SCR脱硝催化反应及催化剂活性的研究
|
摘要
选择性催化还原(SCR)是主要的商业化烟气脱硝技术,SCR脱硝反应机理很复杂。本论文采用数值模拟技术研究V205-W03／Ti02和V205／C催化剂的脱硝催化反应,通过改变操作条件(反应温度、NH3／NOx摩尔比、烟气在催化剂层的停留时间)分析各自对催化反应的影响并计算出脱硝效率,从而得出最优的操作条件,为电厂SCR装置优化运行提供参考。
在小型实验台上,通过模拟电厂烟气,测试了某电厂SCR脱硝催化剂在运行19870小时后的活性并在试验过程中测试了S02／S03转化率。参考设计标准,可对催化剂的使用寿命做出一个合理的预测,能够更好地及时计划对催化剂的更换或再生工作,对SCR系统安全、经济运行具有指导作用。
Selective Catalytic Reduction (SCR) is a major commercial technology for NOx removal in power plants. The reaction mechanism of SCR is rather complex. In this paper, catalytic reactions were simulated for V2O5-WO3/TiO2 and V2O5/C catalysts, then NO removal efficiencies were calculated. The impact of operating conditions such as reaction temperature, ammonia-nitrogen molar ratio and resident time in the catalyst bed layer on catalytic reactions were studied. As a result, optimal operating conditions were known and we can provide a reference for SCR optimal running in power plants.
Flue gases from power plant were simulated and the activity of SCR catalysts was tested after running for 19870 hours. In addition, the conversion rate for SO2 to SO3 was tested. Referring to the designing standards, we can make a reasonable forecast to the service life of the catalysts, and it was able to plan a timely replacement or regeneration for SCR catalysts, which provided a guide for SCR safe and economic operation.
在小型实验台上,通过模拟电厂烟气,测试了某电厂SCR脱硝催化剂在运行19870小时后的活性并在试验过程中测试了S02／S03转化率。参考设计标准,可对催化剂的使用寿命做出一个合理的预测,能够更好地及时计划对催化剂的更换或再生工作,对SCR系统安全、经济运行具有指导作用。
Selective Catalytic Reduction (SCR) is a major commercial technology for NOx removal in power plants. The reaction mechanism of SCR is rather complex. In this paper, catalytic reactions were simulated for V2O5-WO3/TiO2 and V2O5/C catalysts, then NO removal efficiencies were calculated. The impact of operating conditions such as reaction temperature, ammonia-nitrogen molar ratio and resident time in the catalyst bed layer on catalytic reactions were studied. As a result, optimal operating conditions were known and we can provide a reference for SCR optimal running in power plants.
Flue gases from power plant were simulated and the activity of SCR catalysts was tested after running for 19870 hours. In addition, the conversion rate for SO2 to SO3 was tested. Referring to the designing standards, we can make a reasonable forecast to the service life of the catalysts, and it was able to plan a timely replacement or regeneration for SCR catalysts, which provided a guide for SCR safe and economic operation.
引文
[1]赵桂锋,杨文波.SCR脱硝技术概述.锅炉制造,2007,2：41～42
[2]郝吉明,马广大.大气污染控制工程.北京：高等教育出版社,2002
[3]李恒远.中国能源环保与政策法规.环境与科学,2001,10：24-25
[4]刘贵云.新建火电项目氮氧化物控制要求.中国环境在线,2005. http://www.chinaeol.net
[5]熊振湖,费学宁,池勇志.大气污染防治技术及工程运用.北京：机械工业出版社,2003
[6]吴忠标.大气污染控制工程.北京：科学出版社,2003
[7]Denise L, Babar S, Namsoug K, et al. NOx emissions from large point sources: variability in ozone production, resulting health damages and economic costs. Atmospheric Environment,2005,39:2851～2866
[8]Rabl A, Eyre N. An estimate of regional and global O3 damage from precursor NOx and VOC emissions. Environment international,1998,24(8):835 ～ 850
[9]Muzio L J, Quartucy G C. Implementing NOx control:research to application. Energy Combust,1997,23 (3):233～266
[10]岑可法,姚强,骆仲泱,等.燃烧理论与污染控制.北京：机械工业出版社,2004
[11]国家环境保护总局,国家质量监督检验检疫总局.火电厂大气污染排放标准GB13223-2003
[12]高凤,杨嘉谟.燃煤烟气脱硝技术的应用与进展.环境保护科学,2007,33(3)：11-13
[13]祝社民,李伟峰,陈英文,等.烟气脱硝技术研究新进展.环境污染与防治,2005,27(9)：699-703
[14]钟秦.燃煤烟气脱硫脱硝技术及工程实例.北京：化学工业出版社,2002
[15]Isabella Nova, Luca Lietti, Enrico Tronconi, Pio Forzatti. Transient response method applied to the kinetic analysis of the DeNOx-SCR reaction. Chemical Engineering Science,2001,56:1229～1237
[16]R.Willi, B.Roduit, R.A.Koeppel, et al. Selective reduction of NO by NH3 over vanadia-based commercial catalyst:parametric sensitivity and kinetic modeling. Chemical Engineering Science,1996,51 (11):2897～2902
[17]S.R. Dhanushkodi, N. Mahinpey, M.Wilson. Kinetic and 2D reactor modeling for simulation of the catalytic reduction of NOx in the monolith honeycomb reactor.
Process Safety and Environment Protection,2008,86:303～309
[18]Ho Jeong Chae, Soo Tae Choo, Hoon Choi, et al. Direct use of kinetic parameters for modeling and simulation of a selective catalytic reduction process. Ind.Eng.Chem.Res,2000,39 (5):1159～ 1170
[19]王建华,高翔,阎志勇,等.以多孔陶瓷为载体的V205—WO3—SiO2／TiO2催化剂上NH3选择性催化还原NO的实验研究.能源工程,2005,1：11-15
[20]钟秦,曲红霞.NH3选择性催化还原NOx的实验研究.南京理工大学学报,2002,26(1)：68～71
[21]钟秦,曲红霞.V205／Ti02催化剂选择性催化还原脱除NOx的研究.安全与环境学报,2004,4(2)：16-18
[22]闫志勇,高翔,岑可法,等.NH3选择性催化还原烟气中NO的反应动力学.动力工程,2007,27(4)：601-606
[23]刘涛.SCR多元催化剂脱硝性能试验研究及数值模拟：[硕士学位论文].南京：东南大学动力工程系,2006
[24]Ramis Gianguido, Larrubia M.Angeles, Busca Guido. An FT-IR study of the absorption of urea and ammonia over V2O5-MoO3-TiO2 SCR catalysts. Applied Catalysis B:environmental,2000,27(3):145～151
[25]Richard G.Herman, John W.Sale, Harvey G.Stenger. Monitoring aging and deactivation of emission abatement catalysis. Topics in Catalysis,2002,18 (3): 251 ～ 257
[26]V.I.Pavulescu, P.Grange, B.Delmon. Catalytic removal of NO. Catalysis Today, 1998,46:233～316
[27]Pio Forzatti, Isabella Nova, Alessandra Beretta. Catalytic properties in DeNOx and SO2-SO3 reaction. Catalysis Today,2000,56:431 ～ 441
[28]G. Ramis, Li Yi, G. Busca. Ammonia activation over catalysts for the selective catalytic reduction of NOx and the selective catalytic oxidation of NH3:an FT-IR study. Catalysis Today,1996,28:373～380
[29]G.Ramis, GBusca, C.Cristiani, et al. Characterization of tungsta-titania catalysts. Langmuir,1992,8 (7):1744～1749
[30]刘志明,郝吉明,朱天乐,傅立新.富氧条件下NOx催化净化的研究进展.环境污染治理技术与设备,2002,3(8)：41-47
[31]张润泽,郑钟植.制备蜂窝状筛网进行NH3选择性催化还原NO的反应.催化学报,2002,23(1)：46-50
[32]张润泽,郑钟植.蜂窝状筛网催化剂上NH3选择性催化还原NO的动力学.大连理工大学学报,2002,42(2)：158-162
[33]Johc Marangozis. Comparison and Analysis of Intrinsic Kinetics and Effectiveness Factors for the Catalytic Reduction of NO with Ammonia in the Presence of Oxygen. Ind.Eng.Chem.Res,1992,31:987～994
[34]George L, Bauerle,S.C. Wu, Ken Nobe. Parametric and Durability Studies of NOx Reduction with NH3 on V2O5 Catalysts. Ind.Eng.Chem.Res.Dev,1978,17(2):117～ 122
[35]张强.燃煤电站SCR烟气脱硝技术及工程应用.北京：化学工业出版社,2007
[36]Miroslav Radojevic. Reduction of Nitrogen Oxides in Flue Gas. Environmental Pollution,1998,102:685～689
[37]Carlo Orsenigo, Alessandra Beretta, Pio Forzatti, Jiri Svachula. Theoretical and Experimental study of the interaction between NOx Reduction and SO2 Oxidation over DeNOx-SCR Catalysts. Catalysis Today,1996,27:15～21
[38]Ozkan U S, Cai Y P, Kumthekar M W. Investigation of the mechanism of ammonia oxidation and oxygen exchange over vanadia catalysts using N-15 and 0-18 tracer studies. Journal of Catalysis,1994,149(2):375～389
[39]Ozkan U S, Cai Y P, Kumthekar M W. Investigation of the reaction pathways in selective catalytic reduction of NO with NH3 over V2O5 catalysts. Journal of Catalysis,1994,149(2):390～403
[40]Matyshak V A, Krylov O V. In situ IR spectroscopy of intermediates in heterogeneous oxidative catalysis. Catalysis Today,1995,25:1 ～ 88
[41]Schneider H, Tschudin S, Schneider M, et al. In situ diffuse reflectance FTIR study of the selective catalytic reduction of NO by NH3 over vanadia-titania aerogels. Journal of Catalysis,1994,147 (1):5～14
[42]Busca G, Lorenzelli V, Ramis G. Chemistry of olefins at metal oxide surfaces:a tool for surface science investigation of oxide catalysts. Materials Chemistry and Physics,1991,29 (4):175-189
[43]Ramis G, Busca G, Bregani F, et al. Fourier transform infrared study of the adsorption and co-adsorption of nitric oxide, nitrogen dioxide and ammonia on TiO2 anatase. Applied Catalysis,1990,64:243～257
[44]Topsoe N Y, Anstrom M, Dumesic J A. FT-IR and theoretical evidence for dynamic structural rearrangements of Vanadia/Titania DeNOx catalysts. Catalysis Letters, 2001,76 (2):11～12
[45]孙克勤,钟秦.火电厂烟气脱硝技术及工程应用.北京：化学工业出版社,2007
[46]陈甘棠.化学反应工程.北京：化学工业出版社,2002
[47]Rajadhyaksha, Rajeev A, Helmut Knozinger. Ammonia adsorption on Vanadia supported on Titania-silica Catalyst-An Infrared spectroscopic investigation. Applied Catalysis,1989,51:81～92
[48]Isabella Nova, Luca Lietti, Enrico Tronconi, Pio Forzatti. Transient response method applied to the kinetic analysis of the DeNOx-SCR reaction. Chemical Engineering Science,2001,56:1229～1237
[49]Luca Lietti, Isabella Nova, Enrico Tronconi, Pio Forzatti. Transient kinetic study of the SCR-DeNOx reaction. Catalysis Today,1998,45:85～92
[50]Isabella Nova, Luca Lietti, Enrico Tronconi, Pio Forzatti. Dynamics of SCR reaction over a TiO2-supported vanadia-tungsta commercial catalyst. Catalysis Today,2000, 60:73～82
[51]Enrico Tronconi, Luca Lietti. Experimental and theoretical investigation of the dynamics of the SCR-DeNOx reaction. Chemical Engineering Science,1996,51 (11):2965～2970
[52]Dumestic J A, Topsoe N Y. Kinetics of the selective reduction of nitric oxide by ammonia over vanadia/titania. Journal of Catalysis,1996,163:409～417
[53]Enrico Tronconi. Interaction between chemical kinetics and transport phenomena in monolithic catalysts. Catalysis today,1997,34:421 ～ 427
[54]Enrico Tronconi. The role of inter-and intra-phase mass transfer in the SCR-DeNOx reaction over catalysts of different shapes. Catalysis today,1999,52:249～258
[55]Guido Busca, Luca Lietti, Gianguido Ramis, Francesco Berti. Chemical and Mechanistic aspects of the selective catalytic reduction of NOx by ammonia over oxide catalysts:A review. Applied Catalysis B:Environmental,1998,18:1～36
[56]A.Boyano, N.Lombardo, M.E.Galvez, M.J.Lazaro, R.Moliner. Vanadium-loaded carbon-based monoliths for the on-board NO reduction:Experimental study of operating conditions. Chemical Engineering Journal,2008,144:343～351
[57]王琦,王树荣,岑可法,等.燃煤电厂SCR脱硝技术催化剂的特性及进展.电站系统工程,2005,21(3)：4-6
[2]郝吉明,马广大.大气污染控制工程.北京：高等教育出版社,2002
[3]李恒远.中国能源环保与政策法规.环境与科学,2001,10：24-25
[4]刘贵云.新建火电项目氮氧化物控制要求.中国环境在线,2005. http://www.chinaeol.net
[5]熊振湖,费学宁,池勇志.大气污染防治技术及工程运用.北京：机械工业出版社,2003
[6]吴忠标.大气污染控制工程.北京：科学出版社,2003
[7]Denise L, Babar S, Namsoug K, et al. NOx emissions from large point sources: variability in ozone production, resulting health damages and economic costs. Atmospheric Environment,2005,39:2851～2866
[8]Rabl A, Eyre N. An estimate of regional and global O3 damage from precursor NOx and VOC emissions. Environment international,1998,24(8):835 ～ 850
[9]Muzio L J, Quartucy G C. Implementing NOx control:research to application. Energy Combust,1997,23 (3):233～266
[10]岑可法,姚强,骆仲泱,等.燃烧理论与污染控制.北京：机械工业出版社,2004
[11]国家环境保护总局,国家质量监督检验检疫总局.火电厂大气污染排放标准GB13223-2003
[12]高凤,杨嘉谟.燃煤烟气脱硝技术的应用与进展.环境保护科学,2007,33(3)：11-13
[13]祝社民,李伟峰,陈英文,等.烟气脱硝技术研究新进展.环境污染与防治,2005,27(9)：699-703
[14]钟秦.燃煤烟气脱硫脱硝技术及工程实例.北京：化学工业出版社,2002
[15]Isabella Nova, Luca Lietti, Enrico Tronconi, Pio Forzatti. Transient response method applied to the kinetic analysis of the DeNOx-SCR reaction. Chemical Engineering Science,2001,56:1229～1237
[16]R.Willi, B.Roduit, R.A.Koeppel, et al. Selective reduction of NO by NH3 over vanadia-based commercial catalyst:parametric sensitivity and kinetic modeling. Chemical Engineering Science,1996,51 (11):2897～2902
[17]S.R. Dhanushkodi, N. Mahinpey, M.Wilson. Kinetic and 2D reactor modeling for simulation of the catalytic reduction of NOx in the monolith honeycomb reactor.
Process Safety and Environment Protection,2008,86:303～309
[18]Ho Jeong Chae, Soo Tae Choo, Hoon Choi, et al. Direct use of kinetic parameters for modeling and simulation of a selective catalytic reduction process. Ind.Eng.Chem.Res,2000,39 (5):1159～ 1170
[19]王建华,高翔,阎志勇,等.以多孔陶瓷为载体的V205—WO3—SiO2／TiO2催化剂上NH3选择性催化还原NO的实验研究.能源工程,2005,1：11-15
[20]钟秦,曲红霞.NH3选择性催化还原NOx的实验研究.南京理工大学学报,2002,26(1)：68～71
[21]钟秦,曲红霞.V205／Ti02催化剂选择性催化还原脱除NOx的研究.安全与环境学报,2004,4(2)：16-18
[22]闫志勇,高翔,岑可法,等.NH3选择性催化还原烟气中NO的反应动力学.动力工程,2007,27(4)：601-606
[23]刘涛.SCR多元催化剂脱硝性能试验研究及数值模拟：[硕士学位论文].南京：东南大学动力工程系,2006
[24]Ramis Gianguido, Larrubia M.Angeles, Busca Guido. An FT-IR study of the absorption of urea and ammonia over V2O5-MoO3-TiO2 SCR catalysts. Applied Catalysis B:environmental,2000,27(3):145～151
[25]Richard G.Herman, John W.Sale, Harvey G.Stenger. Monitoring aging and deactivation of emission abatement catalysis. Topics in Catalysis,2002,18 (3): 251 ～ 257
[26]V.I.Pavulescu, P.Grange, B.Delmon. Catalytic removal of NO. Catalysis Today, 1998,46:233～316
[27]Pio Forzatti, Isabella Nova, Alessandra Beretta. Catalytic properties in DeNOx and SO2-SO3 reaction. Catalysis Today,2000,56:431 ～ 441
[28]G. Ramis, Li Yi, G. Busca. Ammonia activation over catalysts for the selective catalytic reduction of NOx and the selective catalytic oxidation of NH3:an FT-IR study. Catalysis Today,1996,28:373～380
[29]G.Ramis, GBusca, C.Cristiani, et al. Characterization of tungsta-titania catalysts. Langmuir,1992,8 (7):1744～1749
[30]刘志明,郝吉明,朱天乐,傅立新.富氧条件下NOx催化净化的研究进展.环境污染治理技术与设备,2002,3(8)：41-47
[31]张润泽,郑钟植.制备蜂窝状筛网进行NH3选择性催化还原NO的反应.催化学报,2002,23(1)：46-50
[32]张润泽,郑钟植.蜂窝状筛网催化剂上NH3选择性催化还原NO的动力学.大连理工大学学报,2002,42(2)：158-162
[33]Johc Marangozis. Comparison and Analysis of Intrinsic Kinetics and Effectiveness Factors for the Catalytic Reduction of NO with Ammonia in the Presence of Oxygen. Ind.Eng.Chem.Res,1992,31:987～994
[34]George L, Bauerle,S.C. Wu, Ken Nobe. Parametric and Durability Studies of NOx Reduction with NH3 on V2O5 Catalysts. Ind.Eng.Chem.Res.Dev,1978,17(2):117～ 122
[35]张强.燃煤电站SCR烟气脱硝技术及工程应用.北京：化学工业出版社,2007
[36]Miroslav Radojevic. Reduction of Nitrogen Oxides in Flue Gas. Environmental Pollution,1998,102:685～689
[37]Carlo Orsenigo, Alessandra Beretta, Pio Forzatti, Jiri Svachula. Theoretical and Experimental study of the interaction between NOx Reduction and SO2 Oxidation over DeNOx-SCR Catalysts. Catalysis Today,1996,27:15～21
[38]Ozkan U S, Cai Y P, Kumthekar M W. Investigation of the mechanism of ammonia oxidation and oxygen exchange over vanadia catalysts using N-15 and 0-18 tracer studies. Journal of Catalysis,1994,149(2):375～389
[39]Ozkan U S, Cai Y P, Kumthekar M W. Investigation of the reaction pathways in selective catalytic reduction of NO with NH3 over V2O5 catalysts. Journal of Catalysis,1994,149(2):390～403
[40]Matyshak V A, Krylov O V. In situ IR spectroscopy of intermediates in heterogeneous oxidative catalysis. Catalysis Today,1995,25:1 ～ 88
[41]Schneider H, Tschudin S, Schneider M, et al. In situ diffuse reflectance FTIR study of the selective catalytic reduction of NO by NH3 over vanadia-titania aerogels. Journal of Catalysis,1994,147 (1):5～14
[42]Busca G, Lorenzelli V, Ramis G. Chemistry of olefins at metal oxide surfaces:a tool for surface science investigation of oxide catalysts. Materials Chemistry and Physics,1991,29 (4):175-189
[43]Ramis G, Busca G, Bregani F, et al. Fourier transform infrared study of the adsorption and co-adsorption of nitric oxide, nitrogen dioxide and ammonia on TiO2 anatase. Applied Catalysis,1990,64:243～257
[44]Topsoe N Y, Anstrom M, Dumesic J A. FT-IR and theoretical evidence for dynamic structural rearrangements of Vanadia/Titania DeNOx catalysts. Catalysis Letters, 2001,76 (2):11～12
[45]孙克勤,钟秦.火电厂烟气脱硝技术及工程应用.北京：化学工业出版社,2007
[46]陈甘棠.化学反应工程.北京：化学工业出版社,2002
[47]Rajadhyaksha, Rajeev A, Helmut Knozinger. Ammonia adsorption on Vanadia supported on Titania-silica Catalyst-An Infrared spectroscopic investigation. Applied Catalysis,1989,51:81～92
[48]Isabella Nova, Luca Lietti, Enrico Tronconi, Pio Forzatti. Transient response method applied to the kinetic analysis of the DeNOx-SCR reaction. Chemical Engineering Science,2001,56:1229～1237
[49]Luca Lietti, Isabella Nova, Enrico Tronconi, Pio Forzatti. Transient kinetic study of the SCR-DeNOx reaction. Catalysis Today,1998,45:85～92
[50]Isabella Nova, Luca Lietti, Enrico Tronconi, Pio Forzatti. Dynamics of SCR reaction over a TiO2-supported vanadia-tungsta commercial catalyst. Catalysis Today,2000, 60:73～82
[51]Enrico Tronconi, Luca Lietti. Experimental and theoretical investigation of the dynamics of the SCR-DeNOx reaction. Chemical Engineering Science,1996,51 (11):2965～2970
[52]Dumestic J A, Topsoe N Y. Kinetics of the selective reduction of nitric oxide by ammonia over vanadia/titania. Journal of Catalysis,1996,163:409～417
[53]Enrico Tronconi. Interaction between chemical kinetics and transport phenomena in monolithic catalysts. Catalysis today,1997,34:421 ～ 427
[54]Enrico Tronconi. The role of inter-and intra-phase mass transfer in the SCR-DeNOx reaction over catalysts of different shapes. Catalysis today,1999,52:249～258
[55]Guido Busca, Luca Lietti, Gianguido Ramis, Francesco Berti. Chemical and Mechanistic aspects of the selective catalytic reduction of NOx by ammonia over oxide catalysts:A review. Applied Catalysis B:Environmental,1998,18:1～36
[56]A.Boyano, N.Lombardo, M.E.Galvez, M.J.Lazaro, R.Moliner. Vanadium-loaded carbon-based monoliths for the on-board NO reduction:Experimental study of operating conditions. Chemical Engineering Journal,2008,144:343～351
[57]王琦,王树荣,岑可法,等.燃煤电厂SCR脱硝技术催化剂的特性及进展.电站系统工程,2005,21(3)：4-6