低温深度脱除液相丙烯中微量CO的CuO(y)/CuxCe1-xOδ催化剂表征分析及性能实验  

Characterization of CuO(y)/CuxCe1−xOδmixed-oxide catalysts and their performance in deep removal of trace amount of CO in liquid-phase propylene

作　　者：顾慧劼 李磊 叶丽萍 黄河 罗勇 金政伟 GU Huijie;LI Lei;YE Liping;HUANG He;LUO Yong;JIN Zhengwei(State Key Laboratory of Polyolefins and Catalysis,Shanghai 200062,China;Shanghai Research Institute of Chemical Industry Co.,Ltd.,Shanghai 200062,China;Institute of Coal Chemical Industry Technology,Ningxia Coal Industry Co.,Ltd.,CHN Energy Group,Yinchuan 750411,Ningxia,China;Innovation Centre of Synergetic Technology of Coal-based Value-added Synthetic Resin Industry,Yinchuan 750411,Ningxia,China)

机构地区：[1]聚烯烃催化技术与高性能材料国家重点实验室,上海200062 [2]上海化工研究院有限公司,上海200062 [3]国家能源集团宁夏煤业有限责任公司煤炭化学工业技术研究院,宁夏银川750411 [4]宁夏煤基合成树脂高值化产业技术协同创新中心,宁夏银川750411

出　　处：《化工进展》2020年第12期5104-5111,共8页Chemical Industry and Engineering Progress

基　　金：上海人才发展资金(2018019);宁夏煤基合成树脂高值化产业技术协同创新中心(2017DC57)。

摘　　要：采用柠檬酸络合-浸渍的方法制备了CuO(y)/Cu(x )Ce(1-x)Oδ催化剂,重点研究了CuO的载体掺杂和表面负载对催化剂结构性质、氧化还原性能、吸附性能及CO净化性能等的影响,旨在指导催化剂进一步改性,实现低温下深度脱除液相丙烯中微量CO的工业化应用。采用X射线衍射(XRD)、透射电镜(TEM)、X射线光电子能谱分析仪(XPS)、拉曼光谱仪(Raman)和程序升温化学吸附仪(H2-TPR、CO-TPD)等手段表征了催化剂的结构和性质,结果显示,CuO掺杂的载体,Cu进入Ce O2晶体形成固溶体,有利于催化剂氧化还原性能;浸渍法负载CuO制得的催化剂,表面具有更多的还原态、高分散的Cu物种,有利于表面对CO吸附性能;两者协同作用共同促进了CO催化氧化性能的提升。CuO(0.40)/Cu(0.1)Ce(0.9)Oδ催化剂具有优异的CO净化性能,在50℃、3.0MPa的工况条件下,可将液相丙烯中CO体积分数从1×10^-5脱除至2.65±0.27×10^-8,达到聚合级烯烃对CO脱除深度的要求,稳定性能良好。Three CuO(y)/CuxCe1-xOδ catalysts with different compositions were prepared and evaluated for the removal of trace CO in liquid-phase propylene at low temperature.The effects of the surface Cu species and CuxCe1-xOδ solid solution on the structure,redox ability,surface state and CO oxidation activity were investigated,aiming to gain guide for further modification of the catalysts and finally to realize the industrial application.The catalysts were characterized by XRD,TEM,XPS,H2-TPR,CO-TPD,etc.which showed that in the carrier CuxCe1-xOδ prepared by citric acid complexation,the copper particles could enter into the crystal lattice of cerium oxide,which enhanced the reducibility of the catalyst for oxygen activation.And the catalyst improved by impregnation method on this carrier,had more reduced and highly dispersed Cu species on the surface,which was beneficial to the chemisorption of CO.Therefore,the CO oxidation was promoted by the synergistic interaction.CuO(0.40)/Cu0.1Ce0.9Oδ exhibited the highest activity for CO conversion.Under the conditions of 50℃,LHSV=8 h-1 and 3.0 MPa,the volume fraction of CO in liquid propylene decreased from 1.0×10-5 to 2.65±0.27×10-8 with good stability,which met the requirements of "polymer grade" propylene.

关 键 词：催化剂 载体 吸附作用 一氧化碳 深度脱除 液相丙烯 

分 类 号：TQ032.41[化学工程]