Reconstruction of Cu–ZnO catalyst by organic acid and deactivation mechanism in liquid-phase hydrogenation of dimethyl succinate to 1,4-butanediol

Abstract

A reconstructed Cu–ZnO catalyst with improved stability was fabricated by organic acid treatment method for the liquid-phase hydrogenation of dimethyl succinate to 1,4-butanediol. According to the characterization results of the fresh Cu–ZnO and reconstructed Cu–ZnO, three different forms of ZnO were suggested to be presented on the catalysts: ZnO having strong interaction with Cu species, ZnO that weakly interacted with Cu species and isolated ZnO. The first form of ZnO was believed to be beneficial to the formation of efficient active site Cu⁺, while the latter two forms of ZnO took the main responsibility for the deactivation of Cu–ZnO catalysts in the liquid-phase hydrogenation of diesters. The reconstruction of the Cu–ZnO catalyst by the organic acid treatment method resulted in a new Cu–ZnO catalyst with more Cu⁺ and less ZnO species that leads to deactivation. Furthermore, the deactivation mechanism of Cu–ZnO catalysts in liquid-phase diester hydrogenation in continuous flow system was proposed: the deposition of the polyesters on the catalysts via transesterification catalyzed by weakly interacted ZnO and isolated ZnO leads to the deactivation. These results provided meaningful instructions for designing highly efficient Cu–Zn catalysts for similar ester hydrogenation systems.

Graphical abstract

Keywords

liquid phase / hydrogenation / Cu–ZnO / deactivation mechanism / 1,4-butanediol / diester

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Acknowledgements

We are grateful for the financial support from the National Natural Science Foundation of China (Grant Nos. 21878227 and 22278309).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-022-2281-9 and is accessible for authorized users.

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