Raney Cu催化剂催化草酸二甲酯加氢反应失活与活性再生  

Deactivation and reactivation of Raney Cu catalyst for dimethyl oxalate selective hydrogenation

作　　者：孔祥鹏 武瑞晗 元培红 王瑞虹 吴跃焕 Kong Xiangpeng;Wu Ruihan;Yuan Peihong;Wang Ruihong;Wu Yuehuan(Department of Chemistry and Chemical Engineering,Taiyuan Institute of Technology,Taiyuan 030008,Shanxi,China;School of Chemistry and Chemical Engineering and Technology,North University of China,Taiyuan 030051,Shanxi,China;Center for Disease Control and Prevention,The Third Engineer Group Co.,Ltd.of China Railway,Taiyuan 030012,Shanxi,China)

机构地区：[1]太原工业学院化学与化工系,山西太原030008 [2]中北大学化学与化工学院,山西太原030051 [3]中铁三局集团疾病预防控制中心,山西太原030006

出　　处：《工业催化》2023年第6期22-27,共6页Industrial Catalysis

基　　金：山西省高等学校科技创新项目(2019L0928,2020L0658);山西省“1331工程”(晋教科[2021]2号)。

摘　　要：以催化草酸二甲酯(DMO)加氢反应失活Raney Cu催化剂中Cu纳米粒子为研究对象,采用TG-DTG、XRD和FT-IR等手段分析其失活及活性再生关键因素,并考察其经原位再生催化剂循环的稳定性能。结果表明,Raney Cu催化剂催化DMO选择加氢反应过程中,催化剂表面积炭覆盖表面活性位,致使表面活性位可逆失效,是其失活的主要原因,而不是催化剂中Cu纳米粒子迁移和聚集烧结。以失活催化剂为基体,经300℃以上热处理能够有效脱除其表面积炭,于适宜条件下催化DMO选择加氢反应,DMO完全转化,乙二醇(EG)收率超过95.0%,而其循环催化稳定时间逐渐缩短。此外,催化剂表面CuC_(2)O_(4)化合物生成、热解引起表面活性物种价态频变诱发结构演化及Cu活性物种不可逆流失,进一步加剧Raney Cu催化剂失活。Deactivation and regeneration of Raney Cu catalysts for dimethyl oxalate(DMO)selective hydrogenation to ethylene glycol(EG)were investigated by TG-DTG,XRD and FT-IR.The cycle life of situ regenerated catalyst was also tested.It was found that the main reason for rapid reversible deactivation was carbon deposition on surface active sites instead of migration and sintering of Cu nanoparticles.Surface carbon deposition could be removed by thermal treatment at temperature above 300℃.Under the optimum reaction conditions,conversion of DMO was 100%,and yield of EG was 95.0%.Nonetheless,the cycle life of catalyst became gradually shortened.Additionally,CuC_(2)O_(4) formation on surface,the structure evolution and accessible active species irreversible loss due to pyrolysis of the copper active compounds during the DMO hydrogenation reaction further aggravated the Raney Cu catalyst deactivation.

关 键 词：催化化学 Raney Cu 草酸二甲酯 加氢 失活 再生 

分 类 号：O643.36[理学—物理化学] TQ426.6[理学—化学]