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Reconstruction of Cu-ZnO catalyst by organic acid and deactivation mechanism in liquid-phase hydrogenation of dimethyl succinate to 1,4-butanediol
Frontiers of Chemical Science and Engineering ( IF 4.3 ) Pub Date : 2023-04-12 , DOI: 10.1007/s11705-022-2281-9
Fan Sun , Huijiang Huang , Wei Liu , Lu Wang , Yan Xu , Yujun Zhao

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.



中文翻译:

有机酸重构Cu-ZnO催化剂及丁二酸二甲酯液相加氢制1,4-丁二醇失活机理

采用有机酸处理法制备了一种稳定性得到改善的重构 Cu-ZnO 催化剂,用于丁二酸二甲酯液相加氢制 1,4-丁二醇。根据新鲜 Cu-ZnO 和重构 Cu-ZnO 的表征结果,建议在催化剂上呈现三种不同形式的 ZnO:与 Cu 物种具有强相互作用的 ZnO,与 Cu 物种弱相互作用的 ZnO 和分离的 ZnO。ZnO 的第一种形式被认为有利于有效活性位点 Cu +的形成,而后两种形式的 ZnO 主要负责双酯液相加氢中 Cu-ZnO 催化剂的失活。通过有机酸处理方法对 Cu-ZnO 催化剂进行重构,得到了一种新的 Cu-ZnO 催化剂,其具有更多的 Cu +和更少的导致失活的 ZnO 物种。此外,提出了Cu-ZnO催化剂在连续流系统液相二酯加氢中的失活机理:弱相互作用的ZnO催化的酯交换反应使聚酯沉积在催化剂上,孤立的ZnO导致催化剂失活。这些结果为设计用于类似酯加氢系统的高效 Cu-Zn 催化剂提供了有意义的指导。

更新日期:2023-04-14
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