选择性催化还原工艺中硫酸氢铵形成机理及影响因素Formation mechanism and influencing factors of ammonium bisulfate during the selective catalytic reduction process
马双忱,郭蒙,宋卉卉,陈公达,杨洁红,藏斌,李钊
摘要(Abstract):
论述了选择性催化还原(SCR)烟气脱硝过程中硫酸氢铵(ABS)的形成机理,并分析了温度、氨逃逸量、SO3浓度、飞灰等对ABS形成的影响规律。分析表明:ABS的形成温度为190~240℃;当温度在320~345℃时ABS为气相,当温度高于345℃时ABS开始分解;为减少ABS的生成量,可通过控制NH3/NOx摩尔比在0.8~1.2之间,以减少氨逃逸量,同时尽可能减少烟气中SO2氧化率;调节SCR工艺运行温度,控制ABS在催化剂中的沉积,可避免催化剂堵塞和腐蚀。
关键词(KeyWords): 烟气脱硝;选择性催化还原;硫酸氢铵;氨逃逸;空气预热器
基金项目(Foundation):
作者(Author): 马双忱,郭蒙,宋卉卉,陈公达,杨洁红,藏斌,李钊
参考文献(References):
- [1]张强,许世森,王志强,等.选择性催化还原烟气脱硝技术进展及工程应用[J].热力发电,2004(4):1-6.ZHANG Qiang,XU Shishen,WANG Zhiqiang.Advancement and engineering application of flue gas denitrification technology by using selective catalytic reduction method[J].Thermal Power Generation,2004(4):1-6.
- [2]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.YANG Yang.NOx reduction technology and flue gas denitrification project[M].Beijing:Metallurgical Industry Press,2007(in Chinese).
- [3]马双忱,金鑫,孙云雪,等.SCR烟气脱硝过程硫酸氢铵的生成机理与控制[J].热力发电,2010,39(8):12-17.MA Shuangchen,JIN Xin,SUN Yunxue,et al.The formation mechanism of ammonium bisulfate in SCR flue gas denitrification process and control thereof[J].Thermal Power Generation,2010,39(8):12-17.
- [4]Chothani C.Ammonium bisulfate(ABS)measurement for SCR NOx control and air heater protection[R].Carnegie:Breen Energy Solution,2008:1-13.
- [5]赵宗让.电厂锅炉SCR烟气脱硝系统设计优化[J].中国电力,2005,38(11):69-74.ZHAO Zongrang.Design optimization of SCR system for coal-fired boilers[J].Electric Power:2005,38(11):69-74.
- [6]吴碧君,王述刚,方志星,等.烟气脱硝工艺及其化学反应原理分析[J].热力发电,2006(11):59-60.WU Bijun,WANG Shugang,FANG Zhixing,et al.Flue gas denttrification(denitrification)technologies and analysis of their chemical reactons[J].Thermal Power Generation,2006(11):59-60.
- [7]Moretti A L,Triscori R J,Ritzenthaler D P.A system approach to SO3 mitigation[R].Ohio:The Babcock&Wilcox Company,2006:1-6.
- [8]Hans J H,Lindenhoff P I,Safronov S.SCR design issues in reduction of NOxemissions from thermal power plants[R].Frederikssund:Haldor Topsoe Inc,2007:1-21.
- [9]Scot P,Chris D.SCR catalyst management:enhancing operational flexibility[C]//Power plant air pollutant control mega symposium.2006:1-12.
- [10]Moser R E.Benefits of effective SO3removal in coalfired power plants:beyond opacity control[R].Power Plant Air Pollutant Control Mega Symposium,2006:1-14.
- [11]Ahmad S,Lindenhoff P I,Slaughter J D.Experience with design,installation and operation of a SCR unit after a FCCU[C]//Catalyst Technology at Annual NPRA Meeting.2005:1-10.
- [12]Shomate C H,Naylor B F.High-temperature heat contents of aluminum oxide,aluminum sulfate,potassium sulfate,ammonium sulfate and ammonium bisulfate[J].Journal of the American Chemical Society,1945,67(1):72-75.
- [13]Shikade T,Oba T,Fujimoto K,et al.Chemical product research and development[J].Industrial Engineering,1984,23:417.
- [14]Sutula R A,Hunt J B.Stoichiometry and kinetics of the decomposition of some cobalt(III)ammines in molten ammonium bisulfate and concentrated sulfuric acid[J].Inorganic Chemistry 1972,11(8):1879-1886.
- [15]Wilburn R T,Wright T L.SCR ammonia slip distribution in coal plant effluents and dependence upon SO3[J].Power Plant Chemistry,2004,6:295-314.
- [16]Burke J M,Johnson K L.Ammonium sulfate and bisulfate formation in air preheaters[R].Washington:United States Environment Protection Agency,1982.
- [17]Ando J.NOxabetement for stationary sources in japan[R].Washington:United States Environment Protection Agency,1979.
- [18]Nenad S.Improving the performance of boiler auxiliaries,Part I[J].Coal Power,2010(10):1-35.
- [19]Wright T,DeLallo M.Increased SO3and ammonia slip from SCR:balancing air heater deposits,ammonia in effluent discharge,and SO3 plume[C]//Proceedings of2002conference on selective catalytic reduction(SCR)and selective non-catalytic reduction(SNCR)for NOx control.Pittsburgh,Pennsylvania:National Energy Technology Laboratory(NETL).2002.
- [20]Nenad S.Improving the performance of boiler auxiliaries,Part II[J].Coal Power,2011(2):1-35.
- [21]Thogersen J R,Slabiak T,White N,et al.Ammonium bisulphate inhibition of SCR catalysts[R].Frederikssund:Haldor Topsoe Inc,2007:1-16.
- [22]Zhu Z P,Niu H X,Liu Z Y,et.al.Decomposition and reactivity of NH4HSO4on V2O5/AC catalysts used for NO reduction with ammonia[J].Journal of Catalysis,2000,195(2):268-278.
- [23]李靖华,张桂恩.硫酸氢铵分解动力学及其分解机理的研究[J].物理化学学报,1992,8(1):123-127.LI Jinghua,ZHANG Guien.Investigation of the kinetics and mechanism of decomposition of ammonium hydrogensulfate[J].Acta Physico-chimica Sinica:1992,8(1):123-127.
- [24]Dean W.In situ analysis of ammonia slip and water vapour using a tunable diode laser for SCR/SNCR optimization and boiler tube surveillance in power plants[J].Instrumentation,Systems,and Automation Society Analysis Division Newsletter,2004,25(1):10-16.
- [25]Ando J.Recent developments in SO2and NOx abatement technology for stationary sources in Japan[J].1985.
- [26]Liu Z,Woo S I.Recent advances in catalytic DeNOx science and technology[J].Catalysis Reviews,2006,48(1):43-89.
- [27]Bondurant L P,Counterman W S,Rhodes R B.Minimizing the impact of SCR/SNCR retrofits on the ljungstrom air preheater[R].Wellsville:Alstom Power Air Preheater Inc,1999:1-6.
- [28]Nenad S.Improving the performance of boiler auxiliaries,Part III[J].Coal Power,2011(4):1-35.
- [29]Bilirgen H,Levy E,Romero C,et al.Optimizing combined boiler-SCR operations[J].Lehigh Energy Update,2009,27(1):1-2.
- [30]Romero C E.Optimization of SCR control technology for reduced NOxemissions,improved performance and reduced operating expenses[R].Bethlehem,PA:The New York State Energy Research and Development Authority,2009:1-92.
- [31]匡国强,徐党旗.选择性催化还原(SCR)脱硝装置对锅炉结构的影响[J].热力发电,2006(10):36-39.KUANG Guoqiang,XU Dangqi.Influence of SCR denitrification facility upon the boiler structure[J].Thermal Power Generation,2006(10):36-39.
- [32]Thomas.SCR operation optimization:SO3removal to optimize catalyst life&NH3 distribution in wastewater[R].Chattanooga,Tennessee,Parsons Energy&Chemicals,2003.