铜锰复合氧化物催化甲苯完全氧化反应研究
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摘要
采用沉积沉淀法制备了γ-Al_2O_3负载的铜锰复合氧化物催化剂,并用于催化甲苯完全氧化反应,考察了Cu/Mn摩尔比、负载量、甲苯浓度、反应空速对铜锰复合氧化物催化降解甲苯的活性的影响,对催化剂进行了XRD、BET和TPR表征分析。通过XRD、BET表征结果得出,CuMn_2O_4尖晶石的形成降低了催化剂的还原温度,有利于提高催化剂的催化活性。当催化剂中Cu/Mn摩尔比为1∶2,负载量25%时,催化活性最佳,仅250℃就可以将甲苯完全氧化分解为二氧化碳和水。
The Cu-Mn composite catalyst was prepared by the deposition-precipitation for the complete oxidation of toluene,and the Cu/Mn molar ratio,the loading,the toluene concentration and the reaction space velocity were investigated.The catalysts were characterized by XRD,BET and TPR.The results showed that the formation of CuMn_2O_4 spinel reduced the reduction temperature of the catalyst and improved the catalytic activity.When the molar ratio of Cu/Mn = 1 ∶ 2 and the loading was 25%,the best catalytic activity could be obtained,and toluene was decomposed into carbon dioxide and water with complete oxidation at only 250 ℃.
The Cu-Mn composite catalyst was prepared by the deposition-precipitation for the complete oxidation of toluene,and the Cu/Mn molar ratio,the loading,the toluene concentration and the reaction space velocity were investigated.The catalysts were characterized by XRD,BET and TPR.The results showed that the formation of CuMn_2O_4 spinel reduced the reduction temperature of the catalyst and improved the catalytic activity.When the molar ratio of Cu/Mn = 1 ∶ 2 and the loading was 25%,the best catalytic activity could be obtained,and toluene was decomposed into carbon dioxide and water with complete oxidation at only 250 ℃.
引文
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[2]Zhao P S,Dong F,Yang Y D,et al.Characteristics of carbonaceous aerosol in the region of Beijing,Tianjin,and Hebei,China[J].Atmos Environ,2013,71(3):389-398.
[3]Parmar G R,Rao N N.Emerging control technologies for volatile organic compounds[J].Crit Rev in Environ Sci Technol,2009,39(1):41-78.
[4]Everaert K,Baeyens J.Catalytic combustion of volatile organic compounds[J].J Hazard Mater,2004,109(1-3):113-139.
[5]Saqer S M,Kondarides D I,Verykios X E.Catalytic activity of supported platinum and metal oxide catalysts for toluene oxidation[J].Top Catal,2009,52(5):517-527.
[6]Okumura K,Kobayashi T,Tanaka H.Toluenecombustion over palladium supported on various metal oxidesupports[J].Appl Catal B-Environ,2003,44(4):325-331.
[7]Deng J G,Zhang L,Dai H X,et al.Ultrasound-assisted nanocasting fabrication of ordered mesoporous Mn O2and Co3O4with high surface areas and polycrystalline walls[J].J Phys Chem C,2010,114(6):2 694-2 700.
[8]Chen T,Dou H Y,Li X L,et al.Tunnel structure effect of manganese oxides in complete oxidation of formaldehyde[J].Micropor Mesopor Mater,2009,112(1-3):270-274
[9]Xia Y S,Dai H X,Jiang H Y,et al.Mesoporous chromia with ordered three-dimensional structures for the complete oxidation of toluene and ethyl acetate[J].Environ Sci Technol,2009,43(21):8 355-8 360.
[10]Wang F,Yang,G Y,Zhang etal.Copper and manganese:two concordant partners in the catalytic oxidation of pcresol to p-hydroxybenzaldehyde[J].Chem Commun,2003,34(10):1 172-1 173.
[11]Zimowska M,Michalik-Zym A,Janik R,et al.Catalytic combustion of toluene over mixed Cu-Mn oxides[J].Catal Today,2007,119(1-4):321-326.
[12]Li W B,Chu W B,Zhang M.Catalytic oxidation of toluene on Mn-containing mixed oxides prepared in reverse microemulsions[J].Catal Today,2004,93(3):205-209.
[13]黄海凤,陈银飞,唐伟.VOCs催化燃烧催化剂Mn/γ-Al2O3和Cu Mn/γ-Al2O3的性能研究[J].高校化学工程学报,2004,18(2):152-155.
[14]黄雪敏,乔南利,曹利,等.CuxCe1-xO2/γ-Al2O3催化剂催化燃烧甲苯性能的研究[J].环境科学学报,2012,32(5):1 177-1 182.
[15]朱红法,刘丽芝.催化剂制备及应用技术[M].北京:中国石化出版社,2011:146-157.
[16]Einaga H,Maeda N,Yamamoto S,et al.Catalytic properties of copper-manganese mixed oxides supported on Si O2for benzene oxidation with ozone[J].Catal Today,2014:245,22-27.
[17]Solsona B,Garcia T,Agouram S.The effect of gold addition on the catalytic performance of copper manganese oxide catalysts for the total oxidation of propane[J].Appl Catal B-Environ,2011,101(3-4):388-396.
[18]Njagi E C,Chen C H,Genuino H.Total oxidation of CO at ambient temperature using copper manganese oxide catalysts prepared by a redox method[J].Appl Catal B-Environ,2010,99(1-2):103-110.
[19]Nagase K,Zheng Y,Kodama Y.Dynamic study of the oxidation state of copper in the course of carbon monoxide oxidation over powdered Cu O and Cu2O[J].J Catal,1999,187(1):123-130.
[20]Saqer S M,Kondarides D I,Verykios X E,et al.Catalytic oxidation of toluene over binary mixtures of copper,manganese and cerium oxides supported onγ-Al2O3[J].Appl Catal B-Environ,2011,103(3-4):275-286.
[21]王幸宜,卢冠忠,汪仁,等.铜锰氧化物表面过剩氧及其甲苯催化燃烧活性[J].催化学报,1994,15(2),103-108.
[22]Jones C,Taylor S H,Burrows A,et al.Cobalt promoted copper manganese oxide catalysts for ambient temperature carbon monoxide oxidation[J].Chem Commun.2008,14(14):1 707-1 709.
[23]Cherian M,Rao M S,Yang W T,et al.Oxidation dehydrogenation of propane over Cr2O3/Al2O3and Cr2O3catalysts:effects of loading precursor and surface area[J].Appl Catal A General,2002,233(1-2):21-33.