微波离子交换法制备Cu-ZSM-11及微波辐照MeO_x/Cu-ZSM-11催化分解NO
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摘要
用微波辐照离子交换法制备了Cu-ZSM-11,制备的Cu-ZSM-11和金属氧化物(Me Ox)机械混合制备了微波催化剂Me Ox/Cu-ZSM-11。考察了Me Ox在微波辐照下的升温行为,筛选出吸波性能好的Me Ox(Mn O2>CuO>Ni_2O_3)为吸波组分。分别考察了微波辐照下金属氧化物、Cu-ZSM-11和Me Ox/Cu-ZSM-11直接分解NO性能,并与常规加热条件下比较。结果表明:微波辐照显著提高了NO的转化率,微波催化剂Ni_2O_3/Cu-ZSM-11在350℃时,NO转化率达到99.27%,N2选择性达到99.9%;相同条件下,微波辐照Me Ox/Cu-ZSM-11直接分解NO转化率高于对应金属氧化物或Cu-ZSM-11分解NO的转化率,表明微波具有催化作用。微波辐照下氧气浓度对Ni_2O_3/Cu-ZSM-11直接分解NO性能几乎无影响,微波辐照消除了氧气阻抑作用,表现出微波选择效应。水汽存在对转化率有较小影响。反应进口气体不需要预热,进出口气体温度基本不变。
Cu-ZSM-11 molecular sieve was prepared by the microwave ion-exchange method. The heating behavior of several kinds of metal oxides under microwave irradiation was investigated. Some metal oxide(Mn_O2>Cu O>Ni_2O_3)which is of good absorption property for microwave was selected to be used for mixing with Cu-ZSM-11 catalyst to prepare the microwave catalysts. Direct decomposition of NO over the microwave catalyst Me Ox/Cu-ZSM-11 was conducted with microwave irradiation, and their performance was investigated under microwave irradiation and traditional heating modes respectively. The results show that the conversion rate of decomposing NO is significantly higher under microwave irradiation than under traditional heating; and at catalyst bed temperature 350℃, the NO conversion is achieved up to 99.30% and N2 selectivity 99.9%. Furthermore, under microwave irradiation, the conversion of decomposing NO is higher for the mixture catalyst Me Ox/Cu-ZSM-11 than for alone metal oxides and alone Cu-ZSM-11, indicating that microwave irradiation plays important role in catalytic decomposition of nitrogen oxide. The results indicate also that over Me Ox/Cu-ZSM-11 with microwave irradiation, oxygen concentration in steam has almost no influences on its catalytic activity for NO decomposition, i.e. microwave irradiation can remove oxygen inhibition in decomposition reaction and keep unique selective effect. Similarly, the influence of water vapor in stream is also much less under microwave irradiation. The exit gas temperature is almost not change for Microwave–assisted reaction, and is the same as the reaction temperature 500—600℃ for conventional heating mode reaction.
Cu-ZSM-11 molecular sieve was prepared by the microwave ion-exchange method. The heating behavior of several kinds of metal oxides under microwave irradiation was investigated. Some metal oxide(Mn_O2>Cu O>Ni_2O_3)which is of good absorption property for microwave was selected to be used for mixing with Cu-ZSM-11 catalyst to prepare the microwave catalysts. Direct decomposition of NO over the microwave catalyst Me Ox/Cu-ZSM-11 was conducted with microwave irradiation, and their performance was investigated under microwave irradiation and traditional heating modes respectively. The results show that the conversion rate of decomposing NO is significantly higher under microwave irradiation than under traditional heating; and at catalyst bed temperature 350℃, the NO conversion is achieved up to 99.30% and N2 selectivity 99.9%. Furthermore, under microwave irradiation, the conversion of decomposing NO is higher for the mixture catalyst Me Ox/Cu-ZSM-11 than for alone metal oxides and alone Cu-ZSM-11, indicating that microwave irradiation plays important role in catalytic decomposition of nitrogen oxide. The results indicate also that over Me Ox/Cu-ZSM-11 with microwave irradiation, oxygen concentration in steam has almost no influences on its catalytic activity for NO decomposition, i.e. microwave irradiation can remove oxygen inhibition in decomposition reaction and keep unique selective effect. Similarly, the influence of water vapor in stream is also much less under microwave irradiation. The exit gas temperature is almost not change for Microwave–assisted reaction, and is the same as the reaction temperature 500—600℃ for conventional heating mode reaction.
引文
[1]GALLOWAY J N,TOWNSEND A R,ERISMAN J W,et al.Transformation of the nitrogen cycle:recent trends,questions and potential solutions[J].Science,2008,320(5878):889-892
[2]SOUSA J P S,PEREIRA M F R,FIGUEIREDO J L.Modified activated carbon as catalyst for NO oxidation[J].Fuel Processing Technology,2013,106:727-733.
[3]MARBAN G,ANTUNA R,FUERTES A B.Low-temperature SCR of NOx with NH3 over activated carbon fiber composite-supported metal oxides[J].Applied Catalysis B:Environmental,2003,41(3):323-338.
[4]SHIRAHAMA N,MOCHIDA I,KORAI Y,et al.Reaction of NO2 in air at room temperature with urea supported on pitch based activated carbon fiber[J].Applied Catalysis B:Environmental,2004,52(3):173-179.
[5]ZHU J J,WEI Y C,CHEN W K,et al.Graphitic carbon nitride as a metal-free catalyst for NO decomposition[J].Chemical Communications,2010,46(37):6965-6967.
[6]PARVULESCU V I,GRANGE P,DELMON B.NO decomposition over physical mixtures of Cu-ZSM-5 with zeolites or oxides[J].Applied Catalysis B:Environmental,2001,33(3):223-237.
[7]TANG J,ZHANG T,LIANG D,et al.Direct decomposition of NO by microwave heating over Fe/Na ZSM-5[J].Applied Catalysis B:Environmental,2002,36(1):1-7.
[8]PARVULESCU V I,GRANGE P,DELMON B.Catalytic removal of NO[J].Catalysis Today,1998,46(4):233-316.
[9]KAPPE C O,PIEBER B,DALLINGER D.Microwave effects in organic synthesis:myth or reality?[J].Angewandte Chemie International Edition,2013,52(4):1088-1094.
[10]罗羽裳,周继承,游志敏,等.微波作用于化学反应的研究进展[J].化学工程与技术,2014,4(4):45-62.LUO Y S,ZHOU J C,YOU Z M,et al.Advances in microwave on chemical reactions[J].Chemical Engineering and Technology,2014,4(4):45-62.
[11]田一光,李广钧,孙剑飞,等.La3+,Co2+,Cu2+,Zn2+与X沸石的微波加热离子交换[J].化学研究与应用,1997,9(4):360-365.TIAN Y G,LI G J,SUN J F,et al.Cation-exchange of La3+,Co2+,Cu2+,Zn2+ions into zeolite X using microwave radiation[J].Chemical Research and Application,1997,9(4):360-365.
[12]石照信,谷亨达,仇兴华,等.微波辐射下Zn-X、Zn-Y和Zn-丝光沸石催化剂的制备[J].沈阳化工学院学报,2007,21(2):84-87.SHI Z X,GU H D,QIU X H,et al.Preparation of Zn2+-zeolites using microwave irradiation[J].Journal of Shenyang Institute of Chemical Technology,2007,21(2):84-87.
[13]IWAMOTO M,FURUKAWA H,MINE Y,et al.Copper(Ⅱ)ion-exchanged ZSM-5 zeolites as highly active catalysts for direct and continuous decomposition of nitrogen monoxide[J].Journal of the Chemical Society,Chemical Communications,1986,16:1272-1273.
[14]KUSTOVA M Y,KUSTOV A,CHRISTIANSEN S E,et al.Cu–ZSM-5,Cu–ZSM-11,and Cu–ZSM-12 catalysts for direct NO decomposition[J].Catalysis Communications,2006,7(9):705-708.
[15]韩一帆,汪仁.NO在铜离子交换型沸石上的催化分解[J].催化学报,1996,17(4):336-339.HAN Y F,WANG R.Catalytic decomposition of nitric oxide over Cu2+-exchange zeolites[J].Chinese Journal of catalysis,1996,17(4):336-339.
[16]YANG P F,ZHOU J C,WANG Z.Direct decomposition of NO into N2 and O2 over Cu/ZSM-5 containing Ce and Zr as promoter[J].Advanced Materials Reaearch,2010,113(2):1735-1739.
[17]中国科学院大连化学物理研究所分子筛组.沸石分子筛[M].北京:科学出版社,1978:49.MOLECULAR SIEVE GROUP,DALIAN INSTITUTE OF CHEMICAL PHYSICS,CHINESE ACADEMY OF SCIENCE.Zeolite Molecular Sieve[M].Beijing:Science Press,1978:49.
[18]MINGOS D M P,BAGHURST D R.Applications of microwave dielectric heating effects to synthetic problems in chemistry[J].Chem.Soc.Rev.,1991,20(1):1-47.
[19]谢有畅,朱月香.De NOx催化剂研究进展[J].化学通报,1996,(2):6-10.XIE Y C,ZHU Y X.Research progress of De NOx catalysts[J].Chemistry Bulletin,1996,(2):6-10.
[20]IMANAKA N,MASUI T.Advances in direct NOx decomposition catalysts[J].Applied Catalysis A:General,2012,431/432(26):1-8.
[21]ZHANG Y,FLYTZANI-STEPHANOPOULOS M.Hydrothermal stability of cerium modified Cu ZSM-5 catalyst for nitric oxide decomposition[J].Journal of Catalysis,1996,164(1):131-145.
[22]IWAMOTO M,YAHIRO H,MIZUNO N,et al.Removal of nitrogen monoxide through a novel catalytic process(Ⅱ):Infrared study on surface reaction of nitrogen monoxide adsorbed on copper ion-exchanged ZSM-5 zeolites[J].Journal of Physical Chemistry,1992,96(23):9360-9366.
[23]TAO M,RUI W.Catalytic decomposition of NOx[J].Progress in Chemistry,2008,20(6):798-810.
[24]XU W T,ZHOU J C,OU Y P,et al.Microwave selective effect:a new approach towards oxygen inhibition removal for highly-effective NO decomposition by microwave catalysis over Ba MnxMg1-xO3mixed oxides at low temperature under excess oxygen[J].Chemical Communications,2015,51(19):4073-4076.
[2]SOUSA J P S,PEREIRA M F R,FIGUEIREDO J L.Modified activated carbon as catalyst for NO oxidation[J].Fuel Processing Technology,2013,106:727-733.
[3]MARBAN G,ANTUNA R,FUERTES A B.Low-temperature SCR of NOx with NH3 over activated carbon fiber composite-supported metal oxides[J].Applied Catalysis B:Environmental,2003,41(3):323-338.
[4]SHIRAHAMA N,MOCHIDA I,KORAI Y,et al.Reaction of NO2 in air at room temperature with urea supported on pitch based activated carbon fiber[J].Applied Catalysis B:Environmental,2004,52(3):173-179.
[5]ZHU J J,WEI Y C,CHEN W K,et al.Graphitic carbon nitride as a metal-free catalyst for NO decomposition[J].Chemical Communications,2010,46(37):6965-6967.
[6]PARVULESCU V I,GRANGE P,DELMON B.NO decomposition over physical mixtures of Cu-ZSM-5 with zeolites or oxides[J].Applied Catalysis B:Environmental,2001,33(3):223-237.
[7]TANG J,ZHANG T,LIANG D,et al.Direct decomposition of NO by microwave heating over Fe/Na ZSM-5[J].Applied Catalysis B:Environmental,2002,36(1):1-7.
[8]PARVULESCU V I,GRANGE P,DELMON B.Catalytic removal of NO[J].Catalysis Today,1998,46(4):233-316.
[9]KAPPE C O,PIEBER B,DALLINGER D.Microwave effects in organic synthesis:myth or reality?[J].Angewandte Chemie International Edition,2013,52(4):1088-1094.
[10]罗羽裳,周继承,游志敏,等.微波作用于化学反应的研究进展[J].化学工程与技术,2014,4(4):45-62.LUO Y S,ZHOU J C,YOU Z M,et al.Advances in microwave on chemical reactions[J].Chemical Engineering and Technology,2014,4(4):45-62.
[11]田一光,李广钧,孙剑飞,等.La3+,Co2+,Cu2+,Zn2+与X沸石的微波加热离子交换[J].化学研究与应用,1997,9(4):360-365.TIAN Y G,LI G J,SUN J F,et al.Cation-exchange of La3+,Co2+,Cu2+,Zn2+ions into zeolite X using microwave radiation[J].Chemical Research and Application,1997,9(4):360-365.
[12]石照信,谷亨达,仇兴华,等.微波辐射下Zn-X、Zn-Y和Zn-丝光沸石催化剂的制备[J].沈阳化工学院学报,2007,21(2):84-87.SHI Z X,GU H D,QIU X H,et al.Preparation of Zn2+-zeolites using microwave irradiation[J].Journal of Shenyang Institute of Chemical Technology,2007,21(2):84-87.
[13]IWAMOTO M,FURUKAWA H,MINE Y,et al.Copper(Ⅱ)ion-exchanged ZSM-5 zeolites as highly active catalysts for direct and continuous decomposition of nitrogen monoxide[J].Journal of the Chemical Society,Chemical Communications,1986,16:1272-1273.
[14]KUSTOVA M Y,KUSTOV A,CHRISTIANSEN S E,et al.Cu–ZSM-5,Cu–ZSM-11,and Cu–ZSM-12 catalysts for direct NO decomposition[J].Catalysis Communications,2006,7(9):705-708.
[15]韩一帆,汪仁.NO在铜离子交换型沸石上的催化分解[J].催化学报,1996,17(4):336-339.HAN Y F,WANG R.Catalytic decomposition of nitric oxide over Cu2+-exchange zeolites[J].Chinese Journal of catalysis,1996,17(4):336-339.
[16]YANG P F,ZHOU J C,WANG Z.Direct decomposition of NO into N2 and O2 over Cu/ZSM-5 containing Ce and Zr as promoter[J].Advanced Materials Reaearch,2010,113(2):1735-1739.
[17]中国科学院大连化学物理研究所分子筛组.沸石分子筛[M].北京:科学出版社,1978:49.MOLECULAR SIEVE GROUP,DALIAN INSTITUTE OF CHEMICAL PHYSICS,CHINESE ACADEMY OF SCIENCE.Zeolite Molecular Sieve[M].Beijing:Science Press,1978:49.
[18]MINGOS D M P,BAGHURST D R.Applications of microwave dielectric heating effects to synthetic problems in chemistry[J].Chem.Soc.Rev.,1991,20(1):1-47.
[19]谢有畅,朱月香.De NOx催化剂研究进展[J].化学通报,1996,(2):6-10.XIE Y C,ZHU Y X.Research progress of De NOx catalysts[J].Chemistry Bulletin,1996,(2):6-10.
[20]IMANAKA N,MASUI T.Advances in direct NOx decomposition catalysts[J].Applied Catalysis A:General,2012,431/432(26):1-8.
[21]ZHANG Y,FLYTZANI-STEPHANOPOULOS M.Hydrothermal stability of cerium modified Cu ZSM-5 catalyst for nitric oxide decomposition[J].Journal of Catalysis,1996,164(1):131-145.
[22]IWAMOTO M,YAHIRO H,MIZUNO N,et al.Removal of nitrogen monoxide through a novel catalytic process(Ⅱ):Infrared study on surface reaction of nitrogen monoxide adsorbed on copper ion-exchanged ZSM-5 zeolites[J].Journal of Physical Chemistry,1992,96(23):9360-9366.
[23]TAO M,RUI W.Catalytic decomposition of NOx[J].Progress in Chemistry,2008,20(6):798-810.
[24]XU W T,ZHOU J C,OU Y P,et al.Microwave selective effect:a new approach towards oxygen inhibition removal for highly-effective NO decomposition by microwave catalysis over Ba MnxMg1-xO3mixed oxides at low temperature under excess oxygen[J].Chemical Communications,2015,51(19):4073-4076.
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