The influence of the dehydration by metal oxides on the synthesis of dimethyl carbonate (DMC) via oxidative carbonylation of methanol was studied. A Cu/Y-zeolite catalyst was prepared by the ion exchange method from CuCl2 center dot 2H(2)O and the commercial NH4-form of the Y type zeolite. The catalyst was characterized by X-ray fluorescence (XRF), N-2 adsorption (BET method), X-ray diffraction (XRD), and temperature-programmed desorption of ammonia (NH3-TPD) to evaluate its Cu and Cl content, surface area, structure, and acidity. Reaction tests were carried out using an autoclave (batch reactor) for 18 h at 403 K and 5.5 MPa (2CH(3)OH + 1/2O(2) + CO reversible arrow (CH3O)(2)CO + H2O). The influence of various dehydrating agents (ZnO, MgO, and CaO) was examined with the aim of increasing the methanol conversion (X-MeOH, MeOH conversion). The MeOH conversion increased upon addition of metal oxides in the order CaO >> MgO > ZnO, with the DMC selectivity (S-DMC) following the order MgO > CaO > ZnO. The catalysts and dehydrating agents were characterized before and after the oxidative carbonylation of methanol by thermogravimetric and differential thermogravimetric (TG/DTG), and XRD to confirm that the dehydration reaction occurred via the metal oxide (MO + H2O -> M(OH)(2)). The MeOH conversion increased from 8.7% to 14.6% and DMC selectivity increased from 39.0% to 53.1%, when using the dehydrating agent CaO. (C) 2018 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.