High-efficiency oxidative esterification of furfural to methylfuroate with a non-precious metal Co-N-C/MgO catalyst

doi:10.1016/S1872-2067(17)62841-9

Abstract

Abstract:

From both fundamental and practical perspectives, the production of chemicals from biomass re-sources using high-efficiency non-precious metal catalysts is important. However, many processes require addition of stoichiometric or excess quantities of base, which leads to high energy consump-tion, leaching problems, and side reactions. In this study, we investigated the high-efficiency oxida-tive esterification of furfural to methylfuroate by molecular oxygen with a Co-N-C/MgO catalyst. The catalyst was prepared by direct pyrolysis of a cobalt(Ⅱ) phenanthroline complex on MgO at 800℃ under N₂ atmosphere. From furfural, 93.0% conversion and 98.5% selectivity toward methylfuroate were achieved under 0.5 MPa O₂ with reaction at 100℃ for 12 h without a basic additive. The con-version and selectivity were much higher than those obtained with cobalt catalysts produced by pyrolysis of a cobalt(Ⅱ) phenanthroline complex on activated carbon or typical basic supports, in-cluding NaX, NaY, and CaO. X-ray photoelectron spectroscopy, X-ray diffraction, transmission elec-tron microscopy, and experimental results revealed that the high efficiency of Co-N-C/MgO for pro-duction of methylfuroate was closely related to the cobalt-nitrogen-doped carbon species and its catalytic ability in hydrogen abstraction. In contrast, Co-N-C(HCl) that synthesized by removing MgO with HCl from Co-N-C/MgO, as the catalyst produced mainly an acetal as a condensation prod-uct, and chloride ions had a negative effect on the oxidative esterification. Although the catalytic performance of the cobalt-nitrogen-doped carbon species was greatly affected by HCl treatment, it could be recovered to a great extent by addition of MgO. Moreover, changes in the oxygen pressure hardly affected the oxidative esterification of furfural with Co-N-C/MgO. This study not only pro-vides an effective approach to prepare methylfuroate, but also for designing high-performance non-precious metal catalysts for the oxidative esterification of biomass-derived compounds.

Key words: Catalysis, Cobalt-nitrogen-doped carbon, Furfural, Methylfuroate, MgO, Oxidative esterification

Na Huo, Hong Ma, Xinhong Wang, Tianlong Wang, Gang Wang, Ting Wang, Leilei Hou, Jin Gao, Jie Xu. High-efficiency oxidative esterification of furfural to methylfuroate with a non-precious metal Co-N-C/MgO catalyst[J]. Chinese Journal of Catalysis, 2017, 38(7): 1148-1154.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(17)62841-9

https://www.cjcatal.com/EN/Y2017/V38/I7/1148

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