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The reaction kinetics of the esterification of acetic acid with ethanol, catalyzed both homogeneously by the acetic acid, and heterogeneously by Amberlyst 15, have been investigated. The reactions were carried out at several temperatures between 303.15 and 353.15K and at various starting reactant compositions. Homogeneous and heterogeneous reactions have been described using the models proposed by Popken et al. [T.Popken,L.Gotze,J.Gmehling, Reaction kinetics and chemical equilibrium of homogenously and heterogeneously catalyzed acetic acid
esterification with methanol and methyl acetate hydrolysis, Ind.Eng.Chem.Res.39(2000)2601-2611]. These models use activities instead of
mole fractions.Activity coefficients have been calculated using ASOG[K.Kojima,K.Tochigi,Prediction of Vapor-liquid Equilibria by the ASOG
Method,Elsevier,Tokyo,1979] and UNIFAC (Aa.Fredenslund, J.Gmehling, P.Rasmussen, Vapor-liquid Equilibria Using UNIFAC. A Group Contribution Method,Elsevier,Amsterdam,1977]methods.
A packed bed reactive distillation column filled with Amberlyst 15 has been employed to obtain ethyl acetate.The influence of feed composition and reflux ratio have been analyzed.
Reactive distillation has become an interesting alternative to some conventional processes,especially for equilibrium-limited reactions as esterifications and etherifications. In these reactions, conversion and selectivity are increasing because products are continuously removed from the reaction mixture.In last years,
investigations of thermodynamic, reaction kinetics and simulation for different processes have been made(Bocket al.[4],Vora and Daoutidis [5],Kenig et al.[6], Steinigeweg and Gmehling[7],Teo and Saha [8],Kloker et al. [9]).The aim of this work is the study of the production of ethyl acetate by esteri?cation of acetic acid with ethanol in a reactive distillation column.In a previous work(Calvar et al. [10])the vapor-liquid equilibria of the quaternary reactive system acetic acid+ethanol+ethyl
acetate+water at 101.3kPa have been determined.In this paper,the homogenous and heterogeneous catalyzed esterification kinetics and the results of the operation in a packed bed reactive distillation column are presented.The above mentioned kinetics have been studied previously by Kirbaslar et al. [11] and Hangx et al. [12] but they did not take into account the activity coefficient of the compounds in the mixture.

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