Al_2O_3-TiO_2复合载体制备及其对催化氧化NO性能研究
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摘要
为研究Al_2O_3-TiO_2复合载体制备条件对其结构及性能的影响,同时也考察由它负载的催化剂氧化NO的活性,实验用溶胶凝胶法制备一系列TiO_2包覆比、pH值、包覆次数的Al_2O_3-TiO_2复合载体,借助XRD、BET、SEM等表征手段对复合载体进行表征,在负载10%的金属Mn后对催化剂进行活性评价.结果表明,包覆比为1/16、pH=3时,NO转化率较高,在300℃时达到63%,此条件下TiO_2包覆在Al2O3表面形成较薄的包覆层,使载体的热稳定性提高,而且较薄包覆层的形成对NO的催化氧化反应有利;包覆次数为2次时,载体的比表面积明显增大,由1次包覆的197.97m2·g-1增加到237.41m2·g-1,可能由于添加了2倍的分散剂PEG,有助于堆积形成新的孔,为金属活性组分提供更多的结合位点,提高使用复合载体催化剂的催化活性.
In order to study the influence of preparation conditions on the structure and performance of Al2O3-Ti O2 catalyst support. The Al2O3-Ti O2 is prepared in different coating ratio,p H value and coated times by the sol-gel method. Then,the loading 10% Mn catalyst is characterized by means of catalytic activity evaluation,XRD,BET. The results indicated that the catalyst had good activity( the rate of NO conversion is 63%) when1 /16 Ti O2 covered and p H = 3. The Ti O2 formed relatively thin layer on the surface of Al2O3 not only improves the thermal stability of the support,but also contributes to the catalytic oxidation of NO. When the cladding is two the surface area of catalyst support increased significantly from 197. 97 m2·g- 1to 237. 41 m2·g- 1. It may be that the addition of double amount of PEG contributes to the accumulation and formation of new holes. More binding sites for the metal active components are formed to enhance the catalytic activity of the catalyst.
In order to study the influence of preparation conditions on the structure and performance of Al2O3-Ti O2 catalyst support. The Al2O3-Ti O2 is prepared in different coating ratio,p H value and coated times by the sol-gel method. Then,the loading 10% Mn catalyst is characterized by means of catalytic activity evaluation,XRD,BET. The results indicated that the catalyst had good activity( the rate of NO conversion is 63%) when1 /16 Ti O2 covered and p H = 3. The Ti O2 formed relatively thin layer on the surface of Al2O3 not only improves the thermal stability of the support,but also contributes to the catalytic oxidation of NO. When the cladding is two the surface area of catalyst support increased significantly from 197. 97 m2·g- 1to 237. 41 m2·g- 1. It may be that the addition of double amount of PEG contributes to the accumulation and formation of new holes. More binding sites for the metal active components are formed to enhance the catalytic activity of the catalyst.
引文
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[2]MANFRED K,GIUSEPPE M,FABOI R,et al.Enhanced re-oxidation of vanadia by NO2in the fast SCR reaction[J].J Catal,2002,209(1):159-165.
[3]ERKFELDT S,JOBSON E,LARSSON M.The effect of carbon monoxide and hydrocarbons on NOxstorage at low temperature[J].Topics Catal,2001,16(1):127-131.
[4]王亚军,曾庆轩,冯长根,等.汽车尾气净化催化剂载体[J].工业催化,1999(6):3-7.WANG Y J,ZENG Q X,FENG C G,et al.Carriers for vehide tail-gas purification catalysts[J].Ind Catal,1999(6):3-7.
[5]杨志广,王筠,姚新建,等.二氧化钛纳米管的制备及其应用进展[J].应用化工,2014,43(11):2094-2096,2100.YANG Z G,WANG Y,YAO X J,et al.Progress on preparation of titania nanotubes[J].Appl Chem Ind,2014,43(11):2094-2096,2100.
[6]WANG Z H,LI X J,SONG W J,et al.Synergetic promotional effects between ceium oxides and manganese oxides for NH3-sclective catalyst reduction over Ce-Mn/Ti O2[J].Mater Expr,2011,1(2):167-175.
[7]吴爽,许振冲,李俊,等.Ti O2对In-Ag-O/γ-Al2O3催化剂上CO选择性还原NO的改性研究[J].环境科学学报,2015,35(9):2745-2751.WU S,XU Z C,LI J,et al.Ti O2doped In-Ag-O/γ-Al2O3for selective catalytic reduction of NO with CO[J].Aata Sci Circum,2015,35(9):2745-2751.
[8]蔡振钱,高基伟,申乾宏,等.酸催化剂对Ti O2溶胶晶粒形貌及光催化性能的影响[J].稀有金属材料与工程,2008,37(S2):62-65.CAI Z Q,GAO J W,SHEN Q H,et al.Influence of acid catalyst on crystalline microstructure and photo catalytic property of Ti O2sol[J].Rare Metal Mater Eng,2008,37(S2):62-65.
[9]王秀军,齐秋红,陈丽.Ti O2负载单金属镍(铂)催化剂在甲烷解离反应中抗积碳能力的理论研究[J].高等化学学报,2014,35(10):2138-2145.WANG X J,QI Q H,CHEN L.Theoretical studies on suppression of carbon deposition over Titania supported monometallic Nickel(Platinum)catalysts in methane dissociation[J].Chem J Chin Univ,2014,35(10):2138-2145.
[10]吴少涛.Al2O3-Ti O2负载型催化剂催化氧化NO性能研究[D].广州:广州大学,2015.WU S T.Performance of supported Al2O3-Ti O2catalysts for catalytic oxidation of nitric oxide[D].Guangzhou:Guangzhou University,2015.
[11]刘保顺,何鑫,赵修建,等.纳米Ti O2的表面能态及光电子-空穴对复合过程的研究[J].光谱学与光谱分析,2006,26(2):208-212.LIU B S,HE X,ZHAO X J,et al.The surface states and the electron-hole pair recombination of Ti O2nanopowders[J].Spectrosc Spectr Anal,2006,26(2):208-212.
[12]李礼.二氧化钛表面包覆氧化铝的形态和机理分析[J].无机盐工业,2013,45(8):27-29.LI L.Analysis on morphology and mechanism of Ti O2surface coated with Al2O3[J].Inorg Chem Ind,2013,45(8):27-29.
[13]郭宇,金玉家,吴红梅,等.负载型二氧化钛光催化剂材料的制备及其光催化性能研究[J].光谱学与光谱分析,2015,35(6):1677-1681.GUO Y,JIN Y J,WU H M,et al.Preparation and photo catalytic properties of supported Ti O2photo catalytic material[J].Spectrosc Spectr Anal,2015,35(6):1677-1681.
[14]李波,邵玲玲.氧化铝、氢氧化铝的XRD鉴定[J].无机盐工业,2008,40(2):54-57.LI B,SHAO L L.Appraisal of alumina and aluminium hydroxide by XRD[J].Inorg Chem Ind,2008,40(2):54-57.
[15]AHMED M A,ABDEL-MESSIH M F.Structural and nano-composite features of Al2O3-Ti O2powders prepared by Sol-gel method[J].J Alloy Compoun,2011,509(5):2154-2159.
[16]宋立民,李伟,张明慧,等.Ni2P/Si O2-Al2O3催化剂的制备、表征及其对4,6-二甲基二苯并噻吩加氢脱硫反应的催化性能[J].催化学报,2007,28(2):143-147.SONG L M,LI W,ZHANG M H,et al.Preparation and characterization of Ni2P/Si O2-Al2O3and its catalytic performance for Hydrodesulfurization of 4,6-Dimethyldibenzothiophene[J].Chin J Catal,2007,28(2):143-147.
[17]尚鹏博,郑玉婴,翼峰,等.锌离子掺杂的二氧化钛介孔空心微球的制备及光催化性能[J].无机化学学报,2014,30(10):2323-2331.SHANG P B,ZHENG Y Y,JI F,et al.Zinc doped Ti O2mesoporous hollow microspheres:Preparation and photo catalytic activity[J].Chin J Inorg Chem,2014,30(10):2323-2331.
[18]李咏,宋伟明,韩雪佳,等.软模板法制备二氧化钛纳米晶体及表征[J].人工晶体学报,2014,43(4):923-928.LI Y,SONG W M,HAN X J,et al.Preparation and characterization of Ti O2nanocrystal by soft template method[J].J Syn Cryst,2014,43(4):923-928.