIONS

DIF,N,M,
The basic algorithm that has been developed and
centers on the binary system. In other words, if Tj;j=-M ,..., 0 ,..., N,
the system is binary, the algorithm would be non-
iterative or one-pass. The algorithm and the
with the following equations:
equations are summarized in steps in this section,
and they are discussed in detail in the sections D D
that follow. z<=Fx”‘v+ l-- xi+M;i= l,...,n
( F>
(1) Estimate the feed stage liquid composition.
The feed stage composition is taken to be the X,N = k.Nk,N-1 _ _ _ ,&-M+lk.-MX,-M.
,i= l,...,n (3)
* z t t 1
same as the feed composition if no better esti-
mate is available at the time. For a binary system,
i k&j-’ - - - ki-M+‘,&-MXi = 1;
they are the same. i=1
(2) Use bubble point calculations to obtain
j=-M ,..., 0 ,..., N (4)
stage by stage temperatures and compositions
above the feed. -M = XL-M
XL (5)
(3) Use dew point calculations below the feed
to obtain stage temperatures and compositions. xHN= Q’ (6)

1968
 A rigorous calculation method in multicomponent
The subscript i denotes component i, and the
superscript j denotes stage j which runs from
-M, the reboiler, to N, the condenser. Equa-
tions (2) are the material balance equations; Eqs.
(3) the equilibrium; Eqs. (4) the bubble point
equations and Eqs. (5) and (6) the desired split.
Variables are explained in the section on
Nomenclature.
There are (2n + 3 + iV + M+ 1) unknowns in
(1) but only (2n+2+ N+M+ 1) equations in
(2)-(6). With Eqs. (2)-(6) the quantity (N + M)
may be calculated but not individual values of N
and M. One must define another equation to
separate out N and M. The form of the arbitrary
equation is discussed in a later section on feed
stage composition matching.
In the algorithm, after the initialization, Eqs.
(3), (4) are calculated in steps two and three;
Eqs. (5), (6) in step four; Eqs. (2) in steps 5 and 6.
In essence the algorithm cycles between the
equilibrium calculation and the material balance
calculation, searching for a set of feed stage
compositions. The equation that defines k is
usually
YijPi*
-;i=
k( =
l,...,n,
P
where
-yC= rj(Tj, xkj, k = 1, n) = liquid activity
coefficient for
component i.
pi* e pi*(Tj) = vapor pressure Of
component i.
BUBBLE POINT ALGORITHM
For a given set of XiF’sy the composition on
stage F + 1 can be obtained by a bubble point
calculation:
i kiFxiF = 1
i=l
and
x.F+l=kiFxiF;i=
1 l,...,n.
Since kiF can usually be assumed to be only a
function of XiF and TF, Eq. (10) can be solved
distillation
with a nonlinear one dimensional root finder sub-
program. The independent variable TF is varied
until Eq. (10) is satisfied.
Equations (11) are then used to obtain the
liquid composition of the stage above. The same
procedure is repeated until the heavy key com-
position on stage [N + 11 is such that
+,[N+ll < xHNc +$Nl (12)
where the sumbol [ -1 denotes the function which
has a value equal to the largest integer value not
exceeding the argument in the bracket. The pro-
cedure is stopped also if N has reached a preset
maximum to prevent a possible early runaway of
the program due to poorly estimated XiF’s.
DEW POINT ALGORITHM
For a given set of XiF’s the composition on
stage F - 1 can be obtained by a dew point
calculation:
(13)
and
= xiF/kiF-‘; i = 1, . . . , n.
~.~-l
* (14)
Since kiF--l is a function of XiF-l, the above
equations must be solved iteratively. The n+ 1
variables ~.~--l; i = 1,. . . , n and TF-‘, must be
found which satisfy the Eqs. (13) and (7). Direct
(8) iteration is used for the composition variables
while a quadratic extrapolation method is used
(9) for the temperature. This method, although not
the best, works for most of the problems, and it is
probably one of the more popular ones in use.
Equations (13) and (14) are used repeatedly
down the column until
XL[-M-ll < - -44 <
1 XL . x2-M’ (15)
(10)
or M has reached a preset maximum.
(11) FRACTIONAL STAGE
To have the exact light key composition at the
bottom and the heavy key composition at the
top, the variables N, M, and D/F would have to
1969
 HENRY H. Y. CHIEN

be fractional even though a fractional equilibrium and

stage is not very well defined. In this model, the
concept of Murphree efficiency was found to be XiN = (Xi[N+ll)6N(Xi[M)~l-~N~; i = 1, n
(22)
very conveniently adaptable for our use.
The Murphree efficiency in our notation is where 4N and (1 - c#Y”)are the powers of the
defined to be: quantities xJN+llxJM respectively.
If the total number of stages required for the
separation is large, then the difference in the
(16)
fractional stages calculated by the two equations
(17) and (2 1) would be insignificant. However, if
which can be used to define the relative volatility is large, the difference
would be appreciable.
4N E N_-[N] = %fN-dM (17)
The purpose of the foregoing discussion is to
XJN+ll _ XJM ’ indicate the possibility of getting different results
and from Fenske’s approach and the method used in
this work. It would be straightforward to derive a
shortcut equation similar to the Fenske equation,
also and for fractional stages employ the Murphree
efficiency. However it is outside of our scope to
XiN = x,rNl + 4N(x1[N+ll -Xi[Nl); i = 1, n,
(19) present the derivation here.
X.9 = Xi[-Ml+ @M(Xp+U -Xpfl) ; j = 1, n_ (20)
2
MATERIAL BALANCE AND ACCELERATION
OF SOLUTION
There are two advantages of using the Murphree
After the calculation of the compositions xiN’s
efficiency concept in the calculation of the frac-
and XiWM’s which satisfy the stage to stage material
tional stage. First, Eqs. (19) and (20) are linear
balance and phase equilibria from a set of esti-
with respect to the composition. Therefore given
mated XiF’sIthe set of Xi”s must be searched and
7 x/M = 1, 7 xi[-M’ = 1 determined such that the calculated compositions
XiN’sand XiVM’salso satisfy the component overall
and material balances (2); i.e. if substituted into Eqs.
T xi(Nfl’ = 1, 7 XC-M-l’* 1 (2), they yield a unique D/F. This condition is
always satisfied for a binary system because XiN’s
we will have and XimM’ssatisfy Eqs. (4). Therefore, for a
binary system, calculation will be completed and
7 XiN= 1, T XipM= 1. solution obtained in one pass.
In order to force component overall material
Secondly, the concept of the Murphree efficiency balances and calculate a single D/F, we assume
is well known among the chemical engineers; it is first that
the fractional approach to a full equilibrium stage.
Note that the use of Murphree efficiency in i,N= &-hi ;i= l,...,n. (23)
I
x.-M
I 1
fractional stage calculation is not a generally
accepted concept. In Fenske’s [ 1 l] popular For a 13to be defined later, the above assumption
approach for minimum stages calculation, the
can then be used in conjunction with the equa-
fractional stage is obtained by
tions
In (x~-~/x~~]) D, D
$p=
In (x~~+~~/xJ~~) (21) Zi=FXiN+
( >
l--
F
liPM;i= l,...,n

1970
 A rigorous calculation method in multicomponent distillation

or The ximMand xiN so obtained satisfy the com-

f.-M = zi ponent overall material balances (2) but not the
t ;i= I,...,n (24)
equilibrium equations (3) and (4), nor the specifi-
$&+ 1-s
E ( > cations (5) and (6). The new feed stage composi-
tions are computed by
to obtain a D/F that satisfies
P.-M f.f”
F F LL
Xi.eal = Xi.est
X.-M XiN’
(27)
x Xi-M= 1. (25) 1

Equation (25) can be solved with a nonlinear
single variable root finder subprogram.
Equations (23) were first proposed by Holland
[2] for convergence acceleration use in distilla-
tion calculations. They may be derived by assum-
ing constant relative volatilities. 8 is equivalent
to a temperature correction factor. If 8 is greater
than 1, it is equivalent to a raise in the average
column temperature. The standard procedure as
proposed by Holland has been to adjust the 8 (or
the average column temperature) in Eq. (23)
such that a prespecified D/F results. The cal-
culated compositions can then be used to
accelerate the convergence.
In our application, the specification is not on
D/F but on ~r-,~and zLPM.To satisfy the specifica-
tion we will adjust the 8 (or the average column
temperature) such that either one of the following
conditions results:
Min [ (_fHN- iHN) 2+ (_fLmM
- iLeM) “1,
e ration use. It has been found in [ 151 also that
or
(&yN-X/) - @-M-&-M)
Results of using either one of the above two
equations were nearly the same in numerical
tests. Equation (26) is therefore recommended
for its simplicity. In brief, the procedure is to
solve Eqs. (25) and (26) with independent vari-
ables D/F and 8 respectively maintaining the
general concept of using 8 to force a specifica-
tion. The original 8 method to fix a D/F can be
stated in terms of the general concept as search-
ing D/F to force component overall material
balances and searching 0 to force D/F. In this
context, the 0 method is a general convergence
acceleration method.
The calculated xr,,, ‘s are then used in a direct
or an accelerated iteration mode to force conver-
gence. The acceleration method is discussed in a
later section.
Equation (27) is a simple way of defining a set
of new xIF’s from a set of old xiF’s using the set of
exit compositions from equilibrium and the set
from the material balances. Undoubtedly there
are many other ways of defining the new XiF’s
that would work equally well.
OVERALL CONVERGENCE AND
WEGSTEIN’S METHOD
As mentioned previously, the calculated XiF
from Eq. (27) can be used in a direct iteration
mode as the new estimated xiF for (10) and (13).
However, because each iteration involves very
lengthy calculations, a convergence acceleration
method is considered necessary.
Recently the method of Wegstein[ 141 has
been found quite effective in convergence accele-
some limit or damping must be applied with the
= 0. (26) Wegstein method for it to be effective.
The idea used in the Wegstein method is very
simple; the variables are treated as independent
of each other and each estimation uses linear
inter- or extrapolation after two points are avail-
able in the (xtest, xc,,,) space. The equations that
give the next estimate are
F
Xi.est,k+l =
F
qXi.est.k + ( 1 - dXtcaLk
(28)
q,_-Ln_
m-l
and
F F
Xi.cal,k - Xi,cal.k-l
m,=
XL&k - c?st .k-I

1971
 HENRY H. Y. CHIEN

The bounds for the Wegstein method are usually above criteria provides only an estimate of the
on m, such as: optimal feed location for the final design. Further-
more, the criteria should not be used if the feed
m = min (mmaxr m,) (29) composition lies in the regions defined by points
1-2-O or 3-4-O in Fig. 1, or if one component is
where mmax may be 0 or 0.5 for the easy prob-
used not only as the light but also as the heavy
lems and - 1 for the difficult ones. The bounded
key.
Wegstein method improves the stability of the
If the same component is used both as the light
iteration method and thus speeds up the conver-
key and the heavy key, the optimal feed location
gence. The solution is considered converged if
should be near the place in the column where the
mole fraction of the key component equals its
mole fraction in the feed. If the feed composition
lies in the region 1-2-O as point F on Fig. 1, the
line A-F represents Eq. (30), the line 2-B repre-
FEED STAGE COMPOSITION MATCHING sents Eq. (2) and the curve 2-C-B represents the
As mentioned previously, the total number of composition profile in the column. The intercept,
variables in Eq. (1) is one more than the total I, between the line A-F and the curve 2-C-B
number of equations in Eqs. (2)-(6). Therefore, defines the feed tray composition. Since the
only the combined value of (N+ M) may be curve 2-C-B intercepts line l-3 at points C and
determined uniquely. To determine the values of B, the criterion defined by Eq. ( 12) or (15) would
N and M separately another equation must be not work if the feed tray composition is any-
defined. where on the curve 2-C. In other words, it is im-
The additional equation is defined as follows: possible to obtain a solution for this problem
for liquid feed, using the algorithm in this work if the condition
F
in Eq. (30) is enforced. In such cases only N + M
XL ZL
-=-
(30) can be obtained.
XH” ZH There are cases in which the feed composition
is in the region 1-2-O but the intercept between
for partially vaporized feed,
the column profile and Eq. (30) is in the region
l-O-4. For these problems, a solution can
light key
xLF _ composition in the liquid feed
F- heavy key A
XH
composition in the liquid feed

for superheated vapor feed,

light key liquid

F
XL
-= composition at the dew point
F
XH heavy key liquid ’
composition at the dew point

The above criteria are based on general design

practices. However, because the composition
profile of a column at total reflux is usually
different from that at an optimal reflux, the rela-
tive feed location obtained with any one of the Fig 1. Feasible region.

1972
 A rigorous calculation method in multicomponent distillation

usually be obtained but the relative feed location Table 1. Antoine constants for the example problem
will be either close to the top or the bottom that
its value as an estimate of the feed location in a PC(psi@ A B c
final design is small. Ho-butane 529% 5.611805 3870.419 409.949
N-butane 550.7 3.372 2247.1 303.0
FEASIBILITY OF THE SOLUTION Iso-pentane 483.0 7.897 8241.4 670.4
N-pentane 489.5 7.9295 8250.4 645.3
For a given pair of composition specifications N-hexane 440.0 5.705 4875.5 401.3
(%fIv,XL+), there exists a domain of feed com- N-heptane 3%.9 3.576 2917.4 242.3
position which would satisfy the material balance N-octane 362.10 5.309 4567.9 307.0
N-nonane 331.0 1144 12515.0 592.3
Eqs. (2). The domain may best be shown on a
triangular coordinate (Fig. 1). Equation (2) ln,$=A _B p”: Asia
defines a straight line connecting the lines e t+C t: “F.

Table 2. Material balance for the example

XL= XL-M
Stream names
and (lb moles/hr) Botm 3 Feed Ovhd
X” = XH”. 1 Iso-butane 0.0252 12GnIo 119748
2 N-butane 5.9853 448.000 442.015
The first line, 1-3, represents possible top pro- 3 I-pentane 22.9690 36.0000 13.0310
4 N-pentane 13.9717 15.OOOo 1.0283
duct compositions, and the second, 2-4, repre- 5 N-hexane 22.9949 23.0000 0.005 1
sents possible bottom product compositions. The 6 N-heptane 39.1000 39.1000 0wOO
feed must fall within the closed convex region 7 N-octane 272.200 272.200 0.0000
8 N-nonane 31wOo 310lOO o@OOo
l-2-3-4 which represents all compositions Totals 408.25 876.30 468.05
attainable by mixture of top and bottom product Fraction vapor (mol) 0.0 0.1395 0.0
streams. It would be more difficult to establish Temperature (“F) 314.12 180.00 121.67
Pressure (psia) 8OWO 80.000 80-000
the feasible composition region for the equilib- Enthalpy (mbtu/hr) 717.0 - 3862.0 - 2808.0
rium Eqs. (3) and (4) for a multicomponent Liq. dens. (lb/ft3) 34.824 0.0 33.866
system. Vap. dens. (lb/ft3) 0.0 0.0 0.0
Liq. ht. cp (btu/lb F) 0.7006 0.0 0.6208
Vap. ht. cp 0.0 0.0 0.0
EXAMPLE (Ib/hr)
An example problem taken from Bachelor[6] 1 Iso-butane 1.5 697.4 6%.0
2 N-butane 347.9 26037.8 25689.9
has been solved by using the new algorithm. The 3 I-pentane 1657.2 2597.4 940-2
system is assumed to have ideal solutions in 4 N-pentane 1008.1 1082.2 74.2
vapor liquid equilibrium. The Antoine constants 5 N-hexane 1981.5 1981.9 0.4
6 N-heptane 3917.8 3917.8 o-o
for the eight components in the system are sum- 7 N-octane 31090.6 31090.7 0.0
marized in Table 1. The heavy and light key com- 8 N-nonane 3975.8 3975.8 0.0
ponents are iso-pentane and n-butane respec- Totals 43980.3 71380.9 27400.7
tively. The desired key compositions are
number is 9.26 as compared to 8.44 by Winn’s
x& = O-02784 method. The overall material balance is given in
Table 2.
and
x:,FCd= 0.01466. NOTATION
D distillate rate, lb moles/hr
The minimum number of stages including a con- E Murphree’s efficiency
denser are calculated after 53 iterations to be F feed rate, lb moles/hr
164 above and 7.62 below the feed. The total k vapor liquid equilibrium constant
1973
 HENRY H. Y. CHIEN

M number of stages below the feed L light key component

m,mc slope in the Wegstein method k iteration cycle count
mmax maximum slope cal calculated value
total number of components est estimated value (sometimes represented
G number of stages above the feed by)
P* vapor pressure, psia
weighting in the Wegstein method Superscripts
;
temperature, “F F feed stage
X composition j stage number
desired composition -M bottom stage number
f
composition that satisfies the material N top stage number
balance
2 feed mole fraction Greek symbols
Y liquid activity coefficient
Subscript ?r total pressure, psia
H heavy key component convergence forcing variable
i component index : fractional stages

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1974