纳米二氧化钛催化燃烧固硫机理的实验研究
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摘要
本文对纳米TiO_2催化燃烧固硫进行了实验研究。通过对燃烧后煤灰的成分分析和燃烧烟气中SO_2含量的测定,确定其固硫效果。探讨了纳米TiO_2添加量、Ca/S、燃烧温度和不同条件制备的纳米TiO_2对分析纯CaO固硫的影响。通过对反应产物的红外、X射线衍射、比表面积分析以及原煤的热重分析,讨论了纳米TiO_2催化燃烧固硫的机理。实验结果表明,纳米TiO_2对CaO具有一定的催化燃烧固硫作用,能够提高CaO固硫效果。在最佳实验条件下,纳米TiO_2添加量为8%,钙硫比Ca/S为2,燃烧温度为850℃,通氧量为40ml/min,烟煤固硫率为87.7%,褐煤固硫率为87.8%,比不添加纳米TiO_2时固硫效率分别提高了16.9%和13.4%。
Experiment research of nanometer TiO_2 catalytic combustion to desulfurization is studied in this work. Desulfurization effect is measured by the composition analysis of fly ash that after combustion and the content of SO_2 in flue gas. The effect to analysis pure CaO desulfurization by nanometer TiO_2 addition、Ca/S ratio、combustion temperature and nanometer TiO_2 that prepared at different condition are discussed. The combustion desulfurization mechanisms are discussed by infrared absorption and XRD and BET and TGA analysis. The experiment results show that nanometer TiO_2 have definite combustion catalytic effect to CaO combustion desulfurization, and can promote the desulfurization effect of CaO. The optimal addition of the experiment is that nanometer TiO_2 is 8%,Ca/S ratio is 2, combustion temperature is 850℃,the flux of oxygen is 40ml/min.In this condition, the desulfurization efficiency of bituminous and lignite can achieve to 87.7% and 87.8%, it was respectively increased by 17.1% and 13.4% compared with the efficiency of CaO act only.
Experiment research of nanometer TiO_2 catalytic combustion to desulfurization is studied in this work. Desulfurization effect is measured by the composition analysis of fly ash that after combustion and the content of SO_2 in flue gas. The effect to analysis pure CaO desulfurization by nanometer TiO_2 addition、Ca/S ratio、combustion temperature and nanometer TiO_2 that prepared at different condition are discussed. The combustion desulfurization mechanisms are discussed by infrared absorption and XRD and BET and TGA analysis. The experiment results show that nanometer TiO_2 have definite combustion catalytic effect to CaO combustion desulfurization, and can promote the desulfurization effect of CaO. The optimal addition of the experiment is that nanometer TiO_2 is 8%,Ca/S ratio is 2, combustion temperature is 850℃,the flux of oxygen is 40ml/min.In this condition, the desulfurization efficiency of bituminous and lignite can achieve to 87.7% and 87.8%, it was respectively increased by 17.1% and 13.4% compared with the efficiency of CaO act only.
引文
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[22]Young Sun Mok,In-Sik Nam.Positive pulsed corona discharge process for simultaneous removal of SO2 and NO from iron-ore sintering flue gas.IEEE Transactions on Plasma Science,1999,27(4):1188~1190
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[27]陈亚非.金属氧化物对Ca(OH)2脱硫影响的研究.工程热物理学报,1997,18(4):517~520
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[30]许满贵,李建伟,葛岭梅.粉煤灰添加剂对石灰石脱硫的作用.西安矿业学院学报,1998,18(2):149~153
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[32]Yang.R.T. and Shen.M.S.Fluidized-bed combustion of coal with lime additive catalytic sulfation of lime with iron compounds and coal ash.American Chemical Society,1978,12:915~917
[33]Desal.M.J. and Yang.R.T.Enhancement of sulfation of calcium oxide by iron oxide.Ind. Eng. Chem. Process Des. Dev,1983,22:119~123
[34]Mark R.Stouffer et al.An investigation of CaO sulfation mechanisms in boiler sorbent injection.AICHE J,1989,35(8):1253~1262
[35]Juan Adanez,et al.Study of modified calcium hydroxides for enhancing SO2 removal during sorbent injection in pulverized coal boilers.Fuel,1997,76(3):257~265
[36]DavidA,et al.Structural changes in surfactant-modified sorbents during furnace injection.AICHE J,1990,35(3):500~506
[37]Eiji Sasaoka and Norimasa Sada.Preparation of macroporous lime from natural lime by swelling method with acetic acid forhigh-temperature desulfurization.Ind. Eng. Chem. Res,1998,37:3943~3949
[38]陈鸿伟,王春波.复合调质提高CaO固硫率的试验研究.环境科学学报,1999,19(4):357~361
[39]王春波,陈鸿伟.提高CaO固硫率的实验及分析.华北大力大学学报,1999,26(2):85~90
[40]任有中,董佳芳.洁净型煤中提高碳酸钙脱硫性能的新技术.工程热物理学报,1999,20(1):30~32
[41]蔡卫权.纳米催化技术用于空气净化.环境污染治理技术与设备,2004,5(4):58~61
[42]姜兆华.应用表面化学与技术.哈尔滨:哈尔滨工业大学出版社,2001
[43]张立德.纳米材料和纳米结构.北京:科学技术出版社,2001
[44]葛军,丁辉.纳米二氧化钛的应用与市场研究.材料导报,2004,18(2):65~68
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[46]姚超,林西平.纳米技术与纳米材料-纳米TiO2的液相合成.日用化学工业,2004,34(3):190~197
[47]袁中山,吴迪镛,王树东.采用一体化燃煤添加剂的燃煤中固硫作用研究.燃料化学学报,2002,30(1):36~40
[48]吕欣,林国珍,周广柱等.型煤燃烧过程中CaO的形成及其固硫作用.环境化学,1998,17(6):528~531
[49]程军,周俊虎,刘建忠等.电石渣和铝土粉的高温燃烧脱硫特性及微观分析.环境科学学报,2003,23(5):641~646
[50]湛伦建,赵跃民.工业型煤燃烧固硫的研究进展.矿业安全与环保,2000,27(4):28~30
[51]谭娅.燃煤固硫添加剂的实验研究及其促进固硫机理分析:[湖南大学硕士论文].长沙:湖南大学,2005
[52]聂其红,孙绍增,李争起.褐煤混煤燃烧特性的热重分析法研究.燃料科学与术,2001,7(1):72~76
[53]Ma baoguo,Li xiangguo,Xu li,Wang kai.Investigation on catalyzed combustion of high ash coal by thermogravimetric analysis.Thermochimica Acta,2006,44(5):19~22
[54]马温亮.催化燃烧技术基本原理进展及其应用研究.科技资讯,2007,1:6
[55]马奕.高温燃煤脱硫机理研究及微观物化分析:[浙江大学硕士论文].浙江:浙江大学,2003
[56]H.B.Vuthaluru.Ivestigationas into the Pyrdlytic Behaviour of Coal/Blends Using thermogravimetric Analysis.Bioresource Technalogy,2004(92):187~195
[57]Naruse I,Kim H J,Lu G Q et al.Study on Charaeteristies of Self-Desulufrization and Self-Denitrifieation in Biobriquette Combustion.In Proeeedings of the1998 27th International Symposium on Combustion,USA Boulder Co,1998(2):2973~2979
[58]李莹莹,刘艳华,车得福.添加剂对燃煤 NO 排放的影响.燃烧科学与技术,2004,10(3):275~277
[2]李伟.燃煤固硫添加剂的研究:[硕士学位论文].北京:北京工商大学,2001
[3]刘同华.DCL 型燃煤固硫剂固硫技术在广州石化热电站的应用.安全与环境,2002,9(4):13~16
[4]杨海波,武增华,邱新平.CaO 固硫反应机理研究新进展.燃料化学学报,2003,31(1):92~96
[5]郝吉明.燃煤二氧化硫污染控制技术手册.北京:化学工业出版社,2001
[6]杨丽芬.环保工作者实用手册.北京:冶金工业出版社,2001
[7]王春波.钙基脱硫剂调质发展现状及展望.锅炉技术,2000,3(8):1~4
[8]Jun Cheng,Junhu Zhou,Jianzhong Liu,et al.Sulfur Removal at High Temperature during Coal Combustion in Furnaces.Progress in Energy and Combustion Science,2003,29(5):381~405
[9]Chunbo Wang,Xianglin Shen,Yiqian Xu.Investigation on Sulfation of Modified Ca-based Sorbent.Fuel Procession Technology,2002,79(2):121~133
[10]Burnett,T. A. and W. L. Wells.Conceptual design and economics of an improved magnesium oxide flue gas desulphurization process.ACS Symposium Series,1982,188(3):381~415
[11]张基伟.国外燃煤电厂烟气脱硫技术综述.中国电力,1999,32(7):61~65
[12]李彩亭.燃煤锅炉烟气湿式除尘脱硫技术及粉煤灰利用的研究:[博士学位论文].长沙:湖南大学,2002
[13]郝吉明,马广大.大气污染控制工程.北京:高等教育出版社,2002
[14]Karatepe,Nilgun.A comparison of flue gas desulfurzation processes.Energy Sources,2000,22(3):197~206
[15]中国环境科学学会.脱硫技术.北京:中国环境科学出版社,1995
[16]宋国菡,萧芳.酸雨对环境的影响及防止对策.农业环境保护,1998,17(3):141~143
[17]路春美.钙基材料用于燃煤煅烧固硫过程研究:[博士学位论文].山东:山东大学,2002
[18]毛健雄,毛健全,赵树民.煤的洁净燃烧.北京:科学出版社,1998
[19]罗军.燃煤固硫及其机理的研究:[硕士学位论文].广州:华南理工大学,2001
[20]杨扬.烟气脱硫技术的现状与发展前景.中国环境科学,1994,4(3):10~15
[21]Xu Lusi,Cen Zewen,Zen Hancai.Experimental study on the adsorption of NO and SO2 by activated carbon fibers.Journal of Huazhong University of Science an Technology,2006,34(2):105~108
[22]Young Sun Mok,In-Sik Nam.Positive pulsed corona discharge process for simultaneous removal of SO2 and NO from iron-ore sintering flue gas.IEEE Transactions on Plasma Science,1999,27(4):1188~1190
[23]卢啸凤,王致均.燃煤流化床新型脱硫剂的研究.中国环境科学,1992,12(1):40~43
[24]李斌,葛宜掌,章祥麟等.钙基固硫剂固硫技术概述.煤化工,1996,15(1):48~51
[25]庞亚军.掺加粉煤灰提高含钙脱硫剂的烟气脱硫率的实验研究.工程热物理学报,1992,13(4):443~447
[26]张良全.Fe2O3对型煤固硫作用的机理探讨.环境科学,1997,18(1):65~67
[27]陈亚非.金属氧化物对Ca(OH)2脱硫影响的研究.工程热物理学报,1997,18(4):517~520
[25]肖佩林,李书年.铁硅系添加剂对型煤燃烧时行为的影响.环境科学学报,1996,16(l):97~102
[29]肖佩林.高温固硫反应中锶化合物的促进作用.环境化学,1994,13(5):389~394
[30]许满贵,李建伟,葛岭梅.粉煤灰添加剂对石灰石脱硫的作用.西安矿业学院学报,1998,18(2):149~153
[31]Paolo Davini,et al.An investigation of the influence of sodium chloride on the desulphurization properties of limestone.FUEL,1992,7(1):831~834
[32]Yang.R.T. and Shen.M.S.Fluidized-bed combustion of coal with lime additive catalytic sulfation of lime with iron compounds and coal ash.American Chemical Society,1978,12:915~917
[33]Desal.M.J. and Yang.R.T.Enhancement of sulfation of calcium oxide by iron oxide.Ind. Eng. Chem. Process Des. Dev,1983,22:119~123
[34]Mark R.Stouffer et al.An investigation of CaO sulfation mechanisms in boiler sorbent injection.AICHE J,1989,35(8):1253~1262
[35]Juan Adanez,et al.Study of modified calcium hydroxides for enhancing SO2 removal during sorbent injection in pulverized coal boilers.Fuel,1997,76(3):257~265
[36]DavidA,et al.Structural changes in surfactant-modified sorbents during furnace injection.AICHE J,1990,35(3):500~506
[37]Eiji Sasaoka and Norimasa Sada.Preparation of macroporous lime from natural lime by swelling method with acetic acid forhigh-temperature desulfurization.Ind. Eng. Chem. Res,1998,37:3943~3949
[38]陈鸿伟,王春波.复合调质提高CaO固硫率的试验研究.环境科学学报,1999,19(4):357~361
[39]王春波,陈鸿伟.提高CaO固硫率的实验及分析.华北大力大学学报,1999,26(2):85~90
[40]任有中,董佳芳.洁净型煤中提高碳酸钙脱硫性能的新技术.工程热物理学报,1999,20(1):30~32
[41]蔡卫权.纳米催化技术用于空气净化.环境污染治理技术与设备,2004,5(4):58~61
[42]姜兆华.应用表面化学与技术.哈尔滨:哈尔滨工业大学出版社,2001
[43]张立德.纳米材料和纳米结构.北京:科学技术出版社,2001
[44]葛军,丁辉.纳米二氧化钛的应用与市场研究.材料导报,2004,18(2):65~68
[45]伊荔松,沈辉.二氧化钛光催化研究进展及应用.材料导报,2000,12(4):23~25
[46]姚超,林西平.纳米技术与纳米材料-纳米TiO2的液相合成.日用化学工业,2004,34(3):190~197
[47]袁中山,吴迪镛,王树东.采用一体化燃煤添加剂的燃煤中固硫作用研究.燃料化学学报,2002,30(1):36~40
[48]吕欣,林国珍,周广柱等.型煤燃烧过程中CaO的形成及其固硫作用.环境化学,1998,17(6):528~531
[49]程军,周俊虎,刘建忠等.电石渣和铝土粉的高温燃烧脱硫特性及微观分析.环境科学学报,2003,23(5):641~646
[50]湛伦建,赵跃民.工业型煤燃烧固硫的研究进展.矿业安全与环保,2000,27(4):28~30
[51]谭娅.燃煤固硫添加剂的实验研究及其促进固硫机理分析:[湖南大学硕士论文].长沙:湖南大学,2005
[52]聂其红,孙绍增,李争起.褐煤混煤燃烧特性的热重分析法研究.燃料科学与术,2001,7(1):72~76
[53]Ma baoguo,Li xiangguo,Xu li,Wang kai.Investigation on catalyzed combustion of high ash coal by thermogravimetric analysis.Thermochimica Acta,2006,44(5):19~22
[54]马温亮.催化燃烧技术基本原理进展及其应用研究.科技资讯,2007,1:6
[55]马奕.高温燃煤脱硫机理研究及微观物化分析:[浙江大学硕士论文].浙江:浙江大学,2003
[56]H.B.Vuthaluru.Ivestigationas into the Pyrdlytic Behaviour of Coal/Blends Using thermogravimetric Analysis.Bioresource Technalogy,2004(92):187~195
[57]Naruse I,Kim H J,Lu G Q et al.Study on Charaeteristies of Self-Desulufrization and Self-Denitrifieation in Biobriquette Combustion.In Proeeedings of the1998 27th International Symposium on Combustion,USA Boulder Co,1998(2):2973~2979
[58]李莹莹,刘艳华,车得福.添加剂对燃煤 NO 排放的影响.燃烧科学与技术,2004,10(3):275~277