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Research of Cu-ZnO catalysts for sec-butanol dehydrogenation to methyl ethyl ketone

JIANG Guangshen1,HU Yunfeng1,2,CAI Jun1,XU Peng3,CONG Liang1,FANG Fei1   

  1. 1Department of Chemistry & Chemical Engineering ,Northeast Petroleum University,Daqing 163318,Heilongjiang,China; 2Applied Technology Research Institute of Daqing,Daqing 163318,Heilongjiang,China; 3Daqing Refinery & Chemical Company,PetroChina,Daqing 163316,Heilongjiang,China
  • Online:2013-02-05 Published:2013-02-05

仲丁醇脱氢制甲乙酮的Cu-ZnO催化剂

姜广申1,胡云峰1,2,蔡 俊1,许 鹏3,丛 亮1,方 菲1   

  1. 1东北石油大学化学化工学院,黑龙江 大庆 163318;2大庆应用技术研究院,黑龙江 大庆 163318;3大庆炼化公司,黑龙江 大庆 163316

Abstract: Copper-zinc catalysts prepared by co-precipitation and physical mixing were characterized by TPR,XRD and N2O adsorption-decomposition techniques to analyze the roles of ZnO and Cu in the dehydrogenation of sec-butanol (SBA). The studies suggested that Cu0 were active sites and ZnO was provided with the properties of dispersion and anti-sintering of Cu species. ZnO could effectively disperse Cu species and prevent Cu0 from sintering because (CuZn)x(OH)y(CO3)z(x=1,5;y=2,6;z=1,2) precursor was formed in catalyst preparation and highly dispersed CuO-ZnO solid solution was shaped after calcination. Optimum Cu/Zn molar ratio was also studied for the dehydrogenation tests of SBA. Cu/Zn molar ratio at 1∶1 exhibited excellent reactivity. Conversion of SBA and yield of methyl ethyl ketone (MEK) reached 80.54% and 76.04%,respectively,under atmospheric pressure,at reaction temperature 240 ℃ and weight space velocity 17.5 h?1. The dehydrogenation activity of copper-zinc catalyst was not in linear relationship with Cu0 surface area,indicating that dehydrogenation of SBA could be a structure-sensitive reaction.

Key words: sec-butanol, catalytic dehydrogenation, methyl ethyl ketone, copper-zinc catalyst

摘要: 采用共沉淀法和机械混合法制备了铜锌催化剂,并利用TPR、XRD和N2O吸附分解催化剂表征手段分析了铜锌催化剂中ZnO和Cu在仲丁醇(sec-butanol,SBA)脱氢反应中的作用。研究表明,Cu0是SBA脱氢的活性中心,ZnO具有分散铜物种和抗烧结能力。ZnO能够有效分散铜物种和阻止Cu0烧结的原因是在催化剂制备过程中形成了(CuZn)x(OH)y(CO3)z(x=1,5;y=2,6,z=1,2)前体,经焙烧形成了高分散的CuO-ZnO固溶体。同时,通过SBA催化脱氢反应测试筛选了适宜的Cu/Zn摩尔比,当Cu/Zn为1∶1时,表现出良好的反应活性,常压、240 ℃下质量空速为17.5 h?1时,该催化剂对SBA转化率达到80.54%,甲乙酮(methyl ethyl ketone,MEK)收率达到76.04%。铜锌催化剂的脱氢活性与Cu0比表面积不呈线性关系,SBA脱氢反应是一结构敏感型反应。

关键词: 仲丁醇, 催化脱氢, 甲乙酮, 铜锌催化剂

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