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草酸酯加氢铜基催化剂关键技术与理论研究进展

赵玉军,赵 硕,王 博,吕 静,马新宾   

  1. 天津大学化工学院,绿色合成与转化教育部重点实验室,天津 300072
  • 出版日期:2013-04-05 发布日期:2013-04-05

Technical and theoretical advances in copper-based catalysts for oxalate hydrogenation

ZHAO Yujun,ZHAO Shuo,WANG Bo,Lü Jing,MA Xinbin   

  1. Key Lab for Green Chemical Technology of Ministry of Education,School of Chemical Engineering and Technology,Tianjin University,Tianjin 300072,China
  • Online:2013-04-05 Published:2013-04-05

摘要: 合成气经草酸酯加氢制乙二醇工艺是非石油路线合成大宗化学品的新兴路线。在我国贫油、少气、煤炭相对丰富的能源结构条件下,该工艺路线的研究具有重要的现实意义和战略意义。本文着重介绍了草酸酯加氢制乙二醇铜基催化剂的研究进展。系统讨论了催化剂载体、助剂对活性和选择性的影响规律,以及催化剂的结构与价态的形成机制及其对催化性能的影响,并对草酸酯加氢制乙二醇催化剂中的内扩散问题以及催化剂成型进行综述和分析。此外,还对该草酸酯加氢反应放大和工程化进展进行了简单介绍。提出具有较高加氢活性与机械强度的新型催化剂研究是草酸酯加氢催化剂研究的重要课题,而异型催化剂的研究则有可能解决催化剂床层阻力大这一工程化难题。此外也提出制备高温稳定的铜基催化剂是今后的重要研究方向。

关键词: 草酸酯, 加氢, 乙二醇, 铜基催化剂,

Abstract: The synthesis of ethylene glycol from syngas via hydrogenation of oxalate is a novel non-oil route to obtain bulk chemicals. Due to the “deficient oil,lean gas,rich coal” energy structure in China,research on the technology bears a realistic and strategic significance. This paper introduces recent research on Cu-based catalyst applied in the hydrogenation of oxalate to EG and presents a discussion on the influences of support and additive on the activity and selectivity of catalyst. An insight was made on the catalyst structure and the formation mechanism of copper valence states,as well as its influences on catalytic performance. The internal diffusion and shaping process of the catalyst have also been discussed and analyzed in this paper. Moreover,the paper introduces the progress in scaling up and engineering of the process. Developing new catalyst with high activity and mechanical strength has been proposed as one important subject for the hydrogenation of oxalate. Furthermore,the application of irregular shape catalyst may tackle the engineering problem of the higher bed resistance of catalyst. Finally,developing thermal stable Cu-based catalyst is suggested to be one of the important aspects of this subject.

Key words: oxalate ester, hydrogenation, ethylene glycol, copper based catalyst, copper(Cu)

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