ISSN 00231584, Kinetics and Catalysis, 2015, Vol. 56, No. 4, pp. 419–427. © Pleiades Publishing, Ltd., 2015.
419
INTRODUCTION
1
Organic esters are very important chemicals. There is
a wide range of applications of organic esters such as
production of cosmetics, plasticizers, pharmaceutical
substances, polymers, textiles, flavours and in food
industry. Several synthetic processes are available to
obtain organic esters. A comprehensive review of
esters synthesis is available [1]. Methyl acetate manu
factured commercially is in great demand. It is espe
cially useful for the manufacturing nail polish remov
ers, printing inks, perfumery, paints, dyes, industrial
coatings and as a solvent in adhesives.
Methyl acetate is produced by the esterification
reaction between the acetic acid and methanol. At
room temperature, the reaction is very slow and revers
ible and several days are usually required to attain equi
librium in the absence of the catalyst. The addition of
the catalyst increases the reaction rate and therefore
decreases the time needed to reach an equilibrium
state. One can discriminate between heterogeneous
and homogeneous catalytic reactions. Homogenous
catalysis occurs when the catalyst and the reactants are
both in the same phase while in the case of heteroge
neous catalysis the catalyst and the reactants are in dif
ferent phases. Homogeneous catalysts, such as HCl,
HI, H
2
SO
4
, and HBr, provide an acid medium. Ion
exchange resins are frequently used as heterogeneous
catalysts. Heterogeneous catalysts are preferable to the
1
The article is published in the original.
homogeneous catalysts due to several advantages like
easy separation of catalyst from the post reaction mix
ture, better selectivity towards desired product, high
purity of the product due to suppression of side reac
tions and elimination of the corrosive environment [2].
One of the earliest works relating to kinetics of cat
alytic esterification of acetic acid with methanol was
published by Rolfe and Hinshelwood [3]. Ronnback
et al. [4] investigated the kinetics of esterification of
acetic acid with methanol using a homogeneous
hydrogen iodide as a catalyst. It was observed that
hydrogen iodide also reacted with methanol and pro
duced methyl iodide as a byproduct. Agreda et al. [5]
proposed a rate expression for the esterification reac
tion in which sulphuric acid was used as a homoge
neous catalyst.
Many solid catalysts were used, such as solid acids
and bases, ionexchange resins, zeolites and acid clay
catalysts. Ionexchange resins are the most common
heterogeneous catalysts used for esterification reac
tion [6–8]. These ionexchange resins not only catal
yse the reaction but also improve conversion because
of selective adsorption of reactants and swelling nature
[9, 10]. In the heterogeneous catalysis, the active solid
surface can distort or even dissociate an absorbed reac
tant molecule and increase the rate of reaction [11].
Most of the esterification reactions were studied by
using the solid catalyst Amberlyst 15 [12–18]. Liu
et al. [19] investigated the similarities and differences
between heterogeneous and homogeneous catalysed
Kinetic Study of Esterification of Acetic Acid
with Methanol over Indion 190 Acidic Solid Catalyst
1
Mekala Mallaiah* and Goli Venkat Reddy
Department of Chemical Engineering, National Institute of Technology, Warangal 506004, India
*email: mmyadav2001@gmail.com
Received August 27, 2014
Abstract—Esterification of acetic acid with methanol to synthesize methyl acetate in an isothermal well
mixed batch reactor was studied in the temperature range of 323.15–353.15 K. Indion 190 ionexchange
resin was used as a solid catalyst. Feed molar ratios were varied from 1 : 1 to 1 : 4. The influence of tempera
ture, catalyst loading, stirring rate, catalyst particle size and initial molar ratio on the reaction rate was inves
tigated. Experimental results showed that the reaction is kinetically controlled. The sorption experiments
were carried out independently to find the adsorption constants. For the constituent components the values
of adsorption constants decrease in the order of water > methanol > acetic acid > methyl acetate. The kinetic
data were correlated with the pseudohomogeneous (ideal and nonideal), Eley–Rideal and Langmuir–Hin
shelwood–Hougen–Watson (LHHW) models to determine the kinetic parameters. All the models were suit
able to predict the experimental data, but with the LHHW model a more accurate match of the experimental
data was achieved.
Keywords: kinetics, esterification, Indion 190 catalyst, adsorption, nonideal model, LHHW model
DOI: 10.1134/S0023158415040126