HZSM-5分子筛催化剂脱硫脱硝研究
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摘要
本文对比研究了脱硫脱硝催化剂最佳载体的选取,研究脱硫催化剂V2O5/HZSM-5的最佳钒负载量和助剂改性以及评价,探索脱硝催化剂Ni-Cu-Ce-La-HZSM-5的最佳制备工艺,并且对其进行耐氧性研究以及评价。
实验结果表明,脱硫和脱硝的最佳催化剂载体均是Si/Al=25的HZSM-5分子筛；脱硫催化剂V205的最佳负载量为8%；钴和硫酸钾改性的CoO-K2S04-V205/HZSM-5脱硫催化剂具有很好的催化脱硫活性和热稳定性,XRD及TEM分析结果显示,改性前后晶粒没有明显变化,制备分散度都很好。CoO-K2S04-V205/HZSM-5催化剂的部分孔径稍有变大。
脱硝催化剂Ni-Cu-Ce-La-HZSM-5的最佳制备工艺为先将载体用硫酸酸化酸化,进行镍的离子交换,经过烘干焙烧后,在进行铜、铈、镧的离子交换时调节pH=7.8,最后烘干焙烧；催化脱硝率随氧气含量的增大而减小,镍、铈、镧的含量越大脱硝催化剂的耐氧性越好。调节pH=7.8不利于Ni2+的负载,但有利于Cu2+, Ce3+, La3+负载到催化剂上。
联合反应脱硫脱硝效果好于单独脱硫和脱硝,联合实验NO和SO2最佳脱除率分别达到98.153%和99.416%。
This article focused on the best carrier of desulfurization and denirification catalysts. The loading and modification of desulfurization catalyst V2O5/HZSM-5 were studied, and the best preparation procedure of denitrification catalyst Ni-Cu-Ce-La-HZSM-5 was investigated.
Results showed that the best loading of V2O5 was 8%. CoO-K2S04-V205/HZSM-5 modified by cobalt and potassium sulphate had good activity and thermal stability. XRD and TEM results show modification with CoO, K2SO4 and MoO3 has little impact on the crystalline grain of carrier and catalysts. While the pore volume and pore diameter of CoO-K2SO4-V2O5/HZSM-5 get bigger.
And the best preparation procedure of Ni-Cu-Ce-La-HZSM-5 was that HZSM-5 was acidulated by sulfuric acid solution firstly; and nickel ion exchange was implemented secondly; then the pH of the solution was adjusted to 7.8 thirdly when copper, cerium and lanthanum ion exchange was being implemented; and lastly, the catalyst could be produced after being dried and roasted. And acidic condition is conducive for nickel ion exchange, while pH=7.8 is conducive for copper, cerium and lanthanum ion exchange.
Compared with technologies for desulfurization and denitrification separately, combined removal reaction is better. When the airspeed is 38.96min-1, the best desulfurization efficiency and denitrication efficiency could be up to 98.153% and 99.416% separately when being experimented combinedly.
实验结果表明,脱硫和脱硝的最佳催化剂载体均是Si/Al=25的HZSM-5分子筛；脱硫催化剂V205的最佳负载量为8%；钴和硫酸钾改性的CoO-K2S04-V205/HZSM-5脱硫催化剂具有很好的催化脱硫活性和热稳定性,XRD及TEM分析结果显示,改性前后晶粒没有明显变化,制备分散度都很好。CoO-K2S04-V205/HZSM-5催化剂的部分孔径稍有变大。
脱硝催化剂Ni-Cu-Ce-La-HZSM-5的最佳制备工艺为先将载体用硫酸酸化酸化,进行镍的离子交换,经过烘干焙烧后,在进行铜、铈、镧的离子交换时调节pH=7.8,最后烘干焙烧；催化脱硝率随氧气含量的增大而减小,镍、铈、镧的含量越大脱硝催化剂的耐氧性越好。调节pH=7.8不利于Ni2+的负载,但有利于Cu2+, Ce3+, La3+负载到催化剂上。
联合反应脱硫脱硝效果好于单独脱硫和脱硝,联合实验NO和SO2最佳脱除率分别达到98.153%和99.416%。
This article focused on the best carrier of desulfurization and denirification catalysts. The loading and modification of desulfurization catalyst V2O5/HZSM-5 were studied, and the best preparation procedure of denitrification catalyst Ni-Cu-Ce-La-HZSM-5 was investigated.
Results showed that the best loading of V2O5 was 8%. CoO-K2S04-V205/HZSM-5 modified by cobalt and potassium sulphate had good activity and thermal stability. XRD and TEM results show modification with CoO, K2SO4 and MoO3 has little impact on the crystalline grain of carrier and catalysts. While the pore volume and pore diameter of CoO-K2SO4-V2O5/HZSM-5 get bigger.
And the best preparation procedure of Ni-Cu-Ce-La-HZSM-5 was that HZSM-5 was acidulated by sulfuric acid solution firstly; and nickel ion exchange was implemented secondly; then the pH of the solution was adjusted to 7.8 thirdly when copper, cerium and lanthanum ion exchange was being implemented; and lastly, the catalyst could be produced after being dried and roasted. And acidic condition is conducive for nickel ion exchange, while pH=7.8 is conducive for copper, cerium and lanthanum ion exchange.
Compared with technologies for desulfurization and denitrification separately, combined removal reaction is better. When the airspeed is 38.96min-1, the best desulfurization efficiency and denitrication efficiency could be up to 98.153% and 99.416% separately when being experimented combinedly.
引文
[1]杨飏.二氧化硫减排技术与烟气脱硫工程[M],北京：冶金工业出版社,2004：7.
[2]童志权.工业废气净化与利用[M],北京：化学工业出版社,2001,198-208.
[3]李成益.几种烟气脱硫工艺及技术经济分析[J].扬子石油化工,2006,21(6)：32-37.
[4]叶代启.烟气中氮氧化物污染的治理[J].环境保护科学,1999,25(4)：1-4.
[5]李雪飞,张文辉,杜铭华.干法烟气脱硝综述[J].洁净煤技术,2006,12(3)：43-46.
[6]杨飏.氮氧化物减排技术与烟气脱硝工程[M].北京：冶金工业出版社,2007：8-9.
[7]姚雨,郭占成,赵团.烟气脱硫脱硝技术的现状与发展[J].钢铁,2003,38(1)：5-7.
[8]谢新媛,煤燃烧过程固硫剂的研究发展[J].化工进展,2004,23(10)：1062-1066.
[9]邱鸿恩,吴丹,王睿.烟气同时脱硫脱硝技术进展[J].化学工业与工程技术,2004,25(4)：1-4.
[10]雷士文,雷世晓,王德敏.氨法烟气脱硫脱硝的技术特征[J].电力环境保护,2006,22(2)：32-36.
[11]许涛,张岗,刘波等.烟气脱硫技术及评价方法[J].广东电力,2002,15(4)：13-25.
[12]邱广明.燃煤电站SO2控制技术的发展与方向[J].内蒙古电力技术,2001,19(3)：12-19.
[13]冯治宇,王英刚,马锦等.用于烟气脱硫脱硝的活性焦的研制[J].化工环保,2002,22(5)：293-297.
[14]Hashimoto K, Wasada K, Toukai N, et al. Photocatalytic oxidation of nitrogen monoxide over titanium (VI) oxide nanocrystals large size areas [J]. Photochem and Photobiol. A:Chemistry,2000,136:103-109.
[15]Calis H P, Gerritsen A W, Vandenbleek C M. Zeolites Grown on Wire Gauze:A New Structured Catalyst Packing for Dustproof, Low Pressure Drop DeNOx Processes [J]. The Canadian Journal of Chemical Engineering,1995,73(2): 123-129.
[16]伍斌,童志权.NO分解催化剂的研究进展[J].工业催化,2005,13(7)：53-55.
[17]孙德智.环境工程中的高级氧化技术[M].北京：化学工业出版 社,2003,288-290.
[18]王旭伟,鄢晓忠,陈彦菲,等.国内外电厂燃煤锅炉烟气同时脱硫脱硝技术的研究进展[J].电站系统工程,2007,23(4)：6-9.
[19]许勇毅,查智明,赵翠仙.燃煤烟气中脱硫脱硝技术简述[J].云南化工,2007,34(1)：75-77.
[20]Xu Guangwen. Removal efficiency of the combined desulfurization/denitration process using power-particle fluidized bed [J]. Journal of Chemical Engineering of Japan,1999,32 (1):82-90.
[21]杜鹏.典型脱硫工艺在火电厂的应用探讨[J].四川工业学院学报,2002,(S1)：78-80.
[22]雷士文,雷世晓,王德敏.氨法烟气脱硫脱硝的技术特征[J].电力环境保护,2006,22(2)：32-36.
[23]Pei Yuanji, Li Ge, Wang Xiangqi, et al. A Low Costand High Efficient Facility for Removal of SO2 and NO、 in the Flue Gas from Coal Fire Power Plant [J]. In:2001 Particle Accelerator Conference. Chicago, IL:2001,660-662.
[24]Licki J, Chmielewski A. G, Iller E, Zimek Z, et al. Electron Beam Flue Gas Treatment for Multicom Potent Air Pollution Control [J]. APPlied Energy,2003, 75(3-4):145-154.
[25]Ehmie lewskiAndrzej G, LickiJanusz, paweleeandrzdj, et al. Operational Experience of the Industrial Plant for Electron Beam Flue Gas Treatment [J]. Radiation Physiesand Chemistry,2004,71(1-2):439-442.
[26]J. Sidney Clements, Akira Mizuno, Wright C-Finney, et al. Combined Removal of SO2, NOX, and Fly Ash from Simulated Flue Gas Using Pulsed Streamer Corona [J]. IEEE Transactions on Industry Applications,1989,25(1):62-69.
[27]Toshiaki yramamot, Masaaki Okub, Takao Nagaok, Kunihiro Hayakawa. Simultaneous Removal of NOx, SO2, and CO2 at Elevated Temperature Using a Plasma Chemical Hybrid Process [J]. IEEE Transactions on Industry Applications, 2002,38(5):1168-1173.
[28]Li Mindong, Shou Guosheng, Lu Taoliu, Jia Xiangyang. Removal of NOx and SO2 in Plasm Reactor with Water Film [J]. In:XXth International Symposium on Discharges and Electrical Insulation in Vacuum Tours.2002,423-426.
[29]CengizPerinA, AbbasianJavad, KhaliliNasrinR, et al. Development of Durableand Reactive Regenerable Sorbents for High Temperature Flue Gas Desulphurization [J]. International Journal of Environment and pollution,2002,17(1):82-101.
[30]Chambers A. Conemaugh station adds scrubbers to comply with CAAA mandates [J]. Power Engineering,1995,99(3):8-9.
[31]杜黎明,刘金荣.燃煤锅炉同时脱硫脱硝技术工艺性分析[J].中国电力,2007,40(2)：71-74.
[32]冯治宇,王英刚,马锦等.用于烟气脱硫脱硝的活性焦的研制[J].化工环保,2002,22(5)：293-297.
[33]Tseng Chaoheng. The application of pulsed corona discharge technology in flue gas desulfurization and denitrification [C]. The Air & Waste Management Association's 92nd Annual Meeting & Exhibition, St. Louis, Missouri, USA,1999.
[34]Iwamoto M, Yahiro H. Removal of nitrogen monoxide through a novel catalytic process decomposition on excessively copper ion exchanged ZSM-5 zeolites [J]. The Journal of Chemical Physics,1991,95:3727-3730.
[35]石川,宋志民,付迎,等.Ni2+改性的Cu-ZSM-5催化分解NO的性能[J].环境科学,2001,(6)：24-26.
[36]郭锡坤,李治国,陈庆生.酸处理HZSM-5负载Cu催化剂的制备及其催化性能[J].汕头大学学报(自然科学版),2006,21(3)：12-16.
[37]万家义,余林,陈豫.Cu-M/ZSM-S (M=Ce, La, Ag)催化剂的表征及其对NO直接分解催化活性的研究[J].化学研究与应用,1999,11(1)：8-10.
[38]Giakoumelou I, Parvulescu V, Boghosian S. Oxidation of sulfur dioxide over supported solid V2O5/SiO2 and supported molten salt V2O5-Cs2SO4/SiO2 catalysts: molecular structure and reactivity [J]. Journal of Catalysis,2004,225(2):337-349.
[39]徐云龙,吕冬琴,钱秀珍,等.钒硅催化脱硫脱硝的研究[J].环境污染与防治,2008,30(6)：20-26.
[40]唐旺,丁静,杨建平等.ZSM-5型分子筛对二氧化硫的动态吸附性能[J].无机盐工业,2009,41(8)：21-23.
[41]王尚第,孙俊全.催化剂工程导论[M].北京：化学工业出版社,2004：99-152.
[42]Wagner, Paul, Cook, et al. SCR succeeds at logan generating plant [J]. Power Engineering,1997,101(1):28-31.
[43]徐光,乔力.电子射线电子洗涤工艺研究进展[J].自然杂志,1999,21(4)：227-229.
[2]童志权.工业废气净化与利用[M],北京：化学工业出版社,2001,198-208.
[3]李成益.几种烟气脱硫工艺及技术经济分析[J].扬子石油化工,2006,21(6)：32-37.
[4]叶代启.烟气中氮氧化物污染的治理[J].环境保护科学,1999,25(4)：1-4.
[5]李雪飞,张文辉,杜铭华.干法烟气脱硝综述[J].洁净煤技术,2006,12(3)：43-46.
[6]杨飏.氮氧化物减排技术与烟气脱硝工程[M].北京：冶金工业出版社,2007：8-9.
[7]姚雨,郭占成,赵团.烟气脱硫脱硝技术的现状与发展[J].钢铁,2003,38(1)：5-7.
[8]谢新媛,煤燃烧过程固硫剂的研究发展[J].化工进展,2004,23(10)：1062-1066.
[9]邱鸿恩,吴丹,王睿.烟气同时脱硫脱硝技术进展[J].化学工业与工程技术,2004,25(4)：1-4.
[10]雷士文,雷世晓,王德敏.氨法烟气脱硫脱硝的技术特征[J].电力环境保护,2006,22(2)：32-36.
[11]许涛,张岗,刘波等.烟气脱硫技术及评价方法[J].广东电力,2002,15(4)：13-25.
[12]邱广明.燃煤电站SO2控制技术的发展与方向[J].内蒙古电力技术,2001,19(3)：12-19.
[13]冯治宇,王英刚,马锦等.用于烟气脱硫脱硝的活性焦的研制[J].化工环保,2002,22(5)：293-297.
[14]Hashimoto K, Wasada K, Toukai N, et al. Photocatalytic oxidation of nitrogen monoxide over titanium (VI) oxide nanocrystals large size areas [J]. Photochem and Photobiol. A:Chemistry,2000,136:103-109.
[15]Calis H P, Gerritsen A W, Vandenbleek C M. Zeolites Grown on Wire Gauze:A New Structured Catalyst Packing for Dustproof, Low Pressure Drop DeNOx Processes [J]. The Canadian Journal of Chemical Engineering,1995,73(2): 123-129.
[16]伍斌,童志权.NO分解催化剂的研究进展[J].工业催化,2005,13(7)：53-55.
[17]孙德智.环境工程中的高级氧化技术[M].北京：化学工业出版 社,2003,288-290.
[18]王旭伟,鄢晓忠,陈彦菲,等.国内外电厂燃煤锅炉烟气同时脱硫脱硝技术的研究进展[J].电站系统工程,2007,23(4)：6-9.
[19]许勇毅,查智明,赵翠仙.燃煤烟气中脱硫脱硝技术简述[J].云南化工,2007,34(1)：75-77.
[20]Xu Guangwen. Removal efficiency of the combined desulfurization/denitration process using power-particle fluidized bed [J]. Journal of Chemical Engineering of Japan,1999,32 (1):82-90.
[21]杜鹏.典型脱硫工艺在火电厂的应用探讨[J].四川工业学院学报,2002,(S1)：78-80.
[22]雷士文,雷世晓,王德敏.氨法烟气脱硫脱硝的技术特征[J].电力环境保护,2006,22(2)：32-36.
[23]Pei Yuanji, Li Ge, Wang Xiangqi, et al. A Low Costand High Efficient Facility for Removal of SO2 and NO、 in the Flue Gas from Coal Fire Power Plant [J]. In:2001 Particle Accelerator Conference. Chicago, IL:2001,660-662.
[24]Licki J, Chmielewski A. G, Iller E, Zimek Z, et al. Electron Beam Flue Gas Treatment for Multicom Potent Air Pollution Control [J]. APPlied Energy,2003, 75(3-4):145-154.
[25]Ehmie lewskiAndrzej G, LickiJanusz, paweleeandrzdj, et al. Operational Experience of the Industrial Plant for Electron Beam Flue Gas Treatment [J]. Radiation Physiesand Chemistry,2004,71(1-2):439-442.
[26]J. Sidney Clements, Akira Mizuno, Wright C-Finney, et al. Combined Removal of SO2, NOX, and Fly Ash from Simulated Flue Gas Using Pulsed Streamer Corona [J]. IEEE Transactions on Industry Applications,1989,25(1):62-69.
[27]Toshiaki yramamot, Masaaki Okub, Takao Nagaok, Kunihiro Hayakawa. Simultaneous Removal of NOx, SO2, and CO2 at Elevated Temperature Using a Plasma Chemical Hybrid Process [J]. IEEE Transactions on Industry Applications, 2002,38(5):1168-1173.
[28]Li Mindong, Shou Guosheng, Lu Taoliu, Jia Xiangyang. Removal of NOx and SO2 in Plasm Reactor with Water Film [J]. In:XXth International Symposium on Discharges and Electrical Insulation in Vacuum Tours.2002,423-426.
[29]CengizPerinA, AbbasianJavad, KhaliliNasrinR, et al. Development of Durableand Reactive Regenerable Sorbents for High Temperature Flue Gas Desulphurization [J]. International Journal of Environment and pollution,2002,17(1):82-101.
[30]Chambers A. Conemaugh station adds scrubbers to comply with CAAA mandates [J]. Power Engineering,1995,99(3):8-9.
[31]杜黎明,刘金荣.燃煤锅炉同时脱硫脱硝技术工艺性分析[J].中国电力,2007,40(2)：71-74.
[32]冯治宇,王英刚,马锦等.用于烟气脱硫脱硝的活性焦的研制[J].化工环保,2002,22(5)：293-297.
[33]Tseng Chaoheng. The application of pulsed corona discharge technology in flue gas desulfurization and denitrification [C]. The Air & Waste Management Association's 92nd Annual Meeting & Exhibition, St. Louis, Missouri, USA,1999.
[34]Iwamoto M, Yahiro H. Removal of nitrogen monoxide through a novel catalytic process decomposition on excessively copper ion exchanged ZSM-5 zeolites [J]. The Journal of Chemical Physics,1991,95:3727-3730.
[35]石川,宋志民,付迎,等.Ni2+改性的Cu-ZSM-5催化分解NO的性能[J].环境科学,2001,(6)：24-26.
[36]郭锡坤,李治国,陈庆生.酸处理HZSM-5负载Cu催化剂的制备及其催化性能[J].汕头大学学报(自然科学版),2006,21(3)：12-16.
[37]万家义,余林,陈豫.Cu-M/ZSM-S (M=Ce, La, Ag)催化剂的表征及其对NO直接分解催化活性的研究[J].化学研究与应用,1999,11(1)：8-10.
[38]Giakoumelou I, Parvulescu V, Boghosian S. Oxidation of sulfur dioxide over supported solid V2O5/SiO2 and supported molten salt V2O5-Cs2SO4/SiO2 catalysts: molecular structure and reactivity [J]. Journal of Catalysis,2004,225(2):337-349.
[39]徐云龙,吕冬琴,钱秀珍,等.钒硅催化脱硫脱硝的研究[J].环境污染与防治,2008,30(6)：20-26.
[40]唐旺,丁静,杨建平等.ZSM-5型分子筛对二氧化硫的动态吸附性能[J].无机盐工业,2009,41(8)：21-23.
[41]王尚第,孙俊全.催化剂工程导论[M].北京：化学工业出版社,2004：99-152.
[42]Wagner, Paul, Cook, et al. SCR succeeds at logan generating plant [J]. Power Engineering,1997,101(1):28-31.
[43]徐光,乔力.电子射线电子洗涤工艺研究进展[J].自然杂志,1999,21(4)：227-229.