BACKGROUND: A pervaporation catalyticmembrane reactor (PVCMR) can contain reaction and separation systems in one unit. This separation technique has attracted increasing attention in recent years due to its lowenergy requirement, environmentally friendly technology, easy control and scale-up in integrated systems. The main aim of this present study is to develop a catalytic polymeric composite membrane for application in a PVCMR. RESULTS: In this study, esterification of acetic acid and ethanol were studied as a model reaction in a batch reactor and in a PVCMR. A composite membrane was prepared by coating chitosan membrane with a thin layer of Zr(SO4)(2)center dot 4H(2)O. Tests were carried out to optimize operating conditions such as initial molar ratio, catalyst concentration and temperature. The acetic acid conversion was increased from 22% to 85% using a PVCMR by removal of water from the reaction mixture in the optimum operating conditions. Under the tested conditions, amolar ratio of reactants 1: 1, catalyst concentration 0.25 g L-1 and temperature 70 degrees C were found to be optimum conditions for separation. CONCLUSION: The PVCMR exhibited higher performances than the batch reactor in the esterification of ethanol and acetic acid. The PVCMR can be used efficiently for other esterification reactions. (C) 2014 Society of Chemical Industry