草酸二甲酯加氢制乙二醇铜基催化剂失活原因分析

合成气经草酸二甲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、少气和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。对草酸二甲酯加氢制备乙二醇铜基催化剂的失活原因进行分析,重点讨论催化剂烧结、积炭、中毒、溶剂、反应气氛和物理磨损对催化剂稳定性的影响。通过添加助催化剂以稳定催化剂中Cu价态分布,有效抑制Cu晶粒团聚长大速率。加强反应过程的基础研究,即草酸二甲酯存在的解离方式、反应气氛和溶剂的影响、高聚物的形成机制以及如何抑制高聚物等方面尚待进一步研究。注重催化剂的工程化开发,加强成型方式、扩散过程和反应体系杂质的影响研究。

Deactivation reason analysis of copper-based catalysts for hydrogenation of dimethyl oxalate to ethylene glycol

The synthesis of ethylene glycol from syngas via hydrogenation of dimethyl oxalate is a novel non-oil route to obtain bulk chemicals.It has important realistic and strategic significance to research on the process route because of the energy structure of ‘deficient oil,lean gas,rich coal’ in China.The deactivation causes of Cu-based catalyst for dimethyl oxalate hydrogenation to ethylene glycol was analyzed.The effects of catalyst agglomeration,carbon deposition,poisoning,solvents,reaction atmosphere and physical abrasion on the catalyst stability were reviewed emphatically.Cu crystalline grain agglomeration rate was effectively inhibited by adding additives to stabilize the valence distribution of Cu species in the catalysts.The future research aspects are to strengthen basic study on reaction process,including dissociation modes of dimethyl oxalate,the influence of reaction atmosphere and the solvents,polymer formation mechanism and how to restrain the polymer formation,the engineering development of the catalysts, the catalyst forming method,and the effects of diffusion process and the impurities in the reaction systems,etc.