Co掺入对CeMoO_x/Al_2O_3协同催化NO、CO和C_3H_8的影响
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摘要
采用挤出成型法将Co掺入CeMo_(0.15)O_x/Al_2O_3制备系列催化剂CeMo_(0.15)Co_(0.15)O_x/Al_2O_3,研究Co掺入对协同催化脱除CO、NO和C_3H_8的影响。采用X线衍射仪(XRD)、N2吸附/脱附法、NH3程序升温脱附法(NH_3-TPD)、NO程序升温脱附法(NO-TPD)、H_2程序升温还原法(H_2-TPR)和X线光电子能谱(XPS)等手段对催化剂进行表征。结果表明:Co掺入有利于CeMo_(0.15)O_x/Al_2O_3氧化CO和C_3H_8,CeMo_(0.15)Co_(0.15)O_x/Al_2O_3在空速7 200 h~(-1)条件下,NO的转化率为98.85%,CO的转化率为79.41%,C_3H_8的转化率为81.33%。催化剂中Co的掺入会提高氧化-还原性能、酸量、NO吸附-脱附能力、Ce~(3+)浓度以及化学吸附氧浓度。这些结果均有利于提高协同催化脱除CO、NO和C_3H_8的活性。
A series CeMo_(0.15)Co_(0.15)O_x/Al_2O_3 catalysts were modified from CeMo_(0.15)O_x/Al_2O_3 with Co using an extrusion method.The catalytic activity of the obtained catalysts in the CO,NO and C_3H_8 elimination was investigated to determine the appropriate dosage.The samples were characterized by X-ray diffractometer(XRD),N_2 adsorption/desorption,NH_3 temperature programmed desorption(NH_3-TPD),NO temperature programmed desorption(NO-TPD),H_2 temperature programmed reduction(H_2-TPR)and X-ray photoelectron spectroscope(XPS),respectively.Results showed that CeMo_(0.15)O_x/Al_2O_3 with doped Co favoured catalytic oxidation of CO and C_3H_8 with 98.85% NO,79.41% CO and 81.33% C_3H_8 conversion rate under gas hourly space velocity(GHSV) of 7 200 h-1.It was found that the redox properties,the number of acid sites,the adsorption ability of NO,the concentration of Ce~(3+),and chemisorbed oxygen could be enhanced by CeMo_(0.15)O_x/Al_2O_3 with the addition of Co.These results were beneficial for the catalytic removal of CO,NO and C_3H_8.
A series CeMo_(0.15)Co_(0.15)O_x/Al_2O_3 catalysts were modified from CeMo_(0.15)O_x/Al_2O_3 with Co using an extrusion method.The catalytic activity of the obtained catalysts in the CO,NO and C_3H_8 elimination was investigated to determine the appropriate dosage.The samples were characterized by X-ray diffractometer(XRD),N_2 adsorption/desorption,NH_3 temperature programmed desorption(NH_3-TPD),NO temperature programmed desorption(NO-TPD),H_2 temperature programmed reduction(H_2-TPR)and X-ray photoelectron spectroscope(XPS),respectively.Results showed that CeMo_(0.15)O_x/Al_2O_3 with doped Co favoured catalytic oxidation of CO and C_3H_8 with 98.85% NO,79.41% CO and 81.33% C_3H_8 conversion rate under gas hourly space velocity(GHSV) of 7 200 h-1.It was found that the redox properties,the number of acid sites,the adsorption ability of NO,the concentration of Ce~(3+),and chemisorbed oxygen could be enhanced by CeMo_(0.15)O_x/Al_2O_3 with the addition of Co.These results were beneficial for the catalytic removal of CO,NO and C_3H_8.
引文
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[2]ARVAHOVA A,KOCI P,SCHMEIβER V,et al.The impact of CO and C3H6pulses on PtOxreduction and NO oxidation in a diesel oxidation catalyst[J].Applied catalysis B:environmental,2016,181:644.
[3]SHEN Y S,ZONG Y H,MA Y F,et al.Synergistic catalytic removals of NO,CO and C3H8 over Ce Sn0.8W0.6Ox/Ti Al0.2Si0.1Ox[J].Fuel,2016,180:727.
[4]杨波,沈岳松,祝社民,等.Mn-La-Ce-Ni-Ox低温脱硝的影响因素[J].南京工业大学学报(自然科学版),2015,37(5):6.
[5]TANG C J,ZHANG H L,DONG L.Ceria-based catalysts for lowtemperature selective catalytic reduction of NO with NH3[J].Catalysis science&technology,2016,6(5):1248.
[6]GE C Y,LIU L C,LIU Z T,et al.Improving the dispersion of CeO2 onγ-Al2O3to enhance the catalytic performances of CuO/CeO2/γ-Al2O3catalysts for NO removal by CO[J].Catalysis communications,2014,51:95.
[7]任国卿,张宏科,陈晓蓉,等.Ru/Al2O3催化对苯二甲酸二甲酯合成1,4-环己烷二甲酸二甲酯[J].南京工业大学学报(自然科学版),2015,37(4):1.
[8]TAO F,YANG S S,YANG P,et al.Effects of support property on the catalytic performance of CeO2-ZrO2-CrOxfor 1,2-dichloroethane oxidation[J].Journal of rare earths,2016,34(4):381.
[9]杜君,吴相英,潘兴朋,等.CeO2/Na Y催化剂的氧合及其催化氧化脱硫性能[J].物理化学学报,2016,32(9):2337.
[10]刘俊,王亮亮,费兆阳,等.非晶态CeO2@TiO2催化剂的结构、性质及其选择催化还原脱硝性能[J].燃料化学学报,2016,44(8):954.
[11]YAN W,SHEN Y S,ZHU S M,et al.Promotional effect of molybdenum additives on catalytic performance of CeO2/Al2O3for selective catalytic reduction of NOx[J].Catalysis letters,2016,146(7):1221.
[12]蔺卓玮,陆强,唐昊,等.平板式V2O5-MoO3/TiO2型SCR催化剂的中低温脱硝和抗中毒性能研究[J].燃料化学学报,2017,45(1):113.
[13]SHANG D H,ZHONG Q,CAI W.Influence of the preparation method on the catalytic activity of Co/Zr1-xCexO2for NO oxidation[J].Journal of molecular catalysis A:chemical,2015,399:18.
[14]LIETTI L,NOVA I,RAMIS G,et al.Characterization and reactivity of V2O5-MoO3/TiO2De-NOxSCR catalysts[J].Journal of catalysis,1999,187(2):419.
[15]YANG L,TAN Y,SHENG Z Y,et al.The poisoning effect of Na doping over Mn-Ce/TiO2catalyst for low-temperature selective catalytic reduction of NO by NH3[J].Journal of nanomaterials,2014,2014:1.
[16]ZHANG S L,ZHONG Q,SHEN Y G,et al.New insight into the promoting role of process on the CeO2-WO3/TiO2catalyst for NO reduction with NH3at low-temperature[J].Journal of colloid and interface science,2015,448:417.
[17]RAMIS G,BUSCA G,LORENZELLI V,et al.Fourier transform infrared study of the adsorption and coadsorption of nitric oxide,nitrogen dioxide and ammonia on TiO2anatase[J].Applied catalysis,1990,64:243.
[18]ZHANG G Z,ZHAO Z,XU J F,et al.Comparative study on the preparation,characterization and catalytic performances of 3DOM Ce-based materials for the combustion of diesel soot[J].Applied catalysis B:environmental,2011,107(3/4):302.
[19]JIN B F,WEI Y C,ZHAO Z,et al.Synthesis of threedimensionally ordered macroporous Al-Ce mixed oxide catalysts with high catalytic activity and stability for diesel soot combustion[J].Catalysis today,2015,258:487.
[20]GAO X,JIANG Y,FU Y C,et al.Preparation and characterization of CeO2/TiO2catalysts for selective catalytic reduction of NO with NH3[J].Catalysis communications,2010,11(5):465.
[21]NDIFOR E N,GARCIA T,SOLSONA B,et al.Influence of preparation conditions of nano-crystalline ceria catalysts on the total oxidation of naphthalene,a model polycyclic aromatic hydrocarbon[J].Applied catalysis B:environmental,2007,76(3/4):248.
[22]LARACHI F A,PIERRE J M,ADNOT A,et al.Ce3d XPS study of composite CexMn1-xO2-ywet oxidation catalysts[J].Applied surface science,2002,195(1/2/3/4):236.
[23]BONINGARI T,PAPPAS D K,ETTIREDDY P R,et al.Influence of SiO2on M/TiO2(M=Cu,Mn,and Ce)formulations for lowtemperature selective catalytic reduction of NOxwith NH3:surface properties and key components in relation to the activity of NOx reduction[J].Industrial&engineering chemistry research,2015,54(8):2261.
[24]KANG M,PARK E D,KIM J M,et al.Manganese oxide catalysts for NOxreduction with NH3at low temperatures[J].Applied catalysis A:general,2007,327(2):261.
[25]WU Z B,JIN R B,LIU Y,et al.Ceria modified MnOx/TiO2as a superior catalyst for NO reduction with NH3at low-temperature[J].Catalysis communications,2008,9(13):2217.