huropean Symposium on Computer Aided Process Engineering - 10

S. Pierucci (Editor)
9 2000 Elsevier Science B.V. All rights reserved. 115

MINLP Optimization of Reactive Distillation Columns

Th. Frey and J. Stichlmair

Lehrstuhl ffir Fluidverfahrenstechnik, TU Mfinchen, Boltzmannstr. 15, D-85748 Garching,

Germany, email: Thomas.Frey@fvt.mw.tum.de

Reactive distillation, i.e. the simultaneous implementation of reaction and distillation in a

counter current column, has proven to be quite advantageous for several reasons. The whole
capacity of reactive distillation and its potential for chemical processes can only be shown at
optimized reactive distillation processes. This requires a rigorous simulation and optimization
of reactive distillation processes which leads to a Mixed Integer Non Linear Programming
(MINLP) problem. This MINLP model is based on the concept of equilibrium stages. In addi-
tion to the rigorous formulation of the thermodynamic equilibrium it is necessary to develop
an appropriate superstructure for the process to be optimized. To guarantee that the super-
structure contains all physical relevant process alternatives, the definition of the superstructure
is based on a thermodynamic background. The MINLP optimization can be performed with
respect to minimum energy requirement or minimum total annual costs. The results are pre-
sented for the synthesis of methyl acetate.
1. I N T R O D U C T I O N
In the last decade the interest in reactive distillation has continuously grown. The reasons
therefore are quite advantageous synergy effects that arise from the simultaneous implementa-
tion of reaction and distillation in a single apparatus and the inherent superimposition of
chemical equilibrium upon the vapor liquid equilibrium. Some of these effects are [ 1]:
9 Continuous withdrawal of products from the reaction section can lead even to total conver-
sion of the reactants.
9 Undesired side reactions can be suppressed.
9 Heat of reaction can be utilized for the simultaneous distillation.
Furthermore, it must be stated that conventional distillation boundaries, as azeotropes or
border distillation lines, can be overcome by reactive distillation. As a negative side effect the
superimposition of two equilibria may lead to so called reactive azeotropes [2]. In analogy to
conventional distillation these reactive azeotropes form a barrier for reactive distillation. Thus,
one of the necessary conditions for process synthesis and for the synthesis of appropriate su-
perstructures for the MINLP-optimization is the determination of the location of reactive
azeotropes and, in turn, the determination of possible products within a reactive distillation
column.
Until now, most of the works dealing with reactive distillation apply so called transformed
compositions for the representation of the thermodynamic equilibrium [2,3]. The advantage
of these transformed variables is that reactive distillation can be described in close analogy to
conventional distillation, because the dimension of the valid concentration space is reduced
by the number of chemical reactions. But the use of transformed compositions implies a se-
vere disadvantage as a lot of information about the vapor-liquid equilibrium is lost. In an
early stage of process design, as it is for the definition of a process superstructure for a
MINLP-optimization, the use of transformed compositions may lead to structures that do not
116

comprise the optimal process configuration. Thus, a novel method for the determination of
reactive azeotropes has been determined that is based on the collinearity of distillation and
reaction steps [4]. Knowledge of the location and the type of reactive azeotropes is a neces-
sary condition for the determination of possible products within a reactive distillation column
and can be used for the design of appropriate superstructures. In previous works the method-
ology has been presented in detail for equilibrium and non equilibrium reactions [4,5]. In this
paper the method is applied to the synthesis of methyl acetate.
2. D E T E R M I N A T I O N OF PROCESS STRUCTURES
The determination of the location and the type of potential reactive azeotropes leads to the
definition of a process structure since possible products can easily be determined. This is to be
presented for the synthesis of methyl acetate [6], which is one of the most important reactive
distillation processes in industry and thus, experimental results are available and can be com-
pared with the results of an optimization. Nevertheless, the method is generally applicable to
multicomponent mixtures and even to kinetically controlled reactive distillation processes [5].
Figure 1a shows the tetrahedron of the mixture methyl acetate (a), methanol (b), water (c)
and acetic acid (d). The letters a to d denote the substances in the order of increasing boiling
temperatures. The mixture contains two minimum azeotropes, one between the methyl acetate
and methanol, the other one between methyl acetate and water. Between these azeotropes there
exists a distillation boundary. This distillation boundary together with a tangential pinch at the
water edge impede the synthesis and purification of methyl acetate in a sequential process.
Figure 1A also presents the chemical equilibrium saddle plane for the esterification of metha-
nol and acetic acid towards methyl acetate and the by-product water.

With the considered phase equilibrium the condition of collinearity between stoichiometric
lines and tangent to residuum lines leads to no lines of possible reactive azeotropes. This con-
dition is met only at the methanol/methyl acetate minimum azeotrope, that lies on the chemi-
cal equilibrium surface, i.e., this non reactive azeotrope is also a reactive azeotrope. All reac-
tive distillation lines run on this equilibrium surface. They start at the high boiler acetic acid
and end at the reactive minimum azeotrope. It can be seen that the desired products methyl
acetate (a) and water (c) are no starting or ending points of reactive distillation lines. In Figure
1B this can be emphasized using the transformed compositions mentioned above [3]. This
transformation is equivalent with a projection of the equilibrium plane along the main stoichi-
ometric line on a two dimensional plane. Thus, the saddle surface of Figure 1a transforms into
a square in Figure lB.
 117

Figure 2: Superstructure for the synthesis of methyl acetate.

In Figure 1B the course of the reactive distillation lines upon the chemical equilibrium
plane is obvious. The desired product methyl acetate (a) and the byproduct water (c) do not lie
on the same distillation line. Thus, the separation in a single feed reactive distillation column
is not possible, as the reactive distillation line represents the liquid concentration profile of a
reactive distillation column for total reflux. In conventional distillation, this limitation can be
overcome by introducing a second feed stream into the column, as it is done in extractive dis-
tillation. In contradiction to the usual temperature profile within a distillation column, the high
boiler is fed near the top of the column and the low boiler near the bottom. Between the two
feed stages a physical absorption takes place and, in turn, products can be reached that do not
lie on the same distillation line. The same can be done in reactive distillation. Figure 2 shows
the structure of the column for the synthesis of methyl acetate.
The high boiler acetic acid is fed near the top of the column. The low boiling reactant
methanol is fed near the bottom of the reactive column, preferably as vapor. Within the reacti-
ve column, three different sections are necessary: a reactive section between the two feed sta-
ges, a conventional rectifying section above the acetic acid feed to separate methyl acetate
from acetic acid and a conventional stripping section beneath the methanol feed to separate
water from methanol. The degree of freedom that remains for a process optimization is still
considerably high. There are three operating parameters that have to be optimized (condenser
and reboiler duty together with the temperature of the liquid feed) and five geometric variables
(total number of stages, number and location of reactive stages together with two feed stages).
This problem has been formulated as a MINLP-problem.
3. M I N L P - M O D E L L
Until now there are only a few works dealing with the MINLP-optimization of reactive dis-
tillation columns. Ciric and coworkers presented a MINLP-model for the optimization of the
ethylene glycol production [7], but under the assumption of ideal vapor-liquid equilibrium.
118

Figure 3: Model of a reactive equilibrium stage.

The MINLP model is based on equilibrium stages with the use of efficiencies when re-
quired. The model for the distillation sections has been taken from [8] and includes the
MESH-equations on every stage with a rigorous description of the vapor-liquid equilibrium
using the Wilson approach. The thermodynamic equilibrium upon a reactive stage is not cal-
culated using a simultaneous approach as proposed in [9]. As we use an Outer-
Approximation/Equality-Relaxation/Augmented-Penalty algorithm for the solution of the
M1NLP-problem [ 10], it is necessary to define a maximum number of possible stages, as well
tbr reactive as for non reactive sections. Thus, there must be several stages within the column
that have been defined as possible reactive stages but as a result of the optimization they turn
out to be conventional distillation stages. A different description of a single phase equilibrium
and a combined phase and chemical equilibrium would lead to a large number of equations on
these trays that have to be solved during optimization although they are not relevant for the
solution and therefore only deteriorate the convergence. Thus, the combination of two differ-
ent equilibria occurring on a reactive stage has been split in two sub-problems (Figure 3).
First the liquid xn-l,i from the stage above undergoes the chemical reaction. The equilibrium
composition x i~q" that can be reached in this stage is calculated with respect to all non-
idealities, i.e. also including the activity coefficients:
K,~ = l-[ (x2'*' 9y,)" (1)
i

In total, the number of equations that have to be solved for the chemical equilibrium
section including the calculation of the value of temperature dependant equilibrium constants
and the heat of reaction is 4n + 5. For a quaternary mixture this means that 21 additional
equations have to be solved on each reactive stage. The liquid stream that leaves the reaction
stage is calculated according to:
iHI
X ,,I __ X , - l , i + breac.t,i 9,.tx~,,
equ - x,_,j) (2)
where b,-~aa,, denotes the integer variable that represents the chemical reaction. If the integer
variable b,.~aa,, equals 0, the term in brackets is not considered, i.e., no reaction occurs on this
stage and, in turn, this stage is treated as a conventional distillation equilibrium stage. If the
integer variable b,.ea~t,, equals 1, the equilibrium composition x2q" after chemical reaction is
reached and, in combination with the following distillation section, the stage represents a re-
active distillation stage. A sequence of these reaction and distillation sections combined in a
reactive stage represents the model of a reactive distillation line as mentioned above and there-
fore is appropriate to describe the concentration profiles within a reactive distillation column.
 119

A second advantage besides the decrease of the number of equations is, that this model
can also be used to optimize kinetically controlled reactive distillation columns. Therefore,
equation (2) must be rewritten into
int equ
x ,,,, = x ,_~,, + b ..... ,,, 9 rl " ( x , , , - x ~,, ) (3)

The parameter r/represents the ratio of residence time of the liquid upon a reactive stage to
the reaction rate. This ratio can also be expressed by a Damk6hler-Number.
Da
r/= ~ (4)
Da+l
In contrast to a Damk6hler-Number, 77 is only defined for values between 0 and 1. In addi-
tion to the calculation of the equilibrium constant and the equilibrium composition, expres-
sions for the reaction rate of the reaction have to be included.

4. RESULTS
Figure 4 presents the results of an economic optimization of the superstructure presented in
Figure 3. The objective function is the minimum of the total annual costs of the process, with
the use of industry relevant cost functions [8]. It is assumed that a heterogeneous catalyst is
applied, i.e., the reaction section can be located anywhere within the column. Each reactant is
fed in an amount of 10 mole/s. The distillate contains 99 mole percent methyl acetate, the
bottom product contains 96,3 mole percent water.
The total annual costs of the column are 430 000 $. The total number of stages is 45. The
reactive stages are located between the 10th and the 40 th stage. The condenser and reboiler du-
ties are 788 kW and 606 kW, respectively. The liquid acetic acid is fed on stage 6 at a tem-
perature of 349 K. It is quite advantageous to feed the vapor methanol at several stages be-
tween the 36 th and the 40 th.
Looking at the concentration profiles published by [6,11] there are always two points of
intersection between the water and the methanol concentration near the bottom of the column,
i.e., on several stages near a single methanol feed the amount of methanol is higher than the
amount of water. This ratio changes if one approaches the bottom of the column, as the whole
methanol is vaporized and moves upwards the column to react with the acetic acid and the
bottom products is almost pure water. This disadvantage can be overcome by multiple vapor
feeding. Figure 4 presents the optimal solution which includes five methanol feed stages.
Limiting the number of feed stages to two leads to similar results as shown in Figure 4. The
methanol is introduced at the 35 th stage with an amount of 4.6 mole/s and at the 40 th stage with
an amount of 5.4 mole/s. The total annual costs of the process increase by less than one per-
cent.
Similar to the results presented by [6,11 ] there exists an extractive section between the li-
quid acetic acid feed on stage 6 and the reactive section beginning on stage 10 (Figure 4a).
Looking at the concentration profiles there is nearly no change in concentration on these four
stages. In order to determine whether or not this extractive section is necessary for the separa-
tion or only advantageous as the costs for a reactive stage is higher than the cost for a conven-
tional distillation stage, an energetic optimization has been carried out where the number of
stages has been fixed to 45. As a result of this optimization the number of reactive stages is
increased and the reaction section is located between stage 5 and stage 40. The liquid acetic
acid is fed at stage 5 and 6, the methanol is fed between the stages 33 and 38. This implies that
the extractive section in usual column designs is not necessary. Due to the multiple feeding of
the reactants the energy demand is decreased by 11 kW to 595 kW.
120

Figure 4: Results of a rigorous economic optimization for the synthesis of methyl acetate
together with the concentration profiles

OUTLOOK
As mentioned above, the model is formulated to consider further chemical reactions or re-
actions that do not reach equilibrium but are limited by their reaction kinetics. In this case the
liquid holdup, i.e. the residence time of the liquid in the column plays a important role for the
calculation of reactive distillation processes. This is to be shown for several kinetically con-
trolled reactive distillation processes in near future.

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