文献类型：期刊文献

英文题名：Hydrogenation of dimethyl malonate to 1,3-propanediol catalyzed by a Cu/SiO2 catalyst: the reaction network and the effect of Cu+/Cu0 on selectivity

作者：Zheng, Sainan[1];Zhu, Kake[1];Li, Wei[1];Ji, Yang[2]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, State Key Lab Chem Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]Shanghai Pujing Chem Ind Co Ltd, 1305 Huajing Rd, Shanghai 200231, Peoples R China

年份：2017

卷号：41

期号：13

起止页码：5752

外文期刊名：NEW JOURNAL OF CHEMISTRY

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000404350900061)】；

基金：Support from the Research Centre of Pujing Chemical Industry Co. Ltd is gratefully acknowledged. The assistance of Yongzheng Li in performing the N2O titration and Jingyu Zhou in performing CO-adsorption estimates is greatly appreciated.

语种：英文

摘要：1,3-Propanediol, a vital monomer for the manufacture of commodity polytrimethylene-terephthalate, is commercially produced nowadays through either hydration of acrolein or hydroformylation of ethylene oxide. Herein, for the first time, we present the investigation of an alternative route for 1,3-propanediol production from vapor-phase catalytic hydrogenation of syngas-derived dimethyl malonate on a Cu/SiO2 catalyst. The catalytic reaction network has been disclosed for the Cu/SiO2 catalyst, and the reaction proceeds through sequential hydrogenation with methyl 3-hydroxypropionate as the primary product, which can be further converted into 1,3-propanediol or methyl propionate. Excessive hydrogenation of 1,3-propanediol or methyl propionate leads to the formation of n-propanol. Meanwhile, a small amount of dimethyl malonate cracks into methyl acetate. The structural and textural properties of Cu/SiO2 catalysts with varied copper loadings were extensively characterized by X-ray diffraction, Fourier transform infrared spectroscopy, H-2-temperature programmed reduction, X-ray photoelectron spectroscopy, N-2 physisorption, CO chemisorption, N2O titration, and transmission electron microscopy. A correlation of the areal activity to copper components suggests that metallic copper modified by the co-present Cu+ species may be the active site for the hydrogenation. The highest 1,3-propanediol selectivity was achieved on a catalyst with a maximum Cu+/(Cu-0 + Cu+) ratio of 0.41. The revelation of catalytic networks and insights into the active species can provide guidance for future rational design of catalysts for regioselective hydrogenation of C=O bonds in dimethyl malonate.