基于热力学平衡计算的燃煤电厂烟气中SO3形态研究Reseach on SO3 morphological characteristics in flue gas of coal-fired power plants based on thermodynamic equilibrium calculation
于伟静,马超,谭闻濒,崔磊,李昌浩
YU Weijing,MA Chao,TAN Wenbin,CUI Lei,LI Changhao
摘要(Abstract):
SO_3是燃煤电厂烟气排放常见污染物之一,对系统设备稳定运行和大气环境质量有较大影响。为深化相关研究,基于热力学及酸露点理论建立了SO_3形态转化计算模型,计算了不同烟气温度、湿度和SO_3浓度的形态特征,确定了常规燃煤电厂烟气中SO_3形态的分布特征,结果表明:燃煤电厂烟气中SO_3主要以SO_3气体、H_2SO_4气体和H_2SO_4气溶胶3种形态存在,形态转化基于化学反应和物理反应2个过程,化学反应指气态SO_3与H_2O结合形成气态H_2SO_4的过程,物理反应指在烟气温度降至酸露点以下时气态H_2SO_4通过均相或非均相成核形成H_2SO_4气溶胶的过程。此外,假设烟气湿度为8%,烟气温度低于202℃时,全部以H_2SO_4形态存在;烟气温度高于495℃时,全部以SO_3形态存在;烟气温度低于95℃时,基本以H_2SO_4气溶胶的形态存在。结合常规燃煤电厂烟气湿度和温度的分布情况,则SO_3形态的分布特征为:烟气脱硝装置前段,主要以SO_3气体形态存在;脱硝装置至空预器段,SO_3气体和H_2SO_4气体共同存在;空预器至脱硫装置段,H_2SO_4气体和H_2SO_4气溶胶共同存在;脱硫装置后段主要以H_2SO_4气溶胶形态存在,粒径<0.1μm。
SO_3 is one of the common pollutants discharged from coal-fired power plants,which has a great impact on the stable operation of system equipment and the quality of atmospheric environment. In order to deepen the relevant research,SO_3 morphologic transformation calculation model was established based on thermodynamics and acid dew point theory. The morphologic characteristics of different flue gas temperature,humidity and SO_3 concentration were calculated,and the distribution characteristics of SO_3 morphologic characteristics in flue gas from conventional coal-fired power plants were determined. The results show that SO_3 in flue gas of coal-fired power plants is mainly composed of SO_3 gas,H_2SO_4 gas and H_2SO_4 aerosol. The transformation of SO_3 is based on chemical reaction and physical reaction. The chemical reaction is that SO_3 gas reacts with H_2O gas to H_2SO_4 gas and the physical reaction is that H_2SO_4 gas condenses to H_2SO_4 aerosol by homogeneous and heterogeneous nucleation when flue gas temperature is lower than dew point,respectively. In addition,assuming the valve of humidity is 8%,when the flue gas temperature is lower than 202 ℃,higher than 495 ℃ and lower than 95 ℃,SO_3 exists in the form of H_2SO_4 gas,SO_3 gas and H_2SO_4 aerosol,respectively. Furthermore,combined with the distribution of flue gas humidity and temperature in conventional coal-fired power plants,the distribution characteristics of SO_3 are as follows: SO_3 gas,SO_3 gas and H_2SO_4 gas,H_2SO_4 gas and H_2SO_4 aerosol,H_2SO_4 aerosol exist the section ahead denitrification device,between denitrification device and air preheater,between air preheater and rear section of desulfurization unit,respectively. What is more,the particle size of H_2SO_4 aerosol is less than 0.1 μm.
关键词(KeyWords):
燃煤电厂;热力学平衡;SO_3;硫酸气体;硫酸气溶胶
coal-fired power plant;thermodynamic equilibrium;SO_3;H_2SO_4 gas;H_2SO_4 aerosol
基金项目(Foundation): 中国华电集团重点科技研发项目(CHDKJ19-01-34)
作者(Author):
于伟静,马超,谭闻濒,崔磊,李昌浩
YU Weijing,MA Chao,TAN Wenbin,CUI Lei,LI Changhao
DOI: 10.13226/j.issn.1006-6772.19071301
参考文献(References):
- [1]BP集团.BP世界能源统计年鉴[EB/OL].(2020-06-07).https://www.bp.com/zh_cn/china/home/news/reports.html.British Petroleum Company.BP statistical review of world energy[EB/OL].(2020-06-07).https://www.bp.com/zh_cn/china/home/news/reports.html.
- [2]TANG L,QU J,MI Z,et al.Substantial emission reductions from Chinese power plants after the introduction of ultra-low emissions standards[J].Nature Energy,2019,4(11):929-938.
- [3]郦建国,朱法华,孙雪丽.中国火电大气污染防治现状及挑战[J].中国电力,2018,51(6):6-14.LI Jianguo,ZHU Fahua,SUN Xueli.Current status and challenges of atmospheric pollution prevention and control of thermal power plants in China[J].Electric Power,2018,51(6):6-14.
- [4]ZHENG C,LI X,YANG Z,et al.Development and experimental evaluation of a continuous monitor for SO3measurement[J].Energy&Fuels,2017,31(9):9684-9692.
- [5]中华人民共和国国家发展和改革委员会.关于印发《煤电节能减排升级与改造行动计划(2014-2020年)的通知[EB/OL].(2014-09-12).http://zfxxgk.nea.gov.cn/auto84/201409/t20140919_1840.htm.
- [6]中华人民共和国生态环境部.关于印发《全面实施燃煤电厂超低排放和节能改造工作方案》的通知[EB/OL].(2015-12-11).http://www.mee.gov.cn/gkml/hbb/bwj/201512/t20151215_319170.htm.
- [7]环境保护部.火电厂污染防治可行技术指南:HJ 2301-2017.[S].北京:中国环境科学出版社,2017.
- [8]CARPENTER A M.Low water FGD technologies[R].London:IEA Clean Coal Centre,2012.
- [9]CAO Y,ZHOU H,JIANG W,et al.Studies of the fate of sulfur trioxide in coal-fired utility boilers based on modified selected condensation methods[J].Environmental Science&Technology,2010,44(9):3429-3434.
- [10]张悠.烟气中SO3测试技术及其应用研究[D].杭州:浙江大学,2013.ZHANG You.Research and application of SO3measurement in flue gas[D].Hangzhou:Zhejiang University,2013.
- [11]WALSH P M,MCCAIN J D,CUSHING K M.Evaluation and mitigation of visible acidic aerosol plumes from coal fired power boilers[R].US:Environmental Protection Agency,2006.
- [12]ZHENG C,LI X,YANG Z,et al.Development and experimental evaluation of a continuous monitor for SO3measurement[J].Energy&Fuels,2017,31(9):9684-9692.
- [13]WANG Z,HU Y,CHENG X,et al.Study of adsorption characteristics of calcium-based sorbents with SO3[J].Energy Procedia,2018,144:43-49.
- [14]刘含笑,陈招妹,王少权,等.燃煤电厂SO3排放特征及其脱除技术[J].环境工程学报,2019,13(5):1128-1138.LIU Hanxiao,CHEN Zhaomei,WANG Shaoquan,et al.Emission characteristics and removal technology of SO3from coal-fired power plants[J].Chinese Journal of Environmental Engineering,2019,13(5):1128-1138.
- [15]STUART D.Acid dewpoint temperature measurement and its use in estimating sulfur trioxide concentration[C]//55th Analysis Division Symposium.USA:Curran Associates,Inc.,2010.
- [16]JAWOROWSKI R J,MACK S S.Evaluation of methods for measurement of SO3/H2SO4in flue gas[J].Journal of the Air Pollution Control Association,1979,29(1):43-46.
- [17]XIONG J,LI Y,WANG J,et al.Evaluation of sulfur trioxide detection with online isopropanol absorption method[J].Journal of Environmental Sciences,2018,72:25-32.
- [18]VAINIO E,FLEIG D,BRINK A,et al.Experimental evaluation and field application of a salt method for SO3measurement in flue gases[J].Energy&Fuels,2013,27(5):2767-2775.
- [19]FLEIG D,VAINIO E,ANDERSSON K,et al.Evaluation of SO3measurement techniques in air and oxy-fuel combustion[J].Energy&Fuels,2012,26(9):5537-5549.
- [20]杨丁,陈永强,陈威祥,等.SO3采样技术改进及烟气处理设备SO3脱除能力测试[J].中国电力,2018,51(7):157-161.YANG Ding,CHEN Yongqiang,CHEN Weixiang,et al.Improvement of SO3sampling technology and SO3removal capability testing of flue gas treatment equipment[J].Electric Power,2018,51(7):157-161.
- [21]HARDMAN R,STACY R,DISMUKES E.Estimating sulfuric acid aerosol emissions from coal-fired power plants[C]//DOE-FETCConference on Formation,Distribution,Impact,and Fate of Sulfur Trioxide in Utility Flue Gas Streams.Pittsburgh,PA:USDepartment of Energy-FETC,1998.
- [22]SRIVASTAVA R K,MILLER C A,ERICKSON C,et al.Emissions of sulfur trioxide from coal-fired power plants[J].Journal of the Air&Waste Management Association,2004,54(6):750-762.
- [23]李欣怡,潘丹萍,胡斌,等.燃煤烟气中SO3迁移转化特性及其控制的研究现状及展望[J].化工进展,2018,37 (12):4887-4896.LI Xinyi,PAN Danping,HU Bin,et al.Research status and prospects of migration,transformation and control of SO3from coalfired flue gas[J].Chemical Industry and Engineering,2018,37(12):4887-4896.
- [24]胡斌,刘勇,杨春敏,等.化学团聚促进电除尘脱除烟气中PM2.5和SO3[J].化工学报,2016,67(9):3903-3909.HU Bing,LIU Yong,YANG Chunmin,et al.Simultaneous control of PM2.5and SO3by chemical agglomeration collaborative electrostatic precipitation[J].CIESC Journal,2016,67 (9):3903-3909.
- [25]PAN D,YANG L,WU H,et al.Removal characteristics of sulfuric acid aerosols from coal-fired power plants[J].Journal of the Air&Waste Management Association,2016,67 (3):352-357.
- [26]BENSON L B.Use of magnesium hydroxide for reduction of plume visibility in coal-fired power plants[C]//Proceedings of the EPA-DOE-EPRI-A and WMA Power Plant Air Pollutant Control Mega Symposium.Pittsburgh:A&WMA,2006.
- [27]潘丹萍,吴昊,鲍静静,等.电厂湿法脱硫系统对烟气中细颗粒物及SO3酸雾脱除作用研究[J].中国电机工程学报,2016,36(16):4356-4362.PAN Danping,WU Hao,BAO Jingjing,et al.Removal effect of wet flue gas desulfurization system on fine particles and SO3acid mist from coal-fired power plants[J].Proceedings of the CSEE,2016,36(16):4356-4362.
- [28]高智溥,胡冬,张志刚,等.碱性吸附剂脱除SO3技术在大型燃煤机组中的应用[J].中国电力,2017,50(7):102-108.GAO Zhipu,HU Dong,ZHANG Zhigang,et al.Application of SO3removal with alkaline sorbent injection in large capacity coal-fired power plants[J].Electric Power,2017,50(7):102-108.
- [29]胡冬,王海刚,郭婷婷,等.燃煤电厂烟气SO3控制技术的研究及进展[J].科学技术与工程,2015,35(35):92-99.HU Dong,WANG Haigang,GU Tingting,et al.Research and development of mitigating technology of SO3in flue gas from coal power plants[J].Science Technology and Engineering,2015,35(35):92-99.
- [30]ZHENG C,WANG Y,LIU Y,et al.Formation,transformation,measurement,and control of SO3in coal-fired power plants[J].Fuel,2019,241:327-346.
- [31]LOVEJOY E R,HANSON D R,HUEY L G.Kinetics and products of the gas-phase reaction of SO3with water[J].The Journal of Physical Chemistry,1996,100(51):19911-19916.
- [32]REINER T,ARNOLD F.Laboratory investigations of gaseous sulfuric acid formation via SO3+H2O+M→H2SO4+M:Measurement of the rate constant and product identification[J].The Journal of Chemical Physics,1994,101(9):7399-7407.
- [33]BRACHERT L,KOCHENBURGER T,SCHABER K.Facing the sulfuric acid aerosol problem in flue gas cleaning:Pilot plant experiments and simulation[J].Aerosol Science and technology,2013,47(10):1083-1091.
- [34]BLYTHE G,DOMBROWSKI K.SO3mitigation guide update[R].US:Electric Power Research Institute,2004.
- [35]李松林,周亚平,刘俊吉.物理化学[M].北京:高等教育出版社,2015.LI Songlin,ZHOU Yaping,LIU Junjie.Physical chemistry[M].Beijing:Higher Education Press,2015.
- [36]Physical properties Table[EB/OL].[2020-07-07].https://www.academia.edu/20319781/Physical_properties_table.
- [37]DOROFEEVA O V,IORISH V S,NOVIKOV V P,et al.NIST-JANAF thermochemical tables.I:Three molecules related to atmospheric chemistry:HNO3,H2SO4,and H2O2[J].Journal of Physical and Chemical Reference Data,2003,32(2):879-901.
- [38]MALCOLM Jr W.NIST-JANAF thermochemical tables[M].US:American Institute of Physics and The American Chemical Society,1998.
- [39]于伟静,马超,崔磊,等.SO3标准气体制备装置:209778305U[P].2019-12-13.YU Weijing,MA Chao,CUI Lei,et al.SO3standard gas preparation device:209778305U[P].2019-12-13.