Gas phase hydrogenation of maleic anhydride to tetrahydrofuran by Cu/ZnO/TiO2 catalysts in the presence of n-butanol

作者:Zhang Ruichao; Yin Hengbo*; Zhang Dongzhi; Qi Lin; Lu Huihong; Shen Yutang; Jiang Tingshun
来源:Chemical Engineering Journal, 2008, 140(1-3): 488-496.
DOI:10.1016/j.cej.2007.11.031

摘要

Cu/ZnO/TiO2 catalysts were prepared via the coprecipitation method. The catalysts were characterized by X-ray diffraction, X-ray photoelectron spectrometry, temperature programmed reduction, and N-2 adsorption. The catalytic activity of Cu/ZnO/TiO2 catalyst in gas phase hydrogenation of maleic anhydride in the presence of n-butanol was studied at 235-280 degrees C and 1 MPa. The conversion of maleic anhydride was more than 95.7% and the selectivity of tetrahydrofuran was up to 92.7%. At the same time, n-butanol was converted to butyraldehyde and butyl butyrate via reactions, namely, dehydrogenation, disproportionation, and esterification. There were two kinds of CuO species present in the calcined Cu/ZnO/TiO2 catalysts. At a lower copper content, the CuO species strongly interacted with ZnO and TiO2; at a higher copper content, both the surface-anchored and bulk CuO species were present. The metallic copper (CuO) produced by the reduction of the surface-anchored CuO species favored the deep hydrogenation of maleic anhydride to tetrahydrofuran. The deep hydrogenation activity of Cu/ZnO/TiO2 catalyst increased with the decrease of crystallite sizes of CuO and the increase of microstrain values. Compensations of reaction heat and H-2 in the coupling reaction of maleic anhydride hydrogenation and n-butanol dehydrogenation were distinct.