整体式Pd/ZSM-5/Cordierite催化剂的制备及其低浓度甲烷燃烧催化性能
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摘要
以蜂窝状堇青石(Cordierite)为载体,采用聚乙烯醇纤维(PVA)溶液辅助涂覆法制备了整体式Pd/ZSM-5/Cordierite催化剂;利用XRD、N2物理吸附、SEM和XPS等手段对催化剂的结构和性质进行了表征。将该催化剂用于低浓度甲烷催化燃烧,研究了PVA溶液浓度、活性组分负载方式和Pd负载量等因素对Pd/ZSM-5/Cordierite催化剂活性涂层稳定性及低浓度甲烷燃烧催化性能的影响。结果表明,以质量分数为3%的PVA溶液制备的分子筛浆料进行涂层涂覆,所得到的整体式催化剂活性涂层具有良好的牢固度。以Pd/ZSM-5为涂层粉体、Pd整体负载量为1.12‰(质量分数,下同)时,所制备的(Pd/ZSM-5)/Cordierite催化剂具有优异的低浓度甲烷(体积分数为1%)燃烧催化性能,甲烷转化率为10%、50%和90%时的反应温度分别为271、337和385℃。此外,在不同温度下435h长周期测试实验中,该整体式(Pd/ZSM-5)/Cordierite催化剂表现出较高的抗热稳定性,表明其具有良好的低浓度甲烷燃烧处理应用前景。
A monolithic Pd/ZSM-5/Cordierite catalyst was prepared by coating the active Pd/ZSM-5component on the Cordierite support with Polyvinyl alcohol(PVA)solution as an assistant agent,and its structure and physicochemical properties were characterized by XRD,N2 sorption,SEM,XPS and ICP-AES.The Pd/ZSM-5/Cordierite catalyst was applied in the combustionof lean methane and the effects of PVA concentration,active component loading mode and Pd loading on the coating stability and catalytic performance in lean methane combustion were then investigated.The results indicate that a stable coating of the active Pd/ZSM-5component can be achieved on the Cordierite support when the mass fraction of PVA in the PVA solution is 3%.With an overall Pd loading of 1.12‰ and Pd/ZSM-5as the coating powder,the(Pd/ZSM-5)/Cordierite catalyst exhibits excellent performance in the lean methane(1%)combustion.The reaction temperatures to reach a methane conversion of 10%,50%and 90%are as low as 271,337 and 385℃,respectively.Moreover,the monolithic(Pd/ZSM-5)/Cordierite catalyst also displays excellent stability in a long term test of 435 hfor the lean methane combustion at different temperatures,suggesting its enormous potential for the application in the mitigation of lean methane through catalytic combustion.
A monolithic Pd/ZSM-5/Cordierite catalyst was prepared by coating the active Pd/ZSM-5component on the Cordierite support with Polyvinyl alcohol(PVA)solution as an assistant agent,and its structure and physicochemical properties were characterized by XRD,N2 sorption,SEM,XPS and ICP-AES.The Pd/ZSM-5/Cordierite catalyst was applied in the combustionof lean methane and the effects of PVA concentration,active component loading mode and Pd loading on the coating stability and catalytic performance in lean methane combustion were then investigated.The results indicate that a stable coating of the active Pd/ZSM-5component can be achieved on the Cordierite support when the mass fraction of PVA in the PVA solution is 3%.With an overall Pd loading of 1.12‰ and Pd/ZSM-5as the coating powder,the(Pd/ZSM-5)/Cordierite catalyst exhibits excellent performance in the lean methane(1%)combustion.The reaction temperatures to reach a methane conversion of 10%,50%and 90%are as low as 271,337 and 385℃,respectively.Moreover,the monolithic(Pd/ZSM-5)/Cordierite catalyst also displays excellent stability in a long term test of 435 hfor the lean methane combustion at different temperatures,suggesting its enormous potential for the application in the mitigation of lean methane through catalytic combustion.
引文
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[22]谢云龙,钟依均,林惠琳.一种有机废气处理用贵金属整体催化剂及其制造方法:CN102366723A[P].2012-03-07.
[23]梁婵,郭松林,肖素萍.Pd/CeO2-ZSM-5/CC催化净化低中温尾气CO的试验研究[J].萍乡学院学报,2014,31(6):44-47.
[24]黄寻,李慧,肖文德.HZSM-5/堇青石规整催化剂的制备及其在甲醇制丙烯反应中的应用[J].石油化工,2016,45(2):156-162.
[25]张佳瑾.低浓度甲烷流向变换催化燃烧实验研究及模型化[D].北京:北京化工大学,2012.
[26]RAMESH R,PRASHANT S C,HOWARD L G.Aging and structure/activity characteristics of CR-ZSM-5catalysts during exposure to chlorinated VOCs[J].Journal of Catalysis,1999,185(1):58-72.
[27]刘翻艳,贾志刚,黄敬敬.堇青石表面涂层对Pd基整体式催化剂结构和性能的影响[J].石油化工,2013,42(9):950-955.
[2]王盈,朱吉钦,李攀,等.低浓度甲烷流向变换催化燃烧的研究[J].燃料化学学报,2005,33(6):760-762.
[3]卢楠,吴志伟,雷丽军,等.核-壳结构Pd-Co3O4@SiO2催化剂的低浓度甲烷催化燃烧性能[J].燃料化学学报,2015,43(9):1120-1127.
[4]ORDONEZ S,PAREDES J R,DIEZ F V.Sulphur poisoning of transition metal oxides used as catalysts for methane combustion[J].Applied Catalysis A:General,2008,341(1/2):174-180.
[5]王胜,高典楠,张纯希,等.贵金属甲烷燃烧催化剂[J].化学进展,2008,20(6):789-797.
[6]GROPPI G,CRISTIANI C,LIETTI L,et al.Effect of ceria on palladium supported catalysts for high temperature combustion of CH4under lean conditions[J].Catalysis Today,1999,50(2):399-412.
[7]SU S,AGNEW J.Catalytic combustion of coal mine ventilation air methane[J].Fuel,2006,85(9):1201-1210.
[8]王珂,林志娇,江志东.甲烷催化燃烧整体型催化剂研究进展[J].天然气化工(C1化学与化工),2009,34(1):71-78.
[9]GELIN P,PRIMET M.Complete oxidation of methane at low temperature over noble metal based catalysts:a review[J].Applied Catalysis B:Environmental,2002,39(1):1-37.
[10]DRANGOS C,LYUBOVSKY M R,ALTMAN E,et al.Catalytic combustion of methane over palladiumbased catalysts[J].Catalysis Reviews,2002,44(4):593-649.
[11]严河清,张甜,王鄂凤,等.甲烷催化燃烧催化剂的研究进展[J].武汉大学学报(理学版),2005,51(2):161-166.
[12]陆富生.甲烷催化燃烧催化剂催化理论与应用研究进展[J].化工时刊,2009,23(8):52-56.
[13]WANG B,QIN Z F,WANG G F,et al.Catalytic combustion of lean methane at low temperature over palladium on a CoOx-SiO2composite support[J].Catalysis Letters,2013,143(5):411-417.
[14]LI Y J,ARMOR J N.Catalytic combustion of methane over palladium exchanged zeolites[J].Applied Catalysis B:Environmental,1994,3(4):275-282.
[15]史春开.甲烷低温燃烧反应分子筛负载Pd催化剂[D].厦门:厦门大学,2003.
[16]JONG B L,DONGHUI J,SUK B H.Palladium-exchanged small-pore zeolites with different cage systems as methane combustion catalysts[J].Applied Catalysis B:Environmental,2017,219:155-162.
[17]KAZUHIRO N,KIYOSHI,YASUHISA N,et al.Pd-Pt bimetallic catalyst supported on SAPO-5for catalytic combustion of diluted methane in the presence of water vapor[J].Catalysis Letters,1998,53(3/4):167-169.
[18]ELMER T H.Ultra-low expansion ceramic articles:US3958058[P].1976-05-18.
[19]BEALL D M,MURTAGH M J.Fabrication of low thermal expansion,high strength cordierite structures:US6319870[P].2001-11-20.
[20]华金铭,郑起,魏可镁,等.酸蚀预处理对蜂窝状堇青石及其不同方法涂敷氧化铝涂层的影响[J].分子催化,2006,20(6):550-555.
[21]刘鹏飞.Fe-Mn/ZSM-5/CC整体式催化剂结构及NOx催化还原性能的研究[D].太原:太原理工大学,2014.
[22]谢云龙,钟依均,林惠琳.一种有机废气处理用贵金属整体催化剂及其制造方法:CN102366723A[P].2012-03-07.
[23]梁婵,郭松林,肖素萍.Pd/CeO2-ZSM-5/CC催化净化低中温尾气CO的试验研究[J].萍乡学院学报,2014,31(6):44-47.
[24]黄寻,李慧,肖文德.HZSM-5/堇青石规整催化剂的制备及其在甲醇制丙烯反应中的应用[J].石油化工,2016,45(2):156-162.
[25]张佳瑾.低浓度甲烷流向变换催化燃烧实验研究及模型化[D].北京:北京化工大学,2012.
[26]RAMESH R,PRASHANT S C,HOWARD L G.Aging and structure/activity characteristics of CR-ZSM-5catalysts during exposure to chlorinated VOCs[J].Journal of Catalysis,1999,185(1):58-72.
[27]刘翻艳,贾志刚,黄敬敬.堇青石表面涂层对Pd基整体式催化剂结构和性能的影响[J].石油化工,2013,42(9):950-955.
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