Compur . t hem. Engng, Vol . 12, No. II, pp.

1141-1149, 1988
Printed in Great Britain. All rights reserved
0098-I 354/88 ~3.00 + 0.00
CopyrIght 0 1988 Pergamon Press plc
REACTIVE DISTILLATION PROCESS
OPTIMIZATION BY EMPIRICAL FORMULAE
CONSTRUCTION
F. DUPRAT, R. GASSEND and G. GAU
ESIPSOI, Universid dAix-Marseille, Avenue Escadrille Normandie-Niemen. F- 13397 Marseille
Cedex 13, France
(Recei ved 15 J anuary 1988; recei ved for publ i cati on 18 February 1988)
Abstract-In this paper we develop an optimization method of the reactive distillation process. We have
demonstrated a technique for constructing a set of empirical formulae which constitutes a simplified model
of the process. This has resulted in a computationally-tractable optimization problem for which we have
obtained reasonable results.
1. I NTRODU~I ~N
1.1. The reacti ve d&i /l oti on process
Reactive distillation is an attractive method for
separation of isomeric mixtures (Saito et al ., 1971;
Gau, 1974; Terrill et al ., 1985; Gassend et al ., 1985;
Duprat, 1986). It is well known that close boiling
point fractionation has a very high cost. Reactive
distillation exploits chemical reactivity differences
between the isomers, using a selective and reversible
reaction carried out in a distillation column. The
complexed reacting products are non-volatile, so the
concentration of the more reactive isomer is in-
creasing in the liquid phase as a complex. At the same
time, the concentration in the vapor phase of the less
reactive isomer is increasing all along the column,
until total separation. The use of a displacement
agent will be necessary to recover the complexed
isomer in a free form. If needed, a solvent can be used
to avoid the complexed isomer precipitation.
Therefore, the general scheme of the reactive dis-
tillation process is composed of six columns (Fig. 1):
column 1 separates the less reactive isomer, column
2 regenerates the more reactive isomer by chemical
equilibrium between the displacement agent and this
isomer, columns 3 and 5, and 4 and 6 are used to
separate each isomer from the displacement agent
and the solvent. Then, the solvent, free and com-
plexed displacement agent are recycled.
Carrying out an isomeric mixture separation by
reactive distillation means:
(i) choosing a chemical reaction which emphasizes
the reactivity difference between the isomers-this
choice is made after equilibrium stage experiments
(Gassend et al ., 1985; Duprat, 1986); (ii) choosing
a displacement agent, the best if possible; and
(iii) flowsheeting the process. The two last results are
provided by process optimization. It should be noted
that this optimization further supplies the possibility
of comparison of reactive distillation with other
separating processes.
This optimization a pri ori seems tricky and time
consuming. The process involves six columns and
three recycle streams, i.e. a lot of parameters. More-
over, calculation of columns 1 and 2, in which the
chemical reactions take place, may be nonconvergent
in some cases: the equilibrium stage model is very
nonlinear and the setting of operating parameters is
sharp.
1.2. Opti mi zati on techni ques
The most common approach for flowsheeting and
optimization of chemical processes is a sequential-
modular approach. This technique is typically simu-
lation oriented: the modelling equations of each unit
of the flowsheet are formulated so that the outlet
streams are calculated in terms of the inlet streams
and equipment variables, and solved in a process
sequence. So this approach may become very slow to
handle design and optimization problems.
Recently, two promising alternatives were devel-
oped: the equation-oriented approach (Stephenson
and Shewchuk, 1986; Westerberg et al ., 1979) and the
simultaneous-modular approach (Chen and Stadt-
herr, 1985a). The first technique expresses the com-
plete model of the process as a single large system of
nonlinear equations which are solved simultaneously
by a Newton-Raphson procedure. This approach is
limited by large storage requirements and by the need
of a good initial guess. Using the simultaneous-
modular approach, only the external variables, or an
appropriate subset thereof, are treated as indepen-
dent. An approximate J acobian matrix of the process
is generated by perturbation of the same unit modules
used in the sequential approach. Then, these equa-
tions are solved simultaneously. Because of the
J acobian approximation, this approach is more
reliable for simulation than for optimization (Chen
and Stadtherr, 1985b).
1141
1142
F. DUPRAT et al.
3 plcoline
-
3 picoline +DA
D
Mixed
I
-
picdim
s
:
k
T
I
SCllVet3l
A
4
D
H
T
I
t
+
I
No
T
1
4 picoline + DA
RecycLe TFA 1 DA salt
I
TFA 14 PIcaLine and TFA / DA saL1s
Fig. 1. The reactive distillation process. Example of 3-picoline/4-picoline separation. TFA = trifluoroacetic
acid; DA = displacement agent.
Using a sequential-modular approach, opti-
mization is performed by adding yet another outer
iteration loop. The entire simulation problem must be
solved for each iteration, so the computation time
may become prohibitive, especially for processes in-
volving recycle streams. An alternative consists of
representing the chemical process by a simplified
model (Adelman and Stevens, 1972). The per-
formance of this method depends to a considerable
extent on the degree of accuracy of the model.
We develop the latter method, using a simplified
model construction methodology that overcomes the
nonconvergent reactive distillation calculations and
provides models whose accuracy is sufficient. Each
column simplified model is composed by a set of
empirical formulae constructed from a training set of
observations. These observations result from exact
calculation of the columns in various working condi-
tions.
An example of process optimization is given in
Section 4 of this paper and concerns the reactive
distillation of a 3-picoline/4_picoline mixture in the
presence of trifluoroacetic acid: the operating vari-
ables and the physicochemical properties of the dis-
placement agent are optimized, starting with specified
final purities. To realize this process optimization, we
built simplified models only for reactive distillation
columns 1 and 2 because one can easily find short-cut
methods for distillation columns design. As simplified
models allow the transformation of an operating
problem into a design one, the training set of obser-
vations has been made up with specified operating
Process optimization by formulae construction 1143
variables. Consequently we described: (i) an un-
published exact calculation method; and (ii) the em-
pirical formulae construction algorithm.
2. EXACT METHOD FOR REACTIVE COLUMNS
CALCULATION
2.1. Columns equati ons
The reactive distillation has been studied in the
case of acid-base reactions which are well known to
be very fast. Consequently, we supposed the chemical
equilibrium immediately reached. The equilibrium
stage model described below has been experimently
established starting with different mixtures of pyri-
dines Bi and strong acid HA stoichiometric deficiency
(Duprat, 1986). One can write:
4
Bj H+ + Bi e B,H+ + B,.
(1)
Liquid-vapor and chemical equilibria can be ex-
pressed in terms of four compounds: the two isomers
to be separated (1 and 2), the displacement agent 3,
which belongs to the same chemical family as the
isomers and the solvent 4. The first three compounds
appear either in free form Bi , or in acidic complexed
form B,H+, so the presence of the strong acid HA is
implicitly taken in account. The following equi-
librium stage model shows good agreement with
experimental results:
1. As pyridinium salts are not volatile, the
liquid-vapor equilibrium depends on free pyridines:
Y,x;
All relative volatilities a, are constant. As far as the
simulation is concerned, only isomers with very close
boiling points are taken into account, i.e. au = 1.
2. Equilibrium constants defined by:
aO-=- withi,i=l to4andX,=x,.
YjX
X.Z
K, = J
x,z, (i ,i = 1 to 3)
1 I
do not depend on the liquid phase composition.
3. The acid-base reaction is stoichiometric:
z,
=z,+z,+z,.
So, equilibrium relationships are for the solvent:
X4
I -z*
s,=-_=_
7
Y4
z+e+e+,,
(24
for compounds 1, 2 and 3:
1
$ = 5 = -
1 - Z*
Y, ai yI
(
Y2 Y?
r,+z+l+Y4
a34
(2b)
During the calculation:
The heat loss to surroundings has not been taken
into account.
As the two isomers and the displacement agent
have roughly the same structure, the heats of
formation of the three (Bi N +, A -) salts are quite
similar, (cf, K,, values), consequently the heat of
the exchange reaction 1 has been neglected.
It has been assumed that the molar flowrate
variation due to the difference of molar heat of
vaporization of the compounds is much smaller
than the flowrate variation caused by the reac-
tion.
In order to adjust the flowrate of recycle stream
between the bottom of column 2 and the top of
column I, a fraction F/(L + F) of the liquid
stream leaving column 2 is vaporized and added
to the vapor feed l,.
Consequently, constant molar overflows L and V, are
assumed. The component material balances are:
for feedplate M, in column 1:
(L + F) SiY8.M + VlY,,.M
= MY,_,,+, + v,Yi,,-, + %.r, (3)
for other plates:
L %Y,,p + v,Y,.p = LSiY,.&?+ 1 + v!a+ 1 3 (4)
with
k = subscript of the column (k = 1 or 2),
p = subscript of the plate (p = 1 to N*),
L= Lin column 1 ifp >M, and L=L +Fi n
other cases.
The acid molar fraction is defined by a constant
molar flowrate of acid: zA corresponds to a flowrate
L and z A = z, L/(L + F) to a flowrate L + F.
The number of plates, feedplate location, condi-
tions of feeds etc. . . . are specified so that the com-
position profiles through the column may be com-
puted.
2.2. Method of computati on
For the treatment of nonideal mixtures, Holland
(1983) recommends to use the molar fractions x,.~or
yi., as iteration variables rather than temperatures,
flowrates or separation factors profiles.
As difficulties involved in reactive distillation are
comparable to those of nonideal mixtures, two meth-
ods according to Holland were chosen. The main
method is a block-tridiagonal matrix linearization.
This matrix is composed of partial derivatives of
component material balances. The compositions are
simultaneously corrected using a multivariate New-
ton (or Newton-Raphson) scheme. In the original
method, the equation set is solved by the Gauss
elimination algorithm (Naphtali and Sandholm,
1971). We rather prefer the Thomas algorithm giving
less truncation errors (Boston and Sullivan, 1972)
1144
F. DUPRAT er al.
and we use the Newman extension to block matrix
(Newman, 1968).
Newton-Raphson convergence can be very rapid
and the solution is reached within 4 to 10 trials.
However, experience shows that convergence is not
guaranteed if the initial values are too far from the
final solution.
A relaxation method, modified by Ishikawa and
Hirata (1972) is used to initialize the composition
profiles. In this method, the composition correction
between two iterations is proportional to the error in
material balance. Thus, convergence tends to become
very slow when nearing the solution but is very stable.
In order to overcome the slowness involved, the
relaxation method is not systematically used: the
Newton-Raphson procedure is first performed start-
ing from some assumed flat set of initial yi,P values,
and in case of divergence, a new set of initial values
is generated by some relaxation iterations.
Reference to the feasability of such a two-stage
strategy is also given by King (1980).
2.3. Internal opti mi zati ons of col umn I
The purpose of these optimizations is to reduce the
number of parameters. As far as isomers separation
is concerned, none of these isomers has to be privi-
leged. That is the reason why it has been assigned the
same isomer purity at each side of column 1. This
purity can be defined by:
p, =Y,
x2
=-
(5)
Y, + YZ diEtl,late XI + x2 bOltOn?
and is very close to the process final purity because
regeneration in column 2 must be severe enough to
avoid isomer 2 recyling in column 1. Of course
columns 3 to 6 are not going to give any improvement
in the p, purity. Equality of purities is very dependent
on the vapor bottom flowrate V,. So, V, is preferred
as control variable and the secant method as an
optimization method.
Furthermore, the isomer feedplate location M is
adjusted to give a maximum purity p, _ According to
the discontinuous character of this parameter, a
step-to-step search has been performed.
3. EMPIRICAL FORMULAE CONSTRUCllON
The main problem in formulae construction is the
a pri ori choice of their analytical form. The most
common models are polynominal correlations: they
are linear so the coefficients calculation is quite easy
but adjustment between experimental results and
model involves a great number of coefficients.
Among these polynominal correlations, the Ivakh-
nenko polynominal, constructed by the GMDH
(group method of data handling) algorithm (Farlow,
1984), is the most interesting on account of very
clever model building which is much the same way as
nature proceeds by natural selection. Construction is
gradual and at every step a reduced number of input
variables is handled, the ineffective variables are
thrown out and the others are kept and combined to
form a new generation of informations.
We also develop a step-to-step building strategy
but we reduce the final number of adjustable
coefficients using input variables changes. Moreover,
formulae are constructed around a center point,
corresponding to stable working conditions, and
consequently the validity range can be restricted in
order to maintain a sufficient accuracy.
The three main steps of formulae construction are:
1. The basic input variables Xi, having a complex
effect on results, are replaced by new linear variables.
Each new variable is a nonlinear function A of the
original input variable, including three adjustable co-
efficients. This function f; is called principal function.
For each X, variable, the function-form most suited
to the experimental curve Yobr =f(Xi) is selected. This
step requires: (i) a training set of observations Yobs
in which only the X, value is changed, the other
variables keeping their center point values; and (ii) a
set of model functions. Two close model functions are
used to represent monotone curves:
fi, = b&q + CiY,
(6)
(7)
Two model functions are employed to represent
extremum curves: a second degree polynominal for
symmetrical curves and a Langmuir model for un-
symmetricals:
_& = bJ l + a,(X, - q)],
(8)
WG
f4; = (Xi + q)P
The three ai. b,, ci coefficients are adjusted using a
nonlinear regression algorithm combining a step-to-
step search and a Newton-Raphson procedure. The
smallest residue function is chosen.
2. f; principal functions are combined using multi-
plication instead of addition, it corresponds to a
better approach of the observed phenomena. Yet the
formula takes the following form:
Y = b7rif;(Xi),
(10)
with all bj coefficients collapsed in 6.
3. This formula is achieved by addition of inter-
action terms; experiment shows that the linear inter-
action terms are the most improving. The definitive
formula is:
Y = (b, + Z&Xi) rril;(Xi), (11)
Interaction coefficients are computed simultaneously
using a new training set composed of random points
taken in the validity range of the formula. Random
points were chosen because in case of nonconvergent
calculation of one point, it can be easily replaced by
Process optimization by formulae construction 1145
First Loop
I
Of
i nt er nal
optimization
i
_ Flat initial
profile
--__
by relaxation
1
I 1
of
optimization
v
Ith step
optimization
Initialization
t t
ith step
of
optimization
4 7
Optimized
profiLe
58% 1 2 % 30 %
----
Fig. 2. Scheme of column
Convergent Newron - Raphson procedure
Non convergent Newton- Raphson procedure followed by relaxation method
Nan convar~~ent Newton- Rophson procedure after reinitializafion by the
reloxatmn method
1 calculation with optimum feedplate location and equality of the two isomers
purities.
another one as a result of the equal level of informa-
tion contained in each random point.
Finally, by comparing the definitive formula
against a new set of independent observations, it is
possible to obtain a model that accurately predicts
new independent observations (Farlow, 1984). This
checking set is again composed of random points.
In conclusion, using this type of formula, it is
possible to correlate a result depending on n input
variables with, at the most, 3n + 1 adjustable
coefficients. Every construction step involves either
nonlinear functions containing three coefficients, or a
linear equation containing n + 1 coefFicients.
4. EXAMPLE: REACTlYE DISTILLATION
OF A 3 AND QPICOLINE MIXTURE
3 and 4-picolines have too close boiling points
(143.5 and 143.1C respectively) to be separated by
distillation. As Cpicoline (referred as isomer 2) is
more basic (pKa = 6.02) (Rousscl et al ., 1983), it is
more complexed with an acid than 3-picoline
(pKa = 5.68). The chemical equilibrium constant &,
is about 1.8 using trifluoroacetic acid in nitromethane
(Duprat, 1986). This solvent avoids pyridinium salts
precipitation.
4.1. Exact cal cul ati on of col umns 1 and 2
Columns 1 and 2 were calculated using the
Newton-Raphson/ relaxation sequence. In order to
define the training set and the checking set, more than
200 different points have been computed.
For each point, column 1 has to be calculated
again about 42 times on account of internal opti-
mization. Progress and performance of the calcu-
lation sequence are schematized in Fig. 2. As there is
no internal optimization in column 2 calculation,
only the first step of this scheme is involved.
Newton-Raphson procedure is quite rapid: starting
from a flat initial composition profile, about 10
iterations are needed to obtain relative composition
changes lower than 10e4. On the other hand, starting
from results of an earlier calculation needs about 3 to
4 iterations. The relaxation procedure is quite slow:
to avoid a too long time in generating initial values
for the Newton-Raphson to take over, the relaxation
iterations are stopped when the relative composition
changes are lower than 10-l; this procedure requires
about 30 iterations.
1146 F. DUPRAT et al.
Table I The reactive ds.tdlabon embirical formulae (note: validitv range of formulae is indicated in Table 3)
F0t7Iltlltle Accuracy
I. Isomer purity in column 1 effluents
p, = 1 -0.73(1 t 1.16~~) exp
(oL1, - 0.31)
oa8[(z- *.27)2+0.15L*]~~q
with L* = (L.z~)~~~~
2. Regeneration efficiency 9.3% over
1% (r)
3. Vapor flowrate controlling the isomers purity equality
(a) v, ~l.22~~~~p*[~~,~+l))x~-o.o*7]o~ 6.23%
(b) I, = 0.01 I(1 + O.Ol9L + 0.6Oz,)[(I/y,, , + 224)(L - 2.39)0ao (-_* ~ O.O64)O(x,,_, + 0.12)md(a,, + 0.90)
0 54
4.54%
x (a,, ~~0.36) - I6 (K,, + 1.91)06*(x, + 0.022)042]
4. Displacement agent molar fraction in column I distillale
4.87%
(b) y, ,,,, = 1.67(l/Y,,,,,+3.66)(_~, ,,,, - 1.79)(L -4.99) 0~(=,+0.051)~~8(a,, + 1.36)-~6(1/x,-0.49)029
5. Displacement aSent molar fraction in column 2 bottom
0 07 0 23
(a) ,Q*.,= 1.12
C
V2
-Lt--oo.49
> (
$_ i* - 0.007
> (
I
-0 50
~ 0.67
Ys. 2. 3 >
(b)
x~,?,~ = 4.21(&, - 5 76)oo59(l/L - 0.053)oo(l/z, - l.39)m2 (l/Ya,z,, - 0.675)-0w(a,, + 6.44)086(a,, + 0.12)
x (K,, + o.54)mo.08
4.91 %
4.95%
4.44%
6 Feed plate location in column I
g=0.00S6[LzA(K;, - I)- I.131 ozp[6.62 + (2 - 3.9Oy] 1% - 0.004j 14(xT.,.l - 0.0026)~7 16.71%
Statistical results pointed out from optimized col-
umn 1 show that the Newton-Raphson method is
sufficient to obtain 58% of the results, the relaxation
method saves 30% thereof. Of course, the relaxation
method is particularly efficient at the beginning of the
internal optimization procedure. The remaining 12%
of random points correspond probably to physical
unfeasible working conditions.
In conclusion, the Newton-Raphson procedure
associated to the relaxation scheme is a stable and
rapid calculation method. It is a very well-suited
method for treating columns with a highly nonlinear
equilibrium stage model.
4.2. Empi ri cal formul ae
Formulae construction were carried out only for 1
and 2 reactive columns, and we used short-cut design
methods described in the literature (J afarey et UC.,
1979; Wagner and Blass, 1977; Eduljee, 1975) for 3-6
conventional distillation columns. Reactive columns
calculation is dependent on 15 input variables and
gives 6 results. Thus 6 formulae were built, as func-
tion of all input variables, although some parameters
such as K,, were not optimized. This way provides
possibility to use formulae in different conditions.
The formulae and their mean accuracy are indi-
cated in Table 1. Accuracy is determined from a
checking set of independent observations. Two types
of formulae are shown: formulae with original input
variables (for example, No. 3b or 4b) and formulae
with regrouped variables. The regrouping of variables
leads to a dramatic decrease in the number of adjust-
able coefficients, but does not improve the accuracy.
As grouping is handmade and not generalizable, it is
finally not an interesting feature of the program.
Impurity of isomers leaving column 1 and regen-
eration efficiency are the main calculation results. In
order to improve these formulae accuracy, the im-
purity logarithms [log (1 -p, ) and log r] were cor-
related. The error between approximate calculations
obtained with formulae and those derived from exact
calculation is about 10% (Fig. 3). One can consider
that a 10% precision is not a good result, but in fact
it corresponds to a 0.4% purity confidence interval
and to a 2% accuracy on K,, value, which is equiv-
alent to the instrumental error. If necessary, it is
Process optimization by formulae construction 1147
I
3 5 7 9 11
-Log (1 -P* )e..ct C(llC.
Fig. 3. Comparison of the isomers purity formulae with result of exact calculation, for random points
taken in the whole validity range.
possible to get a better precision by limiting the
validity range around the center point.
4.3. Conventi onal di sti l l ati on col umns
As it has been shown by J afarey (1979) that the
Eduljee equation (Eduljee, 1975) of the Gilliland plot
is relatively precise, around 5%, we used it. This
equation needs to know the minimum reflux ratio and
the number of theoretical plates at total reflux; they
are computed by Underwood and Fenske methods,
respectively (Wagner and Blass, 1977).
In columns 5 and 6, specifications concerning
impurities have been chosen in the following way: for
example, the isomer 1 quantity in the isomer 2
effluent is equal to the displacement agent plus sol-
vent quantities. Other specifications are of course
dependent and have been optimized.
4.4. Process opti mi zati on
Using calculation methods previously described
and Happel and J ordan (1975) values for the cost
parameters, the total cost of the process has been
optimized with the Rosenbrock method (Him-
melblau, 1972). Input variables are reported in Table
2 and the main results in Table 3.
Finally, the cost optimization shows that two types
of displacement agent can be conveniently employed:
either heavier and less reactive than 3-picoline, or a
lighter and more reactive than dpicoline. Con-
sequently, alkylpyridines are not suitable, but chloro-
pyridine should he a good solution.
In conclusion, optimization using an exact calcu-
lation method would require at least several hours,
whereas the computation time with simplified model
is lower than 5 min, with a Hewlett-Packard-1000
Table 2. 3-picoline/4-picolinc reactive distillation: input variables specified
during the optimization procedure
Variable VAlC
Equilibrium constant 4-picoline/3-picolinee
Picolines purity in column I
&I
1.8
PI
0.98
3-picoline final purity
4-uicolinc final Duritv
P5
0.91
D* 0.97
3-&coline feed AA& fraction
Mfluoraacetic acid molar fraction
Reflux ratio (columns 3-6)
Sol vent rel ati ve volatilitv
.
XF
0.50
=A
0.20
4 I.2 R,,,
Dl.l 4.0
1148 F. DUPRAT et al.
Table 3. 3-eicolinc/4-eicoline reactive distillation: main results of ootimization
Variables
Prwess cost CF oicolines kn 1
DA relative volatility -
DA chemical equilibrium constant
Liquid flowrate
Vawr flowrate (column 1)
DA molar fractibn in V,
Vapor flowrate (column 2)
DA molar fraction in V,
Plates number in column 1
Plates number in column 2
Plates number in column 3
Plates number in column 4
Plates number in column 5
Plates number in column 6
Validity
range of
formulae
DA = displacement agent.
0.42.4 1.82
0.62.0 0.72
3.s15.0 5.9
6.4
0.024.32 0.24
6.0-15.0 6.4
0.364I.96 0.80
-300 288
8-32 9
8
16
44
36
Optimum values
Heavy Light
DA DA
0.34 0.49
0.70
0.81
9.6
12.6
0.17
8.8
0.90
112
16
9
II
47
48
computer programmed in FORTRAN-7X. On the
other hand, the accuracy of our model is satisfactory:
starting with the same optimized input values, exact
calculation results in a 98% purity and the simplified
model in a 97% one. Thus, this model constitutes a
dramatic improvement in interconnected columns
process calculation.
NOMENCLATURE
F = Molar flowrate of the isomers feed
Ku = Chemical equilibrium constant
L = Molar flowrate of the liquid phase in columns 1
and 2
M = Feedplate location in column 1
N,, = Plates number in column k
Pk = Isomers purity in column k
r = Separation efficiency (Lx~,~,~/V~~~,~,~)
s, = Selectivity of liquid-vapor and chemical equilibria
for component i
V, = Vapor molar flowrate in column k
xF = Molar fraction of the less reactive isomer in the
feed
-%k.l
= Molar fraction of free and complexed component
i , in liquid effluent p or in liquid phase on plate p,
in column k
X, = Molar fraction of free component i in the liquid
phase
yp,*., = Molar fraction of component i , in vapor effluent p
or in vapor phase on plate p. in column k
zA = Molar fraction of the reacting acid
Z, = Molar fraction of complexed component i in the
liquid phase
.xv = Relative volatility
Subscri pts
B = Bottom vapor feed
D = Distillate
S = Bottom effluent
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APPENDIX A
Deri vati on of Equati on (2)
Y,, mol ar fracti ons of free component i n rhe l i qui d phase
x,= Y,-2.
I I (1)
z,+z*+z,=z*,
(2)
,* x,=
l ~Y,+Y*+Y,+x~=l -z*,
(3)
Y, x4 Yi x4
aA=--(i =1,3)sY,=--,
Y, Y4 ati Y,
(3) and (4) * 3 = --
1 - z*
Y4
B
,,,jth B = fi
aI4
Yt 1 --IA
(4)and (S)S-Y~=~-.
B
(6)
2,. mol ar fracfi ons of compi exed component i n the l i qui d
phase
(7) and (2) = y =
*A
.
3 K,, Y, + Kz, Y, + Y,
(7) and (8) = 2, = K,, Yi
*A
K,, Y, + K2, Y2 + Y, (i = 73) (9)
KS3
(6) and (9) * 2, = - y,
=A
=a K,,YI K23~2 Y:,
-+-+-
(10)
aI4
Rel ati ons between x, and y,
xi
(1). (3, (lo)--
Y,
+