REACTION KINETICS OF THE ESTERIFICATION OF ETHANOL AND

ACETIC ACID TOWARDS ETHYL ACETATE

Deliverable 22
Workpackage 6
Technical Report

Name of Partner:
DSM

Authors:
Geert Hangx, Gerard Kwant, Harrie Maessen, Peter Markusse, Ioana Urseanu

Date:
24 August 2001

Distribution:
Frdric Gouardres, European Commission,
Andrzej Grak, University of Dortmund
Eugeny Kenig, University of Dortmund
Peter Moritz, SULZER
Klaus Althaus, BASF
Gerard Kwant, DSM
J acob Moulijn, University of Delft
Hans Hasse, University of Stuttgart
Wieslaw Salacki, PLOCK
J iri Klemes, UMIST
Andrzej Kraslawski, Lappeenranta University of Technology
Bjoern Kaibel, MONTZ
Florian Menter, AEA
Maria Majchrzak, ICSO
Andrzej Kolodziej, IIC
Ion Ivanescu, PETROM
Valentin Plesu, University Politehnica of Bucharest

PROGRAMME GROWTH

Intelligent Column Internals for Reactive Separations (INTINT)

Project No. GRD1 CT1999 10596
Contract No. G1RD CT1999 00048

Intelligent Column Internals for Reactive Separations Page 2 of 5
Deliverable 22 Issued: 24.08.01

1 SUMMARY AND CONCLUSIONS 2
2 INTRODUCTION 2
3 EXPERIMENTAL 3
4 RESULTS AND DISCUSSION 3
5 LIST OF SYMBOLS 5
6 SELECTION OF PHYSICAL PROPERTIES 5

1 Summary and conclusions

The kinetic parameters have been determined for INTINT reaction system 3: ethanol/acetic
acid/ethyl acetate. The reactions considered are the esterification of ethanol (CH
3
CH
2
OH, EtOH)
and acetic acid (CH
3
COOH, AcOH) towards ethyl acetate (CH
3
COOCH
2
CH
3
, EtOAc) and water,
and the reverse reaction, ester hydrolysis. The catalyst used is the cation exchange resin Purolite
CT179.
2 Introduction

The work described in this report is a part of the European project Intelligent Column Internals for
Reactive Separations (INTINT). The report contains the kinetics of reaction system 3. Originally,
reaction system 3 was the aldol condensation of acetone towards diacetone alcohol. However, since
no stable catalyst for this reaction was available
1
, this process was abandoned. The reaction studied
instead is the esterification of ethanol (CH
3
CH
2
OH, EtOH) and acetic acid (CH
3
COOH, AcOH),
resulting in the products ethyl acetate (CH
3
COOCH
2
CH
3
, EtOAc) and water, see equation 1:


(1)



AcOH EtOH EtOAc

This reaction is reversible, and the equilibrium composition is a weak function of temperature. The
reaction is acid catalysed, and as for most esterifications usually strong mineral acids (hydrochloric
acid, sulfuric acid) are used
2,3
. Cation exchange resins (typically containing sulfonic acid groups,
e.g. Amberlyst 15, Purolite CT179) are also widely used, because of their high activity and selectiv-
ity (possible side reactions are alcohol dehydration and etherification), and easy separation
2
. Cata-
lyst deactivation appears to be negligible. In practice the equilibrium is often forced towards the

1
INTINT deliverable 21, February 2001
2
Ullmanns Encyclopedia of Industrial Chemistry, vol. A9
3
Chemical Economics Handbook CD-ROM
O
OH
OO
OH
HO HO
O
O
O
O
+
H
+
H
+
+ H
2
O
Intelligent Column Internals for Reactive Separations Page 3 of 5
Deliverable 22 Issued: 24.08.01

ester by azeotropic water removal
2
. In the present investigation the cation exchange resin Purolite
CT179 will be used.

The intrinsic kinetics of the reaction system are more or less known from literature: the forward
reaction rate (ester formation, R
1
) is a function of EtOH and AcOH concentrations, and the reverse
reaction rate (ester hydrolysis, R
2
) is a function of EtOAc and water. See the kinetic equations be-
low:

m
AcOH EtOH
x x k R
1 1
= (2)
O H EtOAc
x x k R
2
2 2
= (3)

The equilibrium constant K
eq
is given by equation 4:

m
AcOH EtOH
O H EtOAc
eq
x x
x x
k
k
K
2
1
2
= = (4)

All concentrations are given as mole fractions. Both k
1
and k
2
are functions of temperature, accord-
ing to the Arrhenius equation:

RT E
o i i
A
e k k
/
,

= (5)

For porous particles with typical particle diameter 1 mm, intra-particle diffusion and mass transfer
from the liquid bulk to the particles are expected to be very important. The kinetics determined in
this study therefore only apply to Purolite CT179 with the same particle size distribution. The ob-
jective of this study is to find kinetic parameters for the reactions described above (formation and
hydrolysis of ethyl acetate).
3 Experimental

The catalyst used is the ion exchange resin Purolite CT179, purchased from Purolite. Purolite
CT179 is a porous cation exchange resin, containing sulfonic acid groups. The particle diameter
was 0.6-1.4 mm. The reagents ethanol (>99.9%), acetic acid (>99%) and ethyl acetate (>99%) were
purchased from J .T. Baker, and used as received. Demineralised water was used. Apart from the
reactants and products (AcOH, EtOH, EtOAc and water) no other solvents were used. The experi-
mental set-up consisted of a thermostated jacketed glass tube, inner diameter 20 mm. Typically 12 g
of catalyst was used, and a constant flow rate of 0.1-25 ml/min was applied. The reactor was kept at
55-65 C. The effluent was analysed off-line by GC over a CP-wax 58CB column, using a flame
ionisation detector. The samples were diluted with acetone prior to injection, and methyl iso-butyl
ketone was used as internal standard.
4 Results and discussion

The equilibrium constant K
eq
was determined by leading 0.1 ml/min of a feed solution containing
ethanol and acetic acid (in several ratios) through the reactor, containing 12.3 g of Purolite CT179.
It was verified that equilibrium was reached by comparison with effluent concentrations reached at
higher flow rates: no difference was observed between 0.1 and 0.5 ml/min. The best fit of the re-
Intelligent Column Internals for Reactive Separations Page 4 of 5
Deliverable 22 Issued: 24.08.01

sults was obtained for 1.5
th
order in AcOH (m in equations 2 and 4 is 1.5). The resulting equilibrium
constants at 55 C and 65 C are 6.68 and 5.51, respectively.

For determination of the kinetic constants k
1
and k
2
the same reactor was used, but at higher liquid
flow rates: 2-25 ml/min. The corresponding W/F ratios are 0.03-0.37 s kg
cat
/m
3
. The kinetic con-
stants were calculated from the product concentrations (EtOAc when AcOH and EtOH were fed,
AcOH and EtOH when EtOAc and water were fed) using a Mathcad worksheet, in which the reac-
tor was modelled as an ideal plug flow reactor. The experimental and calculated ethyl acetate con-
centrations in the reactor effluent are shown in figure 1.
Figure 1. Experimental (x-axis) and simulated (y-axis) ethyl acetate concentrations in the reactor effluent.
The kinetic equations 2 and 3, and the parameters given in table 1 were used for the simulations.

At 65 C the value for k
1
is 0.147 mol kg
cat
-1
s
-1
, and k
2
is 0.0268 mol kg
cat
-1
s
-1
. At 55 C the value
for k
1
is 0.0874 mol kg
cat
-1
s
-1
, and k
2
is 0.0131 mol kg
cat
-1
s
-1
. The activation energy for the ester
formation reaction is 48.3 kJ mol
-1
. The activation energy for the ester hydrolysis reaction is 66.2 kJ
mol
-1
. The pre-exponential factors (see equation 5) are 4.2410
6
mol kg
cat
-1
s
-1
for the ester formation
and 4.5510
8
mol kg
cat
-1
s
-1
for the ester hydrolysis. The most important parameters are summarised
in the table below.

Table 1. Kinetic parameters for ethyl acetate formation and hydrolysis on Purolite CT179.
Parameter Units Value
K
eq
55 C - 6.68
K
eq
65 C - 5.51
k
1
55 C mol kg
cat
-1
s
-1
0.0874
k
1
65 C mol kg
cat
-1
s
-1
0.147
k
2
55 C mol kg
cat
-1
s
-1
0.0131
k
2
65 C mol kg
cat
-1
s
-1
0.0268
k
1,o
mol kg
cat
-1
s
-1
4.2410
6

k
2,o
mol kg
cat
-1
s
-1
4.5510
8

E
A,1
kJ mol
-1
48.3
E
A,2
kJ mol
-1
66.2
Ethyl acetate parity plot (weight%)
0
20
40
60
0 20 40 60
experimental
c
a
l
c
u
l
a
t
e
d
Intelligent Column Internals for Reactive Separations Page 5 of 5
Deliverable 22 Issued: 24.08.01

5 List of symbols

E
A
activation energy J mol
-1
k
1
esterification reaction rate constant mol kg
cat
-1
s
-1
k
2
ester hydrolysis reaction rate constant mol kg
cat
-1
s
-1
K
eq
equilibrium constant -
R gas constant J mol
-1
K
-1
R
1
esterification reaction rate mol kg
cat
-1
s
-1
R
2
ester hydrolysis reaction rate mol kg
cat
-1
s
-1
T temperature K
x
AcOH
mole fraction acetic acid -
x
EtOAc
mole fraction ethyl acetate -
x
EtOH
mole fraction ethanol -
x
H2O
mole fraction water -

6 Selection of physical properties

Azeotrope EtOH/EtOAc
4
EtOH 44.7 m%, bp 71.8 C
Azeotrope water/EtOAc
4
water 32.6 m%, bp 71.5 C
Azeotrope water/EtOH
4
water 10.4 m%, bp 78.2 C
Azeotrope water/EtOH/EtOAc
4
water 28.7 m%, EtOH 17.3 m%, bp 70.4 C
Density AcOH
4
1.047 kg/l (20 C), 0.995 kg/l (70 C)
Density EtOAc
4
0.900 kg/l (20 C), 0.838 kg/l (70 C)
Density EtOH
4
0.790 kg/l (20 C), 0.743 kg/l (70 C)
Density water
4
0.997 kg/l (20 C), 0.971 kg/l (70 C)
Molecular weight AcOH 60.05 g/mol
Molecular weight EtOAc 88.11 g/mol
Molecular weight EtOH 46.07 g/mol
Molecular weight water 18.02 g/mol
Normal boiling point AcOH
4
117.9 C
Normal boiling point EtOAc
4
77.1 C
Normal boiling point EtOH
4
78.3 C
Normal boiling point water
4
100 C
Reaction enthalpy
4
-27.5 kJ /mol (70 C)
Solubility water in EtOAc
4
14.1 m% (25 C), 22.6 m% (70 C)
Solubility EtOAc in water
4
1.6 m% (25 C), 1.1 m% (70 C)

4
Aspen properties