基于氧化还原共沉淀法制备的Mn-Ce催化剂及其低浓度甲烷燃烧催化性能
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摘要
采用氧化还原共沉淀法制备了一系列不同Mn/Ce比的Mn-Ce催化剂,用N_2吸附、XRD、XRF、XPS等手段进行了表征,对其低浓度甲烷催化燃烧活性进行了研究。结果表明,Mn/Ce比对Mn-Ce催化剂的活性有较大的影响;当Mn/Ce比从3∶7增加到9∶1时,其催化活性逐渐增加,甲烷转化率为50%的温度(t_(50))从501℃降低到446℃;而进一步增加Mn含量则会导致其催化活性降低。表征结果显示,Mn-Ce催化剂活性与其比表面积、表面Mn~(4+)浓度、Ce~(3+)含量和晶格氧浓度等密切相关;物相KMn_8O_(16)有利于Mn-Ce催化剂活性的提升。
A series of Mn-Ce catalysts with different Mn/Ce ratios were prepared by a redox co-precipitation method and characterized by N_2 sorption, XRD, XRF and XPS; their catalytic performance in lean methane combustion was investigated. The results indicate that the Mn/Ce ratio has a great influence on the activity of Mn-Ce catalyst in lean methane combustion. With an increase of the Mn/Ce ratio from 3∶7 to 9∶1, the activity of the Mn-Ce catalyst increases gradually and the reaction temperature needed for a methane conversion of 50%(t_(50)) decreases from 501 ℃ to 446 ℃; however, a further increase in the Mn/Ce ratio may lead to a decrease in the catalytic activity. The performance of Mn-Ce catalyst is related to many factors such as the surface area and the concentration of higher valence manganese(Mn~(4+)) species, lower valence cerium(Ce~(3+)) species and lattice oxygen; in particular, KMn_8O_(16) is of benefit to enhancing the activity of Mn-Ce catalyst.
A series of Mn-Ce catalysts with different Mn/Ce ratios were prepared by a redox co-precipitation method and characterized by N_2 sorption, XRD, XRF and XPS; their catalytic performance in lean methane combustion was investigated. The results indicate that the Mn/Ce ratio has a great influence on the activity of Mn-Ce catalyst in lean methane combustion. With an increase of the Mn/Ce ratio from 3∶7 to 9∶1, the activity of the Mn-Ce catalyst increases gradually and the reaction temperature needed for a methane conversion of 50%(t_(50)) decreases from 501 ℃ to 446 ℃; however, a further increase in the Mn/Ce ratio may lead to a decrease in the catalytic activity. The performance of Mn-Ce catalyst is related to many factors such as the surface area and the concentration of higher valence manganese(Mn~(4+)) species, lower valence cerium(Ce~(3+)) species and lattice oxygen; in particular, KMn_8O_(16) is of benefit to enhancing the activity of Mn-Ce catalyst.
引文
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[21]ZHANG P,LU H,ZHOU Y,ZHANG L,WU Z,YANG S,SHI H,ZHU Q,CHEN Y,DAI S.Mesoporous Mn CeOxsolid solutions for low temperature and selective oxidation of hydrocarbons[J].Nat Commun,2015,6:8446.
[22]WU Y,LU Y,SONG C,MA Z,XING S,GAO Y.A novel redox-precipitation method for the preparation ofα-MnO2w ith a high surface M n4+concentration and its activity tow ard complete catalytic oxidation of o-xylene[J].Catal Today,2013,201:32-39.
[23]WANG X,LIU Y,ZHANG Y,ZHANG T,CHANG H,ZHANG Y,JIANG L.Structural requirements of manganese oxides for methane oxidation:XAS spectroscopy and transition-state studies[J].Appl Catal B:Environ,2018,229:52-62.
[24]ARENA F,GUMINA B,LOMBARDO AF,ESPRO C,PATTI A,SPADARO L,SPICCIA L.Nanostructured Mn Oxcatalysts in the liquid phase selective oxidation of benzyl alcohol w ith oxygen:Part I.Effects of Ce and Fe addition on structure and reactivity[J].Appl Catal B:Environ,2015,162:260-267.
[25]ARENA F,TRUNFIO G,NEGRO J,FAZIO B,SPADARO L.Basic evidence of the molecular dispersion of Mn CeOxcatalysts synthesized via a novel“redox-precipitation”route[J].Chem M ater,2007,19(9):2269-2276.
[26]XU J,LI P,SONG X F,HE C H,YU J G,HAN Y F.Operando raman spectroscopy for determining the active phase in one-dimensional M n1-xCexO2±y nanorod catalysts during methane combustion[J].J Phys Chem Lett,2015,1(10):1648-1654.
[27]PAPAVASILIOU J,AVGOUROPOULOS G,IOANNIDES T.In situ combustion synthesis of structured Cu-Ce-O and Cu-Mn-O catalysts for the production and purification of hydrogen[J].Appl Catal B:Environ,2006,66(3):168-174.
[28]李云霞.低温等离子体-锰氧化物联合处理气体中二硫化碳和甲苯[D].合肥:合肥工业大学,2016.(LI Yun-xia.Reasearch on treatment of caron disulfide and toluene gas by low temperature plasma-manganese oxide[D].Heifei:Heifei University of Technology,2016.)
[29]JIRTOVK,MIKULOVJ,KLEMPA J,GRYGAR T,BASTL Z,KOVANDA F.Modification of Co-Mn-Al mixed oxide with potassium and its effect on deep oxidation of VOC[J].Appl Catal A:Gen,2009,361(1):106-116.
[30]KUMAR M,YUN J H,BHATT V,SINGH B,KIM J,KIM J S,KIM B S,LEE CY.Role of Ce3+valence state and surface oxygen vacancies on enhanced electrochemical performance of single step solvothermally synthesized CeO2nanoparticles[J].Electrochim Acta,2018,284:709-720.
[31]CHEN X,SHEN Y F,SUIB S L,O'Young C L.Characterization of manganese oxide octahedral molecular sieve(M-OMS-2)materials with different metal cation dopants[J].Chem M ater,2002,14(2):940-948.
[32]HAN Y F,CHEN L,RAMESH K,WIDJAJA E,CHILUKOTI S,KESUMAWINATA SURJAMI I,CHEN J.Kinetic and spectroscopic study of methane combustion overα-M n2O3nanocrystal catalysts[J].J Catal,2008,253(2):261-268.
[2]CARGNELLO M,JAN J J D,GARRIDO J C H,BAKHMUTSKY K,MONTINI T,GMEZ J J C,GORTE R J,FORNASIERO P.Exceptional activity for methane combustion over modular Pd@CeO2subunits on functionalized Al2O3[J].Science,2012,337(6095):713-717.
[3]KERR R A.A quick(partial)fix for an ailing atmosphere[J].Science,2012,335(6065):156-156.
[4]STOLAROFF J K,BHATTACHARYYA S,SMITH C A,BOURCIER W L,CAMERON-SMITH P J,AINES R D.Review of methane mitigation technologies w ith application to rapid release of methane from the arctic[J].Environ Sci Technol,2012,46(12):6455-6469.
[5]霍春秀,李强.乏风瓦斯催化燃烧实验研究[J].矿业安全与环保,2014,41(4):1-3(GUO Chun-xiu,LI Qiang.Experimental study on catalytic combustion of ventilation air methane[J].Min Saf Environ Prot,2014,41(4):1-3.)
[6]李旭.世界煤层气开发利用现状[J].煤炭加工与综合利用,2006,(6):41-45.(LI Xu.Progress of development and utilization of coalbed methane in the world[J].Coal Process Compr Util,2006,(6):41-45.)
[7]OBER J A.Mineral commodity summaries 2018[R].Reston,VA:U.S.Geological Survey,2018.
[8]MONAI M,MONTINI T,MELCHIONNA M,DUCHOˇN T,K'UˇS P,CHEN C,TSUD N,NASI L,PRINCE KC,VELTRUSKK,M ATOLN V,KHADER M M,GORTE R J,FORNASIERO P.The effect of sulfur dioxide on the activity of hierarchical Pd-based catalysts in methane combustion[J].Appl Catal B:Environ,2017,202:72-83.
[9]CHEN J,ARANDIYAN H,GAO X,LI J.Recent advances in catalysts for methane combustion[J].Catal Surv Asia,2015,19(3):140-171.
[10]WANG B,ALBARRACN-SUAZO S,PAGN-TORRES Y,NIKOLLA E.Advances in methane conversion processes[J].Catal Today,2017,285:147-158.
[11]ZHANG Y,QIN Z,WANG G,ZHU H,DONG M,LI S,WU Z,LI Z,WU Z,ZHANG J.Catalytic performance of Mn Ox-NiO composite oxide in lean methane combustion at low temperature[J].Appl Catal B:Environ,2013,129(2):172-181.
[12]HU Z,QIU S,YOU Y,GUO Y,GUO Y L,WANG L,ZHAN W C,LU G Z.Hydrothermal synthesis of NiCeOxnanosheets and its application to the total oxidation of propane[J].Appl Catal B:Environ,2018,225:110-120.
[13]SHENG Z Y,HU Y F,XUE J M,WANG X M,LIAO W P.A novel co-precipitation method for preparation of Mn-Ce/TiO2composites for NOxreduction w ith NH3at low temperature[J].Environ Technol,2012,33(21):2421-2428.
[14]CYBULSKI A.Catalytic wet air oxidation:Are monolithic catalysts and reactors feasible?[J].Ind Eng Chem Res,2007,46(12):4007-4033.
[15]DING Z Y,LI L X,WADE D,GLOYNA E F.Supercritical water oxidation of NH3over a M nO2/CeO2catalyst[J].Ind Eng Chem Res,1998,37(5):1707-1716.
[16]FIUK M M,ADAMSKI A.Activity of Mn Ox-CeO2catalysts in combustion of low concentrated methane[J].Catal Today,2015,257:131-135.
[17]SHI L M,CHU W,QU F F,LUO S H.Low-temperature catalytic combustion of methane over Mn Ox-CeO2mixed oxide catalysts:Effect of preparation method[J].Catal Lett,2007,113(1/2):59-64.
[18]ZHANG H,YANG W L,LI D,WANG X Y.Influence of preparation method on the performance of Mn-Ce-O catalysts[J].React Kinet Catal Lett,2009,97(2):263-268.
[19]李树娜,宋佩,张金丽,贺小霞,解一昕,张亚刚,王瑞义,李志凯,朱华青.CeO2-M n Ox催化剂形貌对低浓度甲烷催化燃烧反应性能的影响[J].燃料化学学报,2018,46(5):615-624.(LI Shu-na,SONG Pei,ZHANG Jin-li,HE Xiao-xia,XIE Yi-xin,ZHANG Ya-gang,WANG Rui-yi,LI Zhi-kai,ZHU Hua-qing.morphology effect of CeO2-M n Oxcatalyst on their catalytic performance in lean methane combustion[J].J Fuel Chem Technol,2018,46(5):615-624.)
[20]刘长春,於俊杰,蒋政,陶炎鑫,郝郑平,何绪文.Ce(1-x)M nxO(2-a)复合氧化物催化剂甲烷催化燃烧性能的研究[J].无机化学学报,2007,(2):217-224(LIU Chang-chun,YU Jun-jie,JIANG Zheng,TAO Yan-xin,HAO Zheng-ping,HE Xu-wen.Methane catalytic combustion on Ce1-xM nx O2-amixed oxide catalysts[J].Chin J Inorg Chem,2007,(2):217-224.)
[21]ZHANG P,LU H,ZHOU Y,ZHANG L,WU Z,YANG S,SHI H,ZHU Q,CHEN Y,DAI S.Mesoporous Mn CeOxsolid solutions for low temperature and selective oxidation of hydrocarbons[J].Nat Commun,2015,6:8446.
[22]WU Y,LU Y,SONG C,MA Z,XING S,GAO Y.A novel redox-precipitation method for the preparation ofα-MnO2w ith a high surface M n4+concentration and its activity tow ard complete catalytic oxidation of o-xylene[J].Catal Today,2013,201:32-39.
[23]WANG X,LIU Y,ZHANG Y,ZHANG T,CHANG H,ZHANG Y,JIANG L.Structural requirements of manganese oxides for methane oxidation:XAS spectroscopy and transition-state studies[J].Appl Catal B:Environ,2018,229:52-62.
[24]ARENA F,GUMINA B,LOMBARDO AF,ESPRO C,PATTI A,SPADARO L,SPICCIA L.Nanostructured Mn Oxcatalysts in the liquid phase selective oxidation of benzyl alcohol w ith oxygen:Part I.Effects of Ce and Fe addition on structure and reactivity[J].Appl Catal B:Environ,2015,162:260-267.
[25]ARENA F,TRUNFIO G,NEGRO J,FAZIO B,SPADARO L.Basic evidence of the molecular dispersion of Mn CeOxcatalysts synthesized via a novel“redox-precipitation”route[J].Chem M ater,2007,19(9):2269-2276.
[26]XU J,LI P,SONG X F,HE C H,YU J G,HAN Y F.Operando raman spectroscopy for determining the active phase in one-dimensional M n1-xCexO2±y nanorod catalysts during methane combustion[J].J Phys Chem Lett,2015,1(10):1648-1654.
[27]PAPAVASILIOU J,AVGOUROPOULOS G,IOANNIDES T.In situ combustion synthesis of structured Cu-Ce-O and Cu-Mn-O catalysts for the production and purification of hydrogen[J].Appl Catal B:Environ,2006,66(3):168-174.
[28]李云霞.低温等离子体-锰氧化物联合处理气体中二硫化碳和甲苯[D].合肥:合肥工业大学,2016.(LI Yun-xia.Reasearch on treatment of caron disulfide and toluene gas by low temperature plasma-manganese oxide[D].Heifei:Heifei University of Technology,2016.)
[29]JIRTOVK,MIKULOVJ,KLEMPA J,GRYGAR T,BASTL Z,KOVANDA F.Modification of Co-Mn-Al mixed oxide with potassium and its effect on deep oxidation of VOC[J].Appl Catal A:Gen,2009,361(1):106-116.
[30]KUMAR M,YUN J H,BHATT V,SINGH B,KIM J,KIM J S,KIM B S,LEE CY.Role of Ce3+valence state and surface oxygen vacancies on enhanced electrochemical performance of single step solvothermally synthesized CeO2nanoparticles[J].Electrochim Acta,2018,284:709-720.
[31]CHEN X,SHEN Y F,SUIB S L,O'Young C L.Characterization of manganese oxide octahedral molecular sieve(M-OMS-2)materials with different metal cation dopants[J].Chem M ater,2002,14(2):940-948.
[32]HAN Y F,CHEN L,RAMESH K,WIDJAJA E,CHILUKOTI S,KESUMAWINATA SURJAMI I,CHEN J.Kinetic and spectroscopic study of methane combustion overα-M n2O3nanocrystal catalysts[J].J Catal,2008,253(2):261-268.