烟气循环流化床同时脱硫脱硝吸收剂制备及脱除机理研究
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摘要
以粉煤灰﹑Ca(OH)_2、滑石粉和NaClO_2为基础物质采用干法制备了高活性吸收剂,实验条件为粉煤灰与氢氧化钙的质量比为3,添加剂选择滑石粉,含量为1%,NaClO_2含量为1.6%,研磨时间为2小时。在固定床和烟气循环流化床上,对该吸收剂的同时脱硫脱硝性能进行了初步的实验研究,详细分析了影响吸收剂脱硫脱硝效率的若干影响因素。在固定床反应温度为70℃,Ca/(N+S)为1.2时,可获得脱硫效率为100%,脱硝效率为99.2%。同时,还研究了烟气循环流化床运行的最佳实验条件,在最佳条件下,SO_2、NO_X的脱除效率分别为78.7%和53.7%。利用化学方法分析了脱除产物的组成和含量,探讨了高活性吸收剂的脱硫脱硝机理。本文为烟气污染控制提供有益的参考。
Fly ash, Ca(OH)_2, French chalk and NaClO2 were used as the basal materials to prepare the highly active absorbents in dry way, preparation conditions are as follow: fly ash and Ca(OH)_2 quality ration is 3, additive is French chalk which content is 1%, NaClO_2 content is 1.6%, grinding time is 2 hours. Experimental research of simultaneous desulfurization and denitrification were carried out at the fixture bed and CFB, the influencing factors of desulfurization and denitrification efficiencies were analysed in detail. At the fixture bed, the desulfurization and denitrification efficiency is 100% and 99.2% when the reaction conditions is: reaction temperature is 70℃, Ca/(N+S)is 1.2. Under the best reaction conditions of CFB, 78.7% desulfurization and 53.7% denitrification efficiency can be achieved. The absorbents after reaction were analysed with chemical method in the present paper, furthermore, the mechanism of SO_2 and NO_X removal with the prepared highly active absorbents was investigated. The research of this dissertation provides valuable references for pollution control of flue gas.
Fly ash, Ca(OH)_2, French chalk and NaClO2 were used as the basal materials to prepare the highly active absorbents in dry way, preparation conditions are as follow: fly ash and Ca(OH)_2 quality ration is 3, additive is French chalk which content is 1%, NaClO_2 content is 1.6%, grinding time is 2 hours. Experimental research of simultaneous desulfurization and denitrification were carried out at the fixture bed and CFB, the influencing factors of desulfurization and denitrification efficiencies were analysed in detail. At the fixture bed, the desulfurization and denitrification efficiency is 100% and 99.2% when the reaction conditions is: reaction temperature is 70℃, Ca/(N+S)is 1.2. Under the best reaction conditions of CFB, 78.7% desulfurization and 53.7% denitrification efficiency can be achieved. The absorbents after reaction were analysed with chemical method in the present paper, furthermore, the mechanism of SO_2 and NO_X removal with the prepared highly active absorbents was investigated. The research of this dissertation provides valuable references for pollution control of flue gas.
引文
[1]王庆一.1998 年能源数据.能源政策研究,2000,(1):76~81
[2]朱法华.火电建设面临的环保形势与任务分析.环境科学研究,2005,18(4):21～29
[3]韩慧,白敏冬,白希尧. 脱硫脱氮技术展望.环境科学研究,2002,15(1): 55~60
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[5]Sang Mun Jeong,Sang Done Kim.Removal of NO and S02 by CuQ～ 一A1203 SOrbent/Catalyst in a Fluidized –Bed Reactor[J].Ind.Eng.Chem.Res,2000,(39):1911—1988.
[6]James T Yeh, Richard J Demski, James I Joubert.Combined SO2 and NOX Removal from Rue Gas[J].Environmental Progress,1985,4(4):223-228.
[7]Gupta, Himanshu; BenSOn, Steven A.; Fan, Laing~Shih; et al. Pilot-scale studies of NOX reduction by activated high-SOdium lignite chars: A demonstration of the CARBONOX process. Industrial and Engineering Chemistry Research, 2004, 43(18): 5820~5827
[8]王斌,唐茂平,马爱萍.后石电厂超临界压力机组脱 NOX工艺特点.中国电力,2004,37(3): 88~90
[9]田贺忠. 中国氮氧化物排放现状、趋势及综合控制对策研究:[博士学位论文].北京:清华大学,2003
[10]陈子彤.锅炉排污水用于烟气脱硫脱氮的技术.煤炭加工与综合利用,1999,(1):39～41
[11]吴学礼,陈孟,朱蓓蓉.粉煤灰火山灰反应动力学的研究.建筑材料学报,2002,5(2):120～125
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[13]Izquierdo, J.F.; Cunill, F.; Martinez, J.C.; et al. Fly Ash Reactivation for the Desulfurization of Coal-fired Utility Station’s Flue Gas. Separation Science and Technology, 1992, 27(1): 61～72
[14]PeterSOn, Joseph R.; Rochelle, Gary T. Aqueous Reaction of Fly Ash and Ca(OH)2 to Produce Calcium Silicate abSOrbent for Flue Gas Desulfurization. Environmental Science and Technology 1988, 22(11): 1299～1304
[15]Hall, Brent W.; Singer, Carl; Jozewicz, Wojciech; et al. Current Status of the ADVACATE Process for Flue Gas Desulfurization. Journal of the Air & Waste Management AsSOciation, 1992, 42(1): 103～110
[16]Liu, Chiung-Fang; Shih, Shin-Min; Lin, Ren-Bin. Kinetic Model for the Reaction of Ca(OH)2/Fly Ash SOrbents with SO2 at Low Temperatures. Industrial and Engineering Chemistry Research, 2004, 43(15): 4112～4117
[17]Cunill, Fidel; Izquierdo, Jose F.; Martinez, Juan C.; et al. Influence of Different Additives on the Reaction between Hydrated Lime and Sulfur Dioxide. Environmental Progress, 1991, 10(4): 273～277
[18]赵毅、马双忱、李燕中,等. 利用粉煤灰吸收剂对烟气脱硫脱氮的实验研究. 中国电机工程学报. Zhao, Yi; Ma, Shuang-Chen; Li, Yan-Zhong; et al. Experimental Investigation of Desulfurization and Denitrification from Flue Gas by AbSOrbents Based on Fly Ash. Zhongguo Dianji Gongcheng Xuebao/Proceedings of the Chinese SOciety of Electrical Engineering, 2002, 22(3): 108～112
[19]陈锐.排烟循环流化床脱硫的实验和机理研究:[硕士学位论文].北京,清华大学,1996
[20]单志峰,黄友明.国外烟气同步脱硫脱氮技术现状.冶金环境保护, 1999,4:40～45
[21]Xu Guangwen.Innovative combined desulphurization/denitration process using a powder-particle fluidized bed.Process Safety and Environmental Protection :Transactions of the Instituion of Chemical Engineers, 1999,77(2):77～87
[22]Xu Guangwen.Adaptive SOrbent for the combined desulfurization /denitration process using a power-particle fluidized bed. Industrial and Engineering Chemistry Research, 2000,39(7):2190～2198
[23]Xu Guangwen.Removal efficiency of the combined desulfurization /denitration process using power-particle fluidized bed.Journal of Chemical Engineering of Japan,1999,32(1):82～90
[24] 赵鹏高.粉煤灰综合利用.沈阳:辽宁科学技术出版社,1993,68~99
[25] 余文峰,程祖海,张耀宁,孙峰,王寿增.干式高效超微粒子烟气脱硫技术.环境工程,2001,19(4):35-37
[26] 赵毅,马双忱,李燕中,赵建海,付延春.利用粉煤灰吸收剂对烟气脱硫脱氮的实验研究[J].中国电机工程学报,2002,22(3):108-112
[27] 赵毅,马双忱,黄建军,许佩瑶,汪黎东,华伟.高活性吸收剂脱硫和脱氮实验和机理研究[J].电机工程学报,2003,23(10):236-240
[28] Qimin Guo,S.Hikida,Y.Takahashi,et.a1.Drying of microparticleslurry and salt—water SOlution by a powder—Particle spouted bed.Journal of Chemical Engineering of Japan,2000,33(2):223—231
[29] JackSOn IRH. Convergence properties of radial basis functions. Const Approx, 1988(1):243-264
[30] Aoki M., Optimization of stochastic systems: topics in discrete-time dynamics. San Diego, CA:Academic Press, 1989
[31] 赵毅,马双忱,黄建军,许佩瑶,汪黎东,华伟.高活性吸收剂脱硫和脱氮实验及机理研究[J].中国电机工程学报,2003,23(10):236-240
[32] Gao Xiang, Luo Zhongyang, Liu Ni,et al. Desulfurization characteristic of calcium-based SOrbent during activation process[J]. Journalof Chemical Engineering of Japan, 2001, 34(9):39-45
[33] 张凡,张伟,杨霓云,等.半干半湿法烟气脱硫技术研究.环境科学研究,2000,13(1):60~63
[34] Cabriele Centi, Nello Passarini. Combined DeSO2/DeNOX reduction on a copper on alumina SOrbent-catalyst mechanism of SO2 oxidation-adSOrption[J]. Industrial and Engineering Chemistry Research. 1992, 31(8): 1947-1950
[35] 赵毅,李守信.有害气体工程[M].北京:化学工业出版社,2001,136-141
[36] 台炳华.工业烟气净化.北京:冶金工业出版社,1999,45~65
[37] 刘旦初.多相催化原理.上海:复旦大学出版社,1997,321~334
[38] Hori,M.;Matsunga,N.;Malte,P.C.;etc.Twenty-Four Symposium(International) on Combustion/The Combustion Institute Sydney,Australia,1992,909~916
[39] Zamansky,V.M.;Ho,L.;Maly,R.M.,etc. Third International Conference on Combustion Technologies for a Clean Environment,Lisbon Portugal,1995,Vol.2
[40] S.Behrooz Ghorishi,Carl F.Singer,and Wojciech S.Jozewicz,etc. Simultaneous Control of Hg0 ,SO2,and NOX Novel Oxidized Calcium-Based SOrbents, Air & Waste Manage.AsSOc. 2002,5,Volume52:273~278
[41] Tsuchiai H,Ishizuka T,Ueno T et al.Highly Active AbSOrbent for SO2 Removal Prepared from Coal Fly Ash.Ind. Eng. Chem.Res.,1995,34:1404~1411
[42] Tsuchiai H, Ishizuka T, Ueno T et al..Study of Flue Gas Desulfurization AbSOrbent from Coal Fly Ash:Effect of the Composition of the AbSOrbent on the Activity. Ind. Eng. Chem. Res.,1996,35:2322~2326
[43] 樊保国,项光明,祁海鹰,等.常温循环流化床烟气脱硫影响脱硫效率的参数及机理.燃烧科学与技术, 2001,7(3):228~232
[44] 王安杰,周裕之,赵培,化学反应工程学,化学工业出版社,2005:99～132
[45] 伍钦,钟理,传质与分离工程,华南理工大学出版社,2005:329～342
[2]朱法华.火电建设面临的环保形势与任务分析.环境科学研究,2005,18(4):21～29
[3]韩慧,白敏冬,白希尧. 脱硫脱氮技术展望.环境科学研究,2002,15(1): 55~60
[4]JaSOn Makansi.Will combined SO2,NO processes find a niche in the market[J].Power,1990,(9):26-28.
[5]Sang Mun Jeong,Sang Done Kim.Removal of NO and S02 by CuQ～ 一A1203 SOrbent/Catalyst in a Fluidized –Bed Reactor[J].Ind.Eng.Chem.Res,2000,(39):1911—1988.
[6]James T Yeh, Richard J Demski, James I Joubert.Combined SO2 and NOX Removal from Rue Gas[J].Environmental Progress,1985,4(4):223-228.
[7]Gupta, Himanshu; BenSOn, Steven A.; Fan, Laing~Shih; et al. Pilot-scale studies of NOX reduction by activated high-SOdium lignite chars: A demonstration of the CARBONOX process. Industrial and Engineering Chemistry Research, 2004, 43(18): 5820~5827
[8]王斌,唐茂平,马爱萍.后石电厂超临界压力机组脱 NOX工艺特点.中国电力,2004,37(3): 88~90
[9]田贺忠. 中国氮氧化物排放现状、趋势及综合控制对策研究:[博士学位论文].北京:清华大学,2003
[10]陈子彤.锅炉排污水用于烟气脱硫脱氮的技术.煤炭加工与综合利用,1999,(1):39～41
[11]吴学礼,陈孟,朱蓓蓉.粉煤灰火山灰反应动力学的研究.建筑材料学报,2002,5(2):120～125
[12]Kaplan, Norman; Maxwell, Michael A. Removal of SO2 from Industrial Waste Gases. Chemical Engineering (New York), 1977, 84(22): 127～135
[13]Izquierdo, J.F.; Cunill, F.; Martinez, J.C.; et al. Fly Ash Reactivation for the Desulfurization of Coal-fired Utility Station’s Flue Gas. Separation Science and Technology, 1992, 27(1): 61～72
[14]PeterSOn, Joseph R.; Rochelle, Gary T. Aqueous Reaction of Fly Ash and Ca(OH)2 to Produce Calcium Silicate abSOrbent for Flue Gas Desulfurization. Environmental Science and Technology 1988, 22(11): 1299～1304
[15]Hall, Brent W.; Singer, Carl; Jozewicz, Wojciech; et al. Current Status of the ADVACATE Process for Flue Gas Desulfurization. Journal of the Air & Waste Management AsSOciation, 1992, 42(1): 103～110
[16]Liu, Chiung-Fang; Shih, Shin-Min; Lin, Ren-Bin. Kinetic Model for the Reaction of Ca(OH)2/Fly Ash SOrbents with SO2 at Low Temperatures. Industrial and Engineering Chemistry Research, 2004, 43(15): 4112～4117
[17]Cunill, Fidel; Izquierdo, Jose F.; Martinez, Juan C.; et al. Influence of Different Additives on the Reaction between Hydrated Lime and Sulfur Dioxide. Environmental Progress, 1991, 10(4): 273～277
[18]赵毅、马双忱、李燕中,等. 利用粉煤灰吸收剂对烟气脱硫脱氮的实验研究. 中国电机工程学报. Zhao, Yi; Ma, Shuang-Chen; Li, Yan-Zhong; et al. Experimental Investigation of Desulfurization and Denitrification from Flue Gas by AbSOrbents Based on Fly Ash. Zhongguo Dianji Gongcheng Xuebao/Proceedings of the Chinese SOciety of Electrical Engineering, 2002, 22(3): 108～112
[19]陈锐.排烟循环流化床脱硫的实验和机理研究:[硕士学位论文].北京,清华大学,1996
[20]单志峰,黄友明.国外烟气同步脱硫脱氮技术现状.冶金环境保护, 1999,4:40～45
[21]Xu Guangwen.Innovative combined desulphurization/denitration process using a powder-particle fluidized bed.Process Safety and Environmental Protection :Transactions of the Instituion of Chemical Engineers, 1999,77(2):77～87
[22]Xu Guangwen.Adaptive SOrbent for the combined desulfurization /denitration process using a power-particle fluidized bed. Industrial and Engineering Chemistry Research, 2000,39(7):2190～2198
[23]Xu Guangwen.Removal efficiency of the combined desulfurization /denitration process using power-particle fluidized bed.Journal of Chemical Engineering of Japan,1999,32(1):82～90
[24] 赵鹏高.粉煤灰综合利用.沈阳:辽宁科学技术出版社,1993,68~99
[25] 余文峰,程祖海,张耀宁,孙峰,王寿增.干式高效超微粒子烟气脱硫技术.环境工程,2001,19(4):35-37
[26] 赵毅,马双忱,李燕中,赵建海,付延春.利用粉煤灰吸收剂对烟气脱硫脱氮的实验研究[J].中国电机工程学报,2002,22(3):108-112
[27] 赵毅,马双忱,黄建军,许佩瑶,汪黎东,华伟.高活性吸收剂脱硫和脱氮实验和机理研究[J].电机工程学报,2003,23(10):236-240
[28] Qimin Guo,S.Hikida,Y.Takahashi,et.a1.Drying of microparticleslurry and salt—water SOlution by a powder—Particle spouted bed.Journal of Chemical Engineering of Japan,2000,33(2):223—231
[29] JackSOn IRH. Convergence properties of radial basis functions. Const Approx, 1988(1):243-264
[30] Aoki M., Optimization of stochastic systems: topics in discrete-time dynamics. San Diego, CA:Academic Press, 1989
[31] 赵毅,马双忱,黄建军,许佩瑶,汪黎东,华伟.高活性吸收剂脱硫和脱氮实验及机理研究[J].中国电机工程学报,2003,23(10):236-240
[32] Gao Xiang, Luo Zhongyang, Liu Ni,et al. Desulfurization characteristic of calcium-based SOrbent during activation process[J]. Journalof Chemical Engineering of Japan, 2001, 34(9):39-45
[33] 张凡,张伟,杨霓云,等.半干半湿法烟气脱硫技术研究.环境科学研究,2000,13(1):60~63
[34] Cabriele Centi, Nello Passarini. Combined DeSO2/DeNOX reduction on a copper on alumina SOrbent-catalyst mechanism of SO2 oxidation-adSOrption[J]. Industrial and Engineering Chemistry Research. 1992, 31(8): 1947-1950
[35] 赵毅,李守信.有害气体工程[M].北京:化学工业出版社,2001,136-141
[36] 台炳华.工业烟气净化.北京:冶金工业出版社,1999,45~65
[37] 刘旦初.多相催化原理.上海:复旦大学出版社,1997,321~334
[38] Hori,M.;Matsunga,N.;Malte,P.C.;etc.Twenty-Four Symposium(International) on Combustion/The Combustion Institute Sydney,Australia,1992,909~916
[39] Zamansky,V.M.;Ho,L.;Maly,R.M.,etc. Third International Conference on Combustion Technologies for a Clean Environment,Lisbon Portugal,1995,Vol.2
[40] S.Behrooz Ghorishi,Carl F.Singer,and Wojciech S.Jozewicz,etc. Simultaneous Control of Hg0 ,SO2,and NOX Novel Oxidized Calcium-Based SOrbents, Air & Waste Manage.AsSOc. 2002,5,Volume52:273~278
[41] Tsuchiai H,Ishizuka T,Ueno T et al.Highly Active AbSOrbent for SO2 Removal Prepared from Coal Fly Ash.Ind. Eng. Chem.Res.,1995,34:1404~1411
[42] Tsuchiai H, Ishizuka T, Ueno T et al..Study of Flue Gas Desulfurization AbSOrbent from Coal Fly Ash:Effect of the Composition of the AbSOrbent on the Activity. Ind. Eng. Chem. Res.,1996,35:2322~2326
[43] 樊保国,项光明,祁海鹰,等.常温循环流化床烟气脱硫影响脱硫效率的参数及机理.燃烧科学与技术, 2001,7(3):228~232
[44] 王安杰,周裕之,赵培,化学反应工程学,化学工业出版社,2005:99～132
[45] 伍钦,钟理,传质与分离工程,华南理工大学出版社,2005:329～342