ARTHUR ROSE, ROBERT F. SWEENY, and VERLE
SCHRODT
The Pennsylvania State University, University Park, Pa., and Applied Science Laboratories,
Inc., State College, Pa.
Continuous Distillation Calculations by
Relaxation Method
This is an entirely new
method for calculating prod-
uct compositions in multi-
component continuous dis-
tillation, when feed con-
ditions, flow rates, plate
efficiency, number of plates,
and reflux ratio are estab-
lished
THE relaxation method has been de-
veloped for calculating the product com-
positions in multicomponent continu-
ous distillation, when feed conditions,
flow rates of product streams, plate effi-
ciency, number of plates, and reflux
ratio are established. By obtaining
several solutions for various numbers of
plates and various reflux ratios, optimum
operating conditions can be chosen with
certainty for a particular set of product
purities and yields. Although based
on material balance and phase equilib-
rium relations and plate calculations,
the method is entirely different from
any other. Each choice of operating
conditions leads directly to an answer
in terms of product compositions, re-
gardless of the complexity of the problem,
number of components, extent of non-
ideality, irregularity of thermal re-
lations, or number of side streams.
Thus successive solutions lead directly
to the desired optimum solution. No
simplifying assumptions or approxima-
tions are needed. Other methods often
lead to no solution, unless a great deal
of experience and judgment are applied
in choosing trial values.
The relaxation method is not uni-
versally preferable to conventional
methods, but is particularly advanta-
geous for complicated design problems
involving multiple columns or compo-
nents, nonideal equilibrium and thermal
behavior, multiple feed or take-off
streams, extremes of concentration, and
automatic control applications (6). I t
requires an automatic computer, but
this need not be fast, nor large, unless
many components are involved. Digital
computers are indicated because analog
computers are limited to problems
involving relatively few plates and few
components. The method can deal
I
N.
with any type of nonideality for which
data are available. I t is not subject to
the difficulties in conventional methods
when plate compositions change widely
and in a complex manner with slight
changes in end compositions. Some
of these difficulties are particularly
serious when automatic computers are
used, because of the difficulty of pre-
paring adequate instructions for auto-
matic choice of successive trial values.
In the relaxation method calculations
are made for the gradual change in all
the plate and product compositions that
occur in a column from initial startup
until steady state is reached. The
equations previously used for batch
distillation ( 5 ) with appreciable holdup
are used. The calculations may be
started with all plate compositions equal
to the feed composition, but other
starting compositions may be used.
Use of the material balance equations
once for each plate gives a new set of
plate compositions slightly different
from those at the start. Repetition
of this kind of calculation gives one set
after another of plate compositions,
which gradually approach the steady-
state compositions. When these are
reached, no further composition changes
occur upon repetition of the calculating
cycle. The steady-state solution is in-
dependent of starting compositions and
holdup, but if the real starting compo-
sition, holdup, and corresponding flow
rates and time lags are used, the cal-
culations describe the approach to
steady state.
Basic Equations
The basic equation is that for ex-
pressing the change in the moles of a
component present in the holdup on a
particular plate, during any brief in-
terval during the distillation operation.
This equation is, in general terms, when
usual simplifying assumptions of dis-
tillation are applicable,
+
Hxn(i+l) = H ~ n i (VY(~-I).<+
Lxta+~),d- Vyn.6 - LXn.i) (1)
where n refers to the plate number, and
i refers to a particular interval of time,
and (i + 1) refers to the next succeeding
interval. Hrefers to the total moles 03
holdup on the plate; and V and L
refer to the vapor and liquid flow rates.
_,
The equation is merely a material
balance stating that the quantity of
the component present in the holdup
on plate n during interval i +
1 is equal
to that during interval i, increased (or
decreased) by the net quantity added
and removed as the result of the flows
of the two vapor and two liquid streams
to and from the plate. The basic
equation can be immediately solved
to give composition x , ( ~ + ~ )in terms
of the composition and flows for interval
i. This working equation is
Xfl(i+l) = Xni + 1 (VY(n.-,),i +
Lx(n+ - Vya,i - Lxn.i) (2)
An equation of this kind can be written
for each plate and each component,
and similar but slightly different equa-
tions can be written for the top plate,
the feed plate, and the still pot. The
equation takes a more complex form
when simplifying assumptions are not
applicable (4).
If the compositions and flows at any
time,i are known, Equations 1 and 2 may
be used to calculate compositions at
time i +1, and the process repeated
to obtain values for time i +
2, and so
on. The necessary values of vapor
composition, y, are obtained from the
corresponding value of liquid composi-
tion, x, by use of the applicable vapor-
liquid equilibrium relation.
This same general procedure has
Keen used in predicting the course of com-
position changes and effect of operating
variables in batch distillation with ap-
preciable holdup ( 5 ) ,and more recently
in studying the effects of column upsets
in continuous distillation and related
control problems (6). Use of the pro-
cedure for continuous distillation design
calculations is simplified by the fact
that the desired steady-state composi-
tions are independent of the starting
compositions, and of the path toward
steady state. Thus any convenient
set of starting compositions may be
used, without concern as to the path
followed.
Basic Calculation Procedure for
Continuous Distillation Design
I t is most convenient to start the cal-
culations using feed composition values
for all the plate liquid compositions,
VOL. 50, NO. 5 M A Y 1958 737
These are taken as the compositions
for time zero. The first step is the use
of the basic equation for the top plate
to calculate the composition of the
liquid from this plate a t the end of the
first time interval. The second step is
to use the basic plate equation to cal-
culate the composition of the sec-
ond plate from the top, a t the end
of the first time interval. I n the
same manner the compositions at the
end of the first time interval are cal-
culated for each of the other plates
and the still pot or reboiler. Alterna-
tively the calculations can begin at the
still pot and proceed upward. In fact,
the calculations for the various plates
(at any one interval) may be done in
any desired or random order, as the
calculation for each plate is independent
of that for all other plates. When all
the compositions for time interval one
have been obtained, the procedure is
reported over and over to obtain com-
positions for time intervals two, three,
and so on.
I n general, most of the compositions
change rapidly at first and then gradu-
ally approach steady-state values. When
the latter are reached, the compositions
no longer change from one interval to
the next, and these compositions rep-
resent the desired steady-state solution
to the particular continuous distillation
problem under consideration.
Arithmetical Precautions
The calculation procedure is purely
arithmetical, but requires special pre-
cautions. The time interval must be
sufficiently small to avoid distortions
that result when the quantities flowing
during an interval are large compared
with the holdup on a plate. In general,
10o[
I \ Bottoms
'
0 20 40 60 80 100
NUMBER OF INTERVALS
738 INDUSTRIAL AND ENGINEERING CHEMISTRY
flow rates V and L should be one fifth
to one tenth of the plate holdup, H,
to avoid distortions and instability in
the calculations. Arithmetical errors
must be eliminated by making an over-
all material balance of each component
after each new set of compositions is
obtained. I t is also desirable to check
first and secondary differences in the
compositions for successive intervals,
as appreciable changes in these are in-
dicative of arithmetic errors.
Simplifying Assumptions
The procedure as explained involves
some of the usual simplifying assumptions
of distillation calculations, but these are
not inherent in the method. One ad-
vantage is the ease with which these
assumptions can be eliminated to make
the method more rigorous, when de-
sirable.
Constant molal overflow
Perfect plate efficiency
Negligible vapor holdup
Composition of liquid on a plate
identical with that of liquid leaving the
plate
The methods of modifying the cal-
culations to take these complexities
into account have been described in
detail ( 5 ) .
Requirements for Calculation
To carry out the calculation proce-
dure for a specific case, the following
quantities must be known, specified, or
fixed by choice of a trial value:
Total number of theoretical plates,
reflux ratio, and relative quantities of
overhead and bottoms.
Location of feed plate (or feed plates
The curves show how the mole
per cent benzene on various
plates would change from
initial startup until the column
compositions teveled off when
steady state was reached.
The steady-state compositions
are the desired solution to
the continuous distillation
problem
120 140
in the case of multiple feeds) and any
side product streams.
All flow rates (vapor and liquid in the
column, overhead, bottoms, and feed
and side streams). Absolute quantities
are not necessary, but correct relative
values must be used, and the feed rate
per interval must be one fifth to one
tenth of the holdup per plate.
Holdup on each plate and in reboiler.
The final steady-state compositions are
independent of the choice. but arith-
metic relations require that the holdup
be at least five times the feed rate per
interval.
Initial composition of liquid on each
plate and in the reboiler. The final
steady-state compositions are independ-
ent of the choice of initial compositions.
I t is convenient to use feed composition
as the initial plate compositions.
Application to Benzene-
Toluene-Xylene Distillation
The application of new method may
be illustrated by checking the solution
to the benzene-toluene-xylene distilla-
tion described by Robinson and Gilli-
land ( 3 ) .
This involves a 16-theoretical plate
fractionating column with a reboiler
which also acts as a theoretical plate.
The column is to be used to obtain a
purified benzene overhead from a feed
containing 60 mole % ' benzene, 30 mole
% toluene, and 10 mole % xylene. The
feed, which is a liquid at its boiling point,
enters the column on the ninth plate
from the bottom. The reflux ratio is
set at 2 to 1, and 60.17, of the feed is
to be taken overhead.
The moles of feed per interval are
arbitrarily fixed as 10. The correspond-
ing overhead rate is then 6.01 moles with
3.99 moles as the bottom rate. Thus,
V , is 18.03 moles, L, is 12.02 moles. V ,
is 18.03 moles, and L, is 22.2 moles.
The holdup on each plate and in the
reboiler is taken as 50 moles. The cal-
culation is started with liquid of feed
composition on each plate and in the
reboiler.
All the above data were entered into
a digital computer, together with a
program for repeated calculation ac-
cording to Equation 2. The curves at
the left show the variation of typical
plate compositions from the initial in-
terval to steady state. At steady state
the top composition is 99.5% benzene,
0.5% toluene, and no xylene. and the
bottom composition is 0.5% benzene,
74.4%> toluene, and 25.1% xylene.
Robinson and Gilliland (3) obtained the
same result, using the familiar Lewis and
,Matheson method.
General Use of Relaxation Method
If the Robinson and Gilliland solution
to the benzene-toluene-xylene problem
was not available, and it was desired
to solve the general problem by the re-
laxation method described, the number
 MACHINE COMPUTATION IN PETROLEUM RESEARCH
a - ~ - ~ - ~ - ~ - ~ - aBOTTOMS
~ a , ~ ~ oPRODUCT
~o~a
of plates and the feed plate location
would not be known. I t would there- /a-
fore be necessary to choose trial values OoZ4F /
for these items and carry out a series of
trial calculations. The first might be
for ten plates with feed introduced on
plate 5 from the bottom. This would
give inadequate separation. Twenty
plates would give better separation than
that specified. Fifteen plates with feed
on plate 8 would not quite achieve the
desired separation.
The relaxation method does not avoid
repeated trials for a general distillation
design problem. However, each trial
does give the exact answer for distilla-
tion with the chosen conditions. Re-
peated trials give an assembly of correct
solutions for various conditions of op-
eration and a true over-all picture and
understanding of the effect of variation
in conditions on the results. In using
conventional methods, such as the Lewis- 0.0 I I
20
1
40 60
I
80
I I
100
I
120
I
I40
I
160
Matheson, all the trials except the last INTERVAL NUMBER
give no answer at all, but only a dis- The curves show how the mole fraction of component B of the ternary mixture on
crepancy in material balances that aids the various plates changes from its value of 0.01 2 at initial startup, to steady-
in choosing conditions for the next trial. state values that persist during continuous distillation
The successive trials thus provide but TOP PRODUCT
little over-all information about the ,o-o---rcJ-cJ-o-o--o--o-o-n-u~~~o~cr

problem. The relaxation method is

especially useful in more complicated
problems where the conventional method
encounters serious difficulties in that
selection, of trial starting values is so 4
complex that it is difficult or impossible to c
find an answer even after many trials.
a 0 BO 4-cp-c-p-o-~-~-a-~-~-4-~-~ FEED P L A T E

This situation is most likely to arise in H *-*C-*-e-.-*-

5
problems whose solution is most worth P L A T E BELOW FEED P L A T E
i
while-Le., for cases of operation near P
minimum reflux, and where very small 0

changes in composition at one end of

a
a column are associated with very large
differences at the other end. Such ? 0 60
problems are easily solvable by the re-
laxation method, but difficult or impos-
sible to solve by conventional methods.
This is particularly true of nonhydro- 050- \ -0-
o/o~-o-o-o-o
BOTTOMS PRODUCT
carbon mixtures.

Relaxation Solution for I I I I I

Side Stream Problem
The curves at the right give the solu- INTERVAL+ NUMBERS

tion to a problem in which a ternary
mixture consisting of two close boiling
less volatile components (B and C) are
separated from a single more volatile
component (A). Side streams enter and
leave an upper plate, and feed is near the
bottom.
Computer Program
The relaxation type of calculation is
not easy without any automatic com-
puter.
The sample benzene-toluene-xylene
problem was programmed for solution
on Pennstac, a medium-speed digital
computer similar to the IBM 650.
The simplified block diagram for the
The mole fraction of component A of the ternary first decreases and then rises
on the lower plates, as the progression occurs from initial startup to the steady-
state compositions that are indicated b y the flat right-hand portions of the curves,
Component C curves are not shown but would appear as approximately the
inverse of those for component A
program is given on page 740. This the interval by interval calculations
is applicable to any constant molal automatically and prints the answers
overflow three-component fractionation as it proceeds after each interval, or
problem for any number of theoretical after any specified number of intervals.
plates above and below the feed plate, The overhead and bottoms compositions
and any reflux ratio. The various flow are printed, but any other compositions
rates in the enriching and stripping in the column may also be printed as
section, the holdup on the plates and in desired.
the reboiler, th'k feed composition, and
various constants, such as those found l i m e Required for
in the expressions for relative volatility, typical Solutions
are entered as data. The machine does The rate of approach toward steady-

VOL. 50, NO. 5 * MAY 1958 739


E n t e r Initial Data
I n t o C a l c u l a t e Storage
I
I A
Equilibrium Vapor
Reset t r a f f i c c o n t r o l s
an6 c y c l e e s c a p e s f o r
next i n t e r v a l .
Tolerance Check
See i f s t e a d y s t a t e has
been reached.
P r i n t i n t e r v a l number
and d e s i r e d
1 I
Escape
MBSR CYCIE Escape
Determines when a l l t h e new
l i q u i d compositions have
been c a l c u l a t e d .
* I
MESR T r a f f i c Control.
R e g u l a t e s t h e hBSR so i t w i l l o b t a i n c o r r e c t
v a l u e s f o r a given p l a t e and s t o r e
answers in t h e c o r r e c t p l a c e .
state compositions is rapid a t first, but
extremely slow toward the end. Thus
a n approximate solution can be ob-
tained quickly, but a precise answer
requires an unduly long period of com-
putation. The latter can be greatly
reduced by determining the form of the
first portion of the curve, and then extrap-
olating this to steady state. This ex-
trapolation can be included i n the over-
all computer program, so that compu-
tation time is reduced to a nominal
value.
Evaluation of Method
The method presented here is basically
different from the Lewis-Matheson
method in that it determines overhead
and bottoms compositions, given the
flow rates, number of plates, feed plate
location, feed composition, and relative
volatility relations. The Lewis-Mathe-
son method essentially determines the
number of plates necessary to produce
overhead and bottoms compositions
which are specified or desired.
If a problem involves an existing
column with a known number of theo-
retical plates, the relaxation method has
a definite advantage. Using this method
is equivalent to having a pilot plant
column and actually operating it to
obtain the answers. Such a problem
can be solved using a Lewis--Matheson
type method only by trial and error. For
multicomponent problems the choice
740 INDUSTRIAL AND ENGINEERING CHEMISTRY
I culations of the relaxation procedure,
I_
I
S u b m u t i n e (EVSR)
Calculate r e l a t i v e v o l a t i l -
EVSR T r a f f i c Control.
ReguLates t h e EVSR so it Vi
c e r t a i n p l a t e and s t o r e
answers i n proper p l a c e .
EVSR Cycle Escape.
Determines when a l l t h e
I
Vateerial Balance Subroutine
(MESR)
Calculate the liquid
c o m o s i t i o n on a p l a t e
a t t h e end o f an i n t e r v a l .
of successive trial values can many
times become very complex, particularly
if there is but little experience with the
system. Shelton and McIntire (7) have
developed automatic computer pro-
grams for Lewis-Matheson type solution
called the feed mesh methods. Bonner
(2) has developed a similar method.
However, difficulties are sometimes en-
countered in the choice of successive
trial values and these become critical
when they must be completely systema-
tized in advance in the form of program
instructions for the computer. Amund-
son’s (7) method avoids these difficulties
by setting up simultaneous equations
for the steady-state conditions, and
solving these by a matrix inversion tech-
nique which requires a very large, fast
computer.
Another difficulty in using the Lewis-
Matheson method is that of extremes
in composition. For example, the final
solution to a problem might indicate
that the overhead is almost pure light
component and the bottoms contains
only parts per million of the same com-
ponent. Under these conditions, the
top composition will sometimes be
vey sensitive to minute changes in bot-
toms composition. I n the relaxation
method the only effect of very small
quantities of a component is that this
component might disappear entirely
from the computer registers (usually
seven or more decimal places) and appear
as zero. This in no way upsets the cal-
but does cause difficulty in Lewis-
Matheson and other types of conventional
calculations.
The relaxation method can be adapted
for multiple feed and for side stream
products, and can be used to solve mul-
tiple column problems where the col-
umns are interrelated-for example, if
bottoms from column one is the feed to
column two and part of the overhead
from column two is refluxed to column
one. In every case the method proceeds
positively and directly to the correct
product compositions for the conditions
chosen, and when successive trials are
necessary, there is no uncertainty in
selection of new starting values. With
some modification, the method can be
used to determine the time to reach
steady state from an empty column
start, and to study control problems.
Acknowledgment
The investigations underlying this
work would not have been possible
without financial support from the
h’ational Science Foundation in the form
of a grant to the Pennsylvania State
University.
Nomenclature
H = total holdup per plate, moles
L = liquid flow rate, moles per time
interval
V vapor flow rate: moles per time
=
interval
x = liquid composition, mole fraction
of any component
y = vapor composition, mole fraction
of any component
SUBSCRIPTS
i = number of time interval
m = to identify a vapor or liquid rate
below feed plate
n = to identify a vapor or liquid rate
above feed plate
1, 2 . .16 = to identify a plate by num-
ber, counting from bottom up
Literature Cited
(1) Amundson, N. R., Pontinen, A. J.,
IND.ENG.CHEM.50, 730 (1958).
(2) Bonner, J. S., Pittsburgh Meeting, Am.
Inst. Chem. Engrs., September 1956.
(3) Robinson, C. S., Gilliland, E. R.,
“Elements of Fractional Distilla-
tion,” 4th ed., pp. 219-29, McGraw-
Hill, New York, 1950.
(4) Rose, Arthur, Johnson, R. C., Chem.
Eng. Prugr. 49, 15-21 (1953).
(5) Rose, Arthur, Johnson, R. C.
Williams, T. J., Zbid., 48, 549-56
(1952).
(6) Rose, Arthur, Williams, T. J., Harnett,
R. T., IND. ENG.CHEW48,1008-19
(1956).
(7) Shelton, R. O., McIntire, R. L., Pitts-
burgh Meeting, Am. Inst. Chem.
Engrs., September 1956.
RECEIVED for review November 21, 1957
ACCEPTED March 7, 1958
Division of Petroleum Chemistry, Sym-
posium on Application of Machine Com-
putation to Petroleum Research, 132nd
Meeting, ACS, New York, N. Y., September
1957.