Chin.J.Chem.Eng. ›› 2018, Vol. 26 ›› Issue (5): 1059-1063.doi: 10.1016/j.cjche.2018.02.018

• Catalysis, kinetics and reaction engineering • Previous Articles     Next Articles

Influence of dehydrating agents on the oxidative carbonylation of methanol for dimethyl carbonate synthesis over a Cu/Y-zeolite catalyst

Dong-Ho Lee1,2, Jiin You1, Je-Min Woo1, Jung Yoon Seo1, Young Cheol Park1, Jong-Seop Lee1, Hyunuk Kim3, Jong-Ho Moon1, Seung Bin Park2   

  1. 1 Greenhouse Gas Laboratory, Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon, 34129, Korea;
    2 Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology, 291 Daehak-ro, Yuseong-gu, Daejeon, 34141, Korea;
    3 Energy Material Laboratory, Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon, 34129, Korea
  • Received:2017-10-19 Revised:2018-01-19 Online:2018-05-28 Published:2018-06-29
  • Contact: Jong-Ho Moon,E-mail;Seung Bin Park,E-mail;

Abstract: 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 CuCl2·2H2O and the commercial NH4-form of the Y type zeolite. The catalyst was characterized by X-ray fluorescence (XRF), N2 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 (2CH3OH + 1/2O2 + CO ? (CH3O)2CO + H2O). The influence of various dehydrating agents (ZnO, MgO, and CaO) was examined with the aim of increasing the methanol conversion (XMeOH, MeOH conversion). The MeOH conversion increased upon addition of metal oxides in the order CaO >> MgO > ZnO, with the DMC selectivity (SDMC) 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.

Key words: Carbon monoxide, Zeolite, Catalyst, Dimethyl carbonate, Oxidative carbonylation, Dehydrating agent