Chinese Journal of Catalysis ›› 2018, Vol. 39 ›› Issue (8): 1283-1293.DOI: 10.1016/S1872-2067(18)63032-3

• Special Column on the 15th International Conference on Carbon Dioxide Utilization (ICCDU XV) • Previous Articles     Next Articles

An efficient and stable Cu/SiO2 catalyst for the syntheses of ethylene glycol and methanol via chemoselective hydrogenation of ethylene carbonate

Jiaju Liua,c, Peng Hea, Liguo Wanga,b,d, Hui Liuc, Yan Caoa, Huiquan Lia,d   

  1. a National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
    b Jiangsu Collaborative Innovation Center for Ecological Building Materials and Environmental Protection Equipments, Yancheng Institute of Technology, Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province, Yancheng 224051, Jiangsu, China;
    c Beijing University of Chemical Technology, Beijing 100029, China;
    d Sino-Danish College, University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2017-11-15 Revised:2018-01-11 Online:2018-08-18 Published:2018-07-04
  • Contact: 10.1016/S1872-2067(18)63032-3
  • Supported by:

    This work was supported by the National Natural Science Foundation of China (21576272, 21406245), the project from Jiangsu Collaborative Innovation Center for Ecological Building Materials and Environmental Protection Equipments (YCXT201607), and the "Transformational Technologies for Clean Energy and Demonstration", Strategic Priority Research Program of the Chinese Academy of Sciences (XDA21030600).

Abstract:

The efficient synthesis of methanol and ethylene glycol via the chemoselective hydrogenation of ethylene carbonate (EC) is important for the sustainable utilization of CO2 to produce commodity chemicals and fuels. In this work, a series of β-cyclodextrin-modified Cu/SiO2 catalysts were prepared by ammonia evaporation method for the selective hydrogenation of EC to co-produce methanol and ethylene glycol. The structure and physicochemical properties of the catalysts were characterized in detail by N2 physisorption, XRD, N2O titration, H2-TPR, TEM, and XPS/XAES. Compared with the unmodified 25Cu/SiO2catalyst, the involvement of β-cyclodextrin in 5β-25Cu/SiO2 could remarkably increase the catalytic activity-excellent activity of 1178 mgEC gcat-1 h-1 with 98.8% ethylene glycol selectivity, and 71.6% methanol selectivity could be achieved at 453 K. The remarkably improved recyclability was primarily attributed to the remaining proportion of Cu+/(Cu0+Cu+). Furthermore, the DFT calculation results demonstrated that metallic Cu0 dissociated adsorbed H2, while Cu+ activated the carbonyl group of EC and stabilized the intermediates. This study is a facile and efficient method to prepare highly dispersed Cu catalysts-this is also an effective and stable heterogeneous catalyst system for the sustainable synthesis of ethylene glycol and methanol via indirect chemical utilization of CO2.

Key words: Ethylene carbonate, Hydrogenation, β-Cyclodextrin, Cu/SiO2, Methanol, Ethylene glycol