Esterification of acetic acid with methanol : a kinetic study on Amberlyst 15

Abstract

Reaction rate data at 50oC was generated in a batch reactor over a wide range of initial concentrations in the reaction mixture. In each case the reaction was allowed to reach equilibrium. Equilibrium conversion data clearly indicated that it is important to consider the non-ideality of the system. The NRTL activity model proved to be the most suitable model to calculate the activity based equilibrium constant, as the percentage standard deviation of the equilibrium constant calculated in this manner was only 7.6% for all the different experiments as opposed to 17.8% when the equilibrium constant was based on concentration. The NRTL parameters used were obtained from Gmehling&Onken (1977) who determined the parameters from vapour liquid equilibrium. The Langmuir-Hinshelwood kinetics proposed by Song et al. (1998) and Pöpken et al. (2000) provided an excellent representation of the reaction rate over a wide concentration range with an AARE of 6% and 5% respectively. It was shown that when the NRTL activities were used in the rate expression that a power law model provided a similarly accurate prediction of the reaction rate (AARE = 4.1%). When the Eley-Rideal reaction expression (in terms of the adsorption of methanol and water) was used, a slight improvement was achieved (AARE = 2.4%). As both the Langmuir-Hinshelwood and Eley-Rideal models require separate experiments for the measurement of adsorption constants, it seems that the activity based power law model should be the kinetic expression of choice. It can be concluded that a two parameter activity based rate expression predicts the reaction rate with similar accuracy as the multi-parameter adsorption models. This indicates that it is not necessary to know the concentration on the resin surface (adsorption models) or in the resin gel (absorption models) when describing the reaction rate as long as the bulk liquid phase activities can be adequately described.