Chinese Journal of Catalysis ›› 2008, Vol. 29 ›› Issue (7): 643-648.

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Surface Structure and Catalytic Performance of CuCl/SiO2-Al2O3 Catalysts for Methanol Oxidative Carbonylation

LI Zhong*, MENG Fanhui, REN Jun, ZHENG Huayan, XIE Kechang   

  1. Key Laboratory of Coal Science and Technology, Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
  • Received:2008-07-25 Online:2008-07-25 Published:2012-06-07

Abstract: Aluminum was doped into amorphous silica gel to modify its surface structure. The obtained SiO2-Al2O3 support was used to prepare the CuCl/SiO2-Al2O3 catalyst by solid-state ion exchange, and the catalyst activity for liquid-phase oxidative carbonylation of methanol to dimethyl carbonate was investigated. The results showed that the prepared SiO2-Al2O3 support kept the amorphous structure of the silica gel. The BET specific surface area of the silica gel was decreased to 200 m2/g, and the surface acid sites (including Brnsted acid sites) were increased. In the CuCl/SiO2-Al2O3 catalyst, CuCl was not only dispersed on surface but also was ion exchanged with surface Brnsted acid sites of the SiO2-Al2O3 support to form Cu+ species, which resulted in a decrease in BET specific surface area to 148 m2/g. These two kinds of Cu+ species on the catalyst surface were both active centers for the oxidative carbonylation of methanol to dimethyl carbonate. When the catalyst was prepared with Si/Al molar ratio of 5 and was calcined at 500 ℃, the selectivity and space-time yield of dimethyl carbonate reached 74% and 1.27 g/(g·h), respectively.

Key words: cuprous chloride, alumina-silica mixed oxide, methanol, oxidative carbonylation, dimethyl carbonate