A reactive distillation (RD) process directly intensified by an auxiliary reaction is presented. The methyl acetate (MeOAc) hydrolysis intensified by methanol (MeOH) dehydration is studied as an example where the latter serves as the auxiliary reaction. A residue curve maps (RCMs) is developed to analyze the mechanism of intensification for the case with two reactions and multiple components. The analysis of thermodynamics and RCMs reveals that the reaction of MeOH dehydration is the controlling step which limits the conversion of MeOAc. Based on the chemical equilibrium and kinetically controlled design, a novel process is developed to hydrolyze MeOAc and MeOH in the process of polyvinyl alcohol. Compared to traditional processes, no additional water is required to feed into the RD column and the process is significantly simplified. With equal mole of MeOAc and MeOH as teed and a set of pre-reactor, closely 100% conversion of MeOAc and MeOH can be achieved and high purity dimethyl ether and acetic acid are the products in the RD column. (C) 2013 Elsevier Ltd. All rights reserved.