Separation and Purification Technology 16 (1999) 5559

Activity-based model of the hybrid process of an esterification

reaction coupled with pervaporation
R. Krupiczka *, Z. Koszorz
Polish Academy of Sciences, Institute of Chemical Engineering, ul.Baltycka 5, 44-100 Gliwice, Poland
Received 25 March 1998; received in revised form 25 May 1998; accepted 3 September 1998

Abstract

The hybrid process of the esterification of acetic acid with ethanol, coupled with pervaporation, was studied, and
a simple, three-parameter model describing the concentration profiles in the process was built. This work suggests
that the activity-based model is a better method for predicting concentration profiles than the concentration model,
especially in the range of higher component concentrations in which the thermodynamic constants calculated on the
basis of concentrations are not true constants. The experiments were performed using a wide range of initial molar
ratios c /c (1:1; 2:1; 3:1; 5:1) with hydrophilic membrane PERVAP 1005 GFT and ethanolacetic acid as the reaction
et a
mixture. Appropriate activities were calculated using the UNIFAC group contribution method. 1999 Elsevier
Science B.V. All rights reserved.

Keywords: Activity; Esterification; Hydrophilic; Membranes; Modelling

Nomenclature e ethyl acetate

w water
a acetic acid
c concentration, mol/kg cat catalyst ( p-toluenesulfonic acid)
a activities, mol/kg
k forward rate constant, kg2/mol2 h
f
K(c) equilibrium constant (conc.)
K(a) equilibrium constant (activity) 1. Introduction
n permeate flux, mol/h
A membrane area, m2
P permeability coefficient, kg/m2 h Using membranes to separate products in a
M mass, kg reversible reaction is an effective method for pre-
r reaction rate, mol/kg h
M water molar mass, kg/mol
paring some esters. By applying a hybrid process,
w such as esterificationpervaporation, it is possible
t time, h
to shift the equilibrium towards higher reaction
Subscripts yields [1,4,5]. Considerable savings can also be
i component made in the amont of reactants required (as there
et ethanol is no need for a large amount of one of the starting
components) and reduced reaction time. Finally,
* Corresponding author. Tel.: +48 32 31 08 11; such a process eliminates the necessity to add toxic
Fax: +48 32 31 03 18; e-mail: zetk@iich.gliwice.pl substances (such as benzene or toluene) to the

1383-5866/99/$ see front matter 1999 Elsevier Science B.V. All rights reserved.
PII: S1 3 8 3- 5 8 66 ( 9 8 ) 0 01 1 1 -7
56 R. Krupiczka, Z. Koszorz / Separation and Purification Technology 16 (1999) 5559

reaction medium, and may therefore lead to the
development of more ecologically sound technol-
ogies. Any industrial application involved in this
process demands a sound predictive model, and
this work suggests that the activity-based model is
preferable when predicting concentration profiles.
2. Hybrid process modelling
2.1. Kinetics of the reaction
2.2. Kinetics of pervaporation
In the pervaporation of organic solvents con-
taining low volumes of water (below 20 wt.%
ca. 11 mol kg1), an almost linear relationship was
found between the permeation flux and water
concentration [2,3,6 ]. The molar rate of the
removal of water from the reaction mixture by
pervaporation was assumed as the product of the
permeability coefficient and concentration in the
liquid:

The reaction of acetic acid with ethanol displays n =AP c (2)

w w w
first-order kinetics. The equilibrium constant and where A is the area of membrane.
kinetic parameters required for the description of
this reversible reaction could be based on concen-
2.3. Model of the process
trations occurring in the diluted reaction mixture.
Unfortunately, parameters obtained in this way are
The change in water concentration during the
not constant at higher concentrations (Table 1).
process is associated with the volume of water
This problem can be solved by estimating the
formed in the reaction and removed by pervapora-
required parameters using the component activities.
tion. For the combination of pervaporation with

A B
a a the reaction system, we can define the profile of
r=k c a a w e (1) water concentration starting with the water mass
f cat et a K(a)
balance:
where a , a , a and a are the appropriate activi-
et a w e d(Mc )
ties and c ,k , K(a) are the catalyst concentration, w =n +rM
cat f (3)
the forward reaction rate constant and the equilib- dt w
rium constant, respectively, and can be evaluated
by using the activities: where M is total mass of reaction mixture in the
reactor (feed side).
a a Taking this into account, it can be said that only
K(a)= w e .
a a water passes through the membrane (see Table 2),
et a
and it is possible to assume that the total mass
Such an approach enabled us to consider the ther-
balance is:
modynamic and kinetic constants as real constants
(Table 1). The activity coefficients were estimated by dM
using the UNIFAC group contribution method. =n M (4)
dt w w

where M is the molar mass of water.

Table 1 w
Thermodynamic pseudo and real constants and estimated By introducing Eq. (4) into Eq. (3) and rear-
values of the kinetic constant at different initial molar ratios ranging the equation produced, we have:

Initial molar ratio c /c dc n AP c

et a w = w (c M 1)+r= w w (c M 1)+r.
1:1 2:1 3:1 5:1 dt M w w M w w

K(c) 3.698 3.121 2.787 2.640

(5)
K(a) 9.484 10.14 9.993 10.93
k 5.370 4.945 5.156 5.013
By introducing Eq. (1) into Eq. (5), we finally
f obtain the water concentration profile in the
 R. Krupiczka, Z. Koszorz / Separation and Purification Technology 16 (1999) 5559 57

Table 2
Permeate fluxes and permeability coefficients at various feed concentrations

Feed concentration (mol kg1) Permeate flux (mol m2h1) Permeability coefficient P
w
(kg m2h1)
Ester Ethanol Water Acid Ester Ethanol Water Acid

Quaternary system
4.837 7.640 7.800 1.373 1.48 102 10.2 102 20.81 1.87 103 2.668
5.854 7.875 3.844 0.9865 0.91 102 3.91 102 10.68 3.33 103 2.779
4.935 10.91 2.188 0.4108 2.50 102 7.17 102 5.762 8.30 103 2.633
Binary systems
Ethanol Water Ethanol Water
21.16 1.472 4.98 102 4.123 2.801
19.49 5.750 5.87 102 15.04 2.616

i-Propanol Water i-Propanol Water

15.08 5.292 9.09 102 14.70 2.777
13.68 9.944 10.9 102 27.72 2.788

reactor:

A B
dc AP c a a
w= w w (c M 1)+k c a a w e .
dt M w w f cat et a K(a)
(6)
Similarly, it is possible to obtain the concen-
tration profile of the acid:

A B
dc AP c M a a
k= w w w c k c a a w e . (7)
dt M k f cat et a K(a)

The set of differential equations (Eqs. (4), (6)

and (7)) can be solved numerically by the
RungeKutta procedure. During each iteration,
all activity coefficients were calculated using
UNIFAC. The concentration of the other compo-
nents can be calculated by stoichiometry.
3. Experimental
The pervaporation experiments were performed
using hydrophilic membrane PERVAP 1005 deliv-
ered by GFT. Reactions were carried out in the
apparatus consisting of the circulation setup and
the membrane module with a total capacity of
650 ml and 0.01911 m2 of membrane area. A dia-
gram of the experimental setup is presented in
Fig. 1. Concentrations were analyzed chromato-
graphically by VARIAN 3400 using the DB-WAX
Fig. 1. Experimental setup. 1 circulation pump; 2 pervapora-
tion module; 3 condenser; 4 vacuum pump; 5 thermostat.
capillary column. The kinetic and thermodynamic
parameters k and K(a) were determined in the
f
independent experiments [6 ] performed at c /c
et a
1:1, 2:1, 3:1 and 5:1 molar ratios and 70C
[ Table 1]. p-Toluenesulphonic acid was applied as
a catalyst and its concentration remained constant
(0.02100 [mol/kg]) throughout all experiments. All
reagents used were at an analytical grade of
99.5% purity.
4. Results and conclusions
The activity coefficients in the reaction mixture
were calculated using the UNIFAC group contri-
58 R. Krupiczka, Z. Koszorz / Separation and Purification Technology 16 (1999) 5559

Table 3
The example range of activity coefficients

Concentration (mol kg1) Activity coefficient c Concentration (mol kg1) Activity coefficient c

Ester 0.001 1.750 10.14 1.053

Ethanol 9.390 0.9660 0.671 1.753
Water 0.278 1.358 0.391 2.269
Acid 9.390 0.9116 1.080 1.568

bution method for four components. It was
assumed that the low concentration of the catalyst
does not influence the activities of the other com-
ponents. An example of the activity coefficients
variation range is given in Table 3. As K(a) behaves
as a real constant, it is possible to establish the
appropriate forward rate constant k . As was con-
f
cluded, it was possible to estimate the kinetic
parameter k by fitting the kinetic curve to the
f w
experimental data. During this study, this was
achieved by minimizing the mean squared error
Fig. 2. Concentration profiles based on experimental results and
the activity model. Initial mole ratio ethanol:acid=2:1.
method, the calculated results of which are shown
in Table 1, and the mean value k =5.121
f
[kg2/mol2 h] was obtained.
The permeability coefficient used for the model
was calculated on the basis of the pervaporation
experiments using feed mixtures without a catalyst.
This was carried out to prevent the reaction run.
These experiments, using a quaternary mixture,
show that the value P is the same as that obtained
in the binary system (see Table 2) [2,3]. The mean
value of P used in this work was determined to
w
be 2.771 [kg/m2 h].
A comparison of the measured concentrations
with those calculated according to the model shows
sound agreement (Figs. 2 and 3) when the activities
are used. The model is independent of the initial
molar ratios due to the stability of thermodynamic
and kinetic constants. The efficiency of the process
is strongly related to the ratio of membrane area
to the mass of mixture: A/M. Several simulations
were performed with the use of presented model
to indicate the influence of parameter A/M on the
concentrations in reaction mixture. It can be seen
from Fig. 4 that by changing the value of A/M, it

Fig. 4. Concentration changes in ester and water during the

Fig. 3. Concentration profiles based on experimental results and reaction coupled with PV at different A/M ratios. Initial molar
the activity model. Initial mole ratio ethanol:acid=1.5:1. ratio ethanol:acid=1:1.
 R. Krupiczka, Z. Koszorz / Separation and Purification Technology 16 (1999) 5559
is possible to efficiently shift the reaction equilib-
rium and obtain a reasonably pure ester directly
after the reaction. Selection of the A and M values
to be used is determined from an economic point
of view.
Acknowledgment
The work was performed with additional sup-
port from State Committee for Scientific Research
by research project no. 3T09C 01910.
59
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