5%Mn/TiO_2联合臭氧催化氧化NO的性能分析
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摘要
针对臭氧催化氧化脱除烟气中NO的方法,采用浸渍法制备了5%Mn/TiO_2催化剂,研究了催化剂联合臭氧对NO催化氧化性能的影响.发现n(O_3)/n(NO)<1时,催化剂的加入显著提升了臭氧氧化NO的效率.150℃时联合催化氧化NO的效率相对于臭氧单独氧化NO的效率提升了约30%.50℃下,n(O_3)/n(NO)=0.5,联合催化氧化的效率相对于不使用臭氧的单独催化氧化NO提升了约40%.对新鲜的5%Mn/TiO_2催化剂进行了XRD、TGA和H_2-TPR等表征测试以及参与氧化反应前后的催化剂进行了SEM和XPS分析.得知MnO_2、Mn_2O_3和Mn_3O_4是主要活性组分,含有大量Mn~(3+).通过XPS结果分析,可以总结出催化剂促进臭氧分解出活性氧,并吸附在活性金属位点上,再与NO反应生成NO_2.
To remove NO from flue gas by ozonation,5%Mn/TiO_2 catalyst was prepared by impregnation to study the effect of catalyst combined with ozone on the catalytic oxidation performance of NO. When the molar ratio of ozone to NO was less than 1(n(O_3)/n(NO)<1),the addition of catalyst significantly increased the efficiency of NO oxidation by ozone. At 150℃ an d n(O_3)/n(NO)<1,the efficiency of the combined catalytic oxidation of NO was about 30% higher than that of using ozone alone. At 50℃ and n(O_3)/n(NO)=0.5,the efficiency of combined catalytic oxidation was about 40% higher than that of NO catalytic oxidation without ozone. XRD,TGA,and H_2-TPR characterization analyses were carried out on the fresh 5%Mn/Ti O_2 catalyst. SEM and XPS were carried out on 5%Mn/TiO_2 before and after the reaction of NO catalytic oxidation. Results indicated that MnO_2,Mn_2 O_3 and Mn_3 O_4 were the main active components,containing a large amount of Mn~(3+). XPS revealed that the catalyst promoted ozone to decompose reactive oxygen species,which was adsorbed on the active metal sites and reacted with NO to form NO_2.
To remove NO from flue gas by ozonation,5%Mn/TiO_2 catalyst was prepared by impregnation to study the effect of catalyst combined with ozone on the catalytic oxidation performance of NO. When the molar ratio of ozone to NO was less than 1(n(O_3)/n(NO)<1),the addition of catalyst significantly increased the efficiency of NO oxidation by ozone. At 150℃ an d n(O_3)/n(NO)<1,the efficiency of the combined catalytic oxidation of NO was about 30% higher than that of using ozone alone. At 50℃ and n(O_3)/n(NO)=0.5,the efficiency of combined catalytic oxidation was about 40% higher than that of NO catalytic oxidation without ozone. XRD,TGA,and H_2-TPR characterization analyses were carried out on the fresh 5%Mn/Ti O_2 catalyst. SEM and XPS were carried out on 5%Mn/TiO_2 before and after the reaction of NO catalytic oxidation. Results indicated that MnO_2,Mn_2 O_3 and Mn_3 O_4 were the main active components,containing a large amount of Mn~(3+). XPS revealed that the catalyst promoted ozone to decompose reactive oxygen species,which was adsorbed on the active metal sites and reacted with NO to form NO_2.
引文
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[2]张健,毕德贵,张忠孝,等.煤粉炉高温还原性氛围下NH3还原NOx[J].燃烧科学与技术,2017,23(5):406-411.Zhang Jian,Bi Degui,Zhang Zhongxiao,et al.NOx reduction with NH3 reagent injected into high temperature and reducing atmosphere in pc-boiler[J].Journal of Combustion Science and Technology,2017,23(5):406-411(in Chinese).
[3]J?gi Indrek,Stamate Eugen,Irimiea Cornelia,et al.Comparison of direct and indirect plasma oxidation of NO combined with oxidation by catalyst[J].Fuel,2015,144:137-144.
[4]Li Kai,Tang Xiaolong,Yi Honghong,et al.Lowtemperature catalytic oxidation of NO over Mn-CoCe-Ox catalyst[J].Chemical Engineering Journal,2012,192:99-104.
[5]Ma Qiang,Wang Zhihua,Lin Fawei,et al.Characteristics of O3 oxidation for simultaneous desulfurization and denitration with limestone-gypsum wet scrubbing:Application in a carbon black drying kiln furnace[J].Energy&Fuels,2016,30(3):2302-2308.
[6]Skalska Kinga,Miller Jacek S,Ledakowicz Stanislaw.Trends in NOx abatement:A review[J].Science of the Total Environment,2010,408(19):3976-3989.
[7]Wu Zhongbiao,Tang Nian,Xiao Ling,et al.Mn Ox/TiO2 composite nanoxides synthesized by deposition-precipitation method as a superior catalyst for NO oxidation[J].Journal of Colloid and Interface Science,2010,352(1):143-148.
[8]Park Eunseuk,Chin Sungmin,Jeong Juyoung,et al.Low-temperature NO oxidation over Mn/TiO2nanocomposite synthesized by chemical vapor condensation:Effects of Mn precursor on the surface Mn species[J].Microporous and Mesoporous Materials,2012,163:96-101.
[9]Sun Chenglang,Zhao Nan,Zhuang Zhukai,et al.Mechanisms and reaction pathways for simultaneous oxidation of NOx and SO2 by ozone determined by in situ IR measurements[J].Journal of Hazardous Materials,2014,274:376-383.
[10]Li Honghu,Wang Shengkai,Wang Xu,et al.Catalytic oxidation of Hg0 in flue gas over Ce modified TiO2supported Co-Mn catalysts:Characterization,the effect of gas composition and co-benefit of NO conversion[J].Fuel,2017,202:470-482.
[11]Qi Gongshin,Li Wei.NO oxidation to NO2 over manganese-cerium mixed oxides[J].Catalysis Today,2015,258:205-213.
[12]Shang Danhong,Zhong Qin,Cai Wei.High performance of NO oxidation over Ce-Co-Ti catalyst:The interaction between Ce and Co[J].Applied Surface Science,2015,325:211-216.
[13]Han Jianyu,Wang Danping,Du Yonghua,et al.Metal-organic framework immobilized cobalt oxide nanoparticles for efficient photocatalytic water oxidation[J].Journal of Materials Chemistry A,2015,3(41):20607-20613.
[14]Zhang Xiao,Shen Boxiong,Shen Feng,et al.The behavior of the manganese-cerium loaded metal-organic framework in elemental mercury and NO removal from flue gas[J].Chemical Engineering Journal,2017,326:551-560.
[15]Fang De,Xie Junlin,Hu Hua,et al.Identification of Mn Ox species and Mn valence states in Mn Ox/TiO2catalysts for low temperature SCR[J].Chemical Engineering Journal,2015,271:23-30.
[16]Pozan Gulin Selda.Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion[J].Journal of Hazardous Materials,2012,221/222:124-130.
[17]Sudarsanam Putla,Hillary Brendan,Amin Mohamad Hassan,et al.Structure-activity relationships of nanoscale MnOx/CeO2 heterostructured catalysts for selective oxidation of amines under eco-friendly conditions[J].Applied Catalysis B:Environmental,2016,185:213-224.
[18]Wang Fang,Dai Hongxing,Deng Jiguang.Manganese oxides with rod-,wire-,tube-,and flower-like morphologies:Highly effective catalysts for the removal of toluene[J].Environmental Science&Technology,1974,33(3):493-496.
[19]Lin Fawei,Wang Zhihua,Ma Qiang,et al.Catalytic deep oxidation of NO by ozone over MnOx loaded spherical alumina catalyst[J].Applied Catalysis B:Environmental,2016,198:100-111.
[20]Venkataswamy Perala,Rao Komateedi N,Jampaiah Deshetti,et al.Nanostructured manganese doped ceria solid solutions for CO oxidation at lower temperatures[J].Applied Catalysis B:Environmental,2015,162:122-132.
[21]Zhang Lei,Shi Liyi,Huang Lei,et al.Rational design of high-performance DeNOx catalysts based on MnxCo3-xO4 nanocages derived from metal-organic frameworks[J].ACS Catalysis,2014,4(6):1753-1763.
[22]Wen Zhengcheng,Du Mengmeng,Li Yuan,et al.Quantum chemistry study on the oxidation of NO catalyzed by ZSM5 supported Mn/Co-Al/Ce[J].Journal of Theoretical&Computational Chemistry,2017,16(5):1750044-01-12.
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