1000MW燃煤电厂商业SCR脱硝催化剂的失活
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摘要
以浙江某燃煤电厂1000MW商业SCR脱硝催化剂为研究对象,通过催化表征和活性评价综合分析该电厂1000MW商业SCR脱硝催化剂的失活原因.研究表明,催化剂的失活是多种因素共同作用的结果,(1)Fe,S,K和As元素中毒,其元素含量较新鲜催化剂分别增加了318.0%,233.3%,199.3%和99.8%;(2)催化剂表面孔道的飞灰堵塞,硫酸盐类沉积以及长时间高温反应造成催化剂的烧结和颗粒物的团聚,导致失活SCR脱硝催化剂比表面积较新鲜催化剂下降了20.3%;(3)活性组分V的价态变化造成V~(4+)/V~(5+)的比值由6.46下降至1.35,以及Lewis酸位点减少了34.2%,从而导致催化剂的失活.
Fresh and used commercial SCR catalysts(40000 hours) obtained from a 1000 MW coal-fired plant in Zhejiang Province(China) were examined by catalyst characterization and De-NOx activity test to investigate the deactivation mechanism. The resultsshowed that the deactivation of the catalyst wasattributed to different aspects.(1)Commercial SCR catalyst was poisoned by Fe,S,Kand As. The content of Fe, S, K and As on deactivated catalyst increased by 318.0%, 233.3%, 199.3% and 99.8% compared withfresh catalyst, respectively.(2)Deposition of sulphate species and fly ash blocked the pores of SCR catalyst were blocked byDeposition of sulphate species and fly ash, resulting in the decrease of about 20.3%for surface area.(3)Valence of active component(vanadium) and Lewis acid site were changed during the process of deactivation. Compared with fresh catalyst, the V~(4+)/V~(5+)ratio ofdeactivated catalyst fell from 6.46 to 1.35, as well as the reduction of 34.2% for Lewis acid site.
Fresh and used commercial SCR catalysts(40000 hours) obtained from a 1000 MW coal-fired plant in Zhejiang Province(China) were examined by catalyst characterization and De-NOx activity test to investigate the deactivation mechanism. The resultsshowed that the deactivation of the catalyst wasattributed to different aspects.(1)Commercial SCR catalyst was poisoned by Fe,S,Kand As. The content of Fe, S, K and As on deactivated catalyst increased by 318.0%, 233.3%, 199.3% and 99.8% compared withfresh catalyst, respectively.(2)Deposition of sulphate species and fly ash blocked the pores of SCR catalyst were blocked byDeposition of sulphate species and fly ash, resulting in the decrease of about 20.3%for surface area.(3)Valence of active component(vanadium) and Lewis acid site were changed during the process of deactivation. Compared with fresh catalyst, the V~(4+)/V~(5+)ratio ofdeactivated catalyst fell from 6.46 to 1.35, as well as the reduction of 34.2% for Lewis acid site.
引文
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[2]李新艳,李恒鹏.中国大气NH3和NOx排放的时空分布特征[J].中国环境科学, 2012,32(1):37-42.Li X Y, LI H P. Emission and distribution of NH3and NOx in China[J].China Environmental Science, 2012,32(1):37-42.
[3]李帅英,武宝会,姚皓,等.SCR催化剂活性评估对NOx超低排放影响[J].中国电力, 2017,50(8):163-167.Li S W, Wu B H, Yao H, et al. Effect of SCR catalyst activity assessment onultra-low NOx emission[J]. Electric Power, 2017,50(8):163-167.
[4]王志轩.论我国火电厂氮氧化物控制[J].中国电力企业管理,2009,(22):16-19.Wang Z X. Discussion on nitrogen oxide control of thermal power plant inChina[J]. China Power Enterprise Management, 2009,(22):16-19.
[5]王春兰,宋浩,韩东琴.SCR脱硝催化剂再生技术的发展及应用[J].中国环保产业, 2014,(4):22-25.WangCL,SONGH,HanDQ.DevelopmentandApplicationofRecyclingTechnologyofSCRDenitrationCatalyticAgent[J].Technology&Engineering Application, 2014,(4):22-25.
[6]李德波,廖永进,徐齐胜,等.燃煤电站SCR脱硝催化剂更换策略研究[J].中国电力, 2014,47(3):155-159.Li D B, Liao Y J, Xu Q S, et al. Study on replacement strategy of SCRdenitrification catalyst in coal-fired power station[J]. Electric Power,2014,47(3):155-159.
[7]雷嗣远,孔凡海,王乐乐,等.燃煤电厂SCR脱硝催化剂磨损诊断及对策研究[J].中国电力, 2018,51(1):158-163.Lei S Y, Kong F H, Wang L L, et al. Diagnosis and countermeasures ofSCRdenitrificationcatalystwearincoal-firedpowerplants[J].Electric Power, 2018,51(1):158-163.
[8]YanKY,ChiHE,ChenJS,etal.DeactivationmechanismofDe-NOx catalyst(V2O5-WO3/Ti O2)used in coal fired power plant[J].Journal of Fuel Chemistry&Technology, 2012,40(11):1359-1365.
[9]曹俊,傅敏,周林,等.SCR脱硝催化剂中毒的研究进展[J].应用化工, 2018,(2):380-385.Cao J, Fu M, Zhou L, et al.Research progress of SCR denitrificationcatalyst poisoning[J]. Applied Chemical Industry, 2018,(2):380-385.
[10]孙晓亮.Cu O-CexZr(1-x)O2/Ti O2催化剂NH3选择性催化还原柴油机NOx的基础研究[D].天津:天津大学, 2014.SunXL.StudyonCu O-Cex Zr1-x O2/Ti O2catalystsfortheselectivecatalyticreductionofNOxwithNH3fromdieselengines[D].TianjinUniversity, 2014.
[11]KamataH,TakahashiK,OdenbrandCUI.TheroleofK2OintheselectivereductionofNOwithNH3overaV2O5(WO3)/Ti O2commercialselectivecatalyticreductioncatalyst[J].JournalofMolecular Catalysis A Chemical, 1999,139(2/3):189-198.
[12]HilbrigF,GoebelHE,KnoezingerH,etal.X-rayabsorptionspectroscopystudyofthetitania-andalumina-supportedtungstenoxide system[J]. Cheminform, 1991,22(47):6973-6978.
[13]ChenJP,YangRT.MechanismofpoisoningoftheV2O5/Ti O2catalystforthereductionofNObyNH3[J].JournalofCatalysis,1990,125(2):411-420.
[14]ZhengY,AndADJ,JohnssonJE.LaboratoryInvestigationofSelectiveCatalyticReductionCatalysts:DeactivationbyPotassiumCompoundsandCatalystRegeneration[J].Industrial&EngineeringChemistry Research, 2004,43(4):941-947.
[15]张秋林.Ca O对SCR催化剂选择的影响[J].能源研究与利用, 2006,(6):34-35.ZhangQL.TheinfluenceofCa OonSCRcatalystselection[J].Energy Research&Utilization, 2006,(6):34-35.
[16]何德良,任慧莺,朱天时,等.V2O5-WO3/Ti O2SCR催化剂的钙中毒机理研究[J].应用基础与工程科学学报, 2018,(1):1-11.HeDL,RenHY,ZhuTS,etal.CalciumpoisoningmechanismofV2O5-WO3/Ti O2SCRcatalyst[J].JournalofBasicScienceandEngineering, 2018,(1):1-11.
[17]FoersterM.Methodforregenerationiron-loadedDe-NOxcatalysts[M]. US. 2009.
[18]商雪松,陈进生,赵金平,等.SCR脱硝催化剂失活及其原因研究[J].燃料化学学报, 2011,39(6):465-470.Shang X S, Chen J S, Zhao J P, et al. Discussion on the deactivation ofSCRdenitrificationcatalystanditsreasons[J].JournalofFuelChemistry and Technology, 2011,39(6):465-470.
[19]Emeis C A. Chem Inform Abstract:Determination of Integrated MolarExtinction Coefficients for IR Absorption Bands of Pyridine Adsorbedon Solid Acid Catalysts[J]. Cheminform, 2010,24(38).
[20]ForzattiP.PresentstatusandperspectivesinDe-NOxSCRcatalysis[J]. Applied Catalysis A General, 2001,222(1):221-236.
[21]HandbookoftheElementsandNativeOxides.XPSInternational,Inc.1999[Z].
[22]段瑞瑞.V4+/V5+比值调变影响因素及其V4+和V5+转化的氧化还原速率与SCR脱硝活性[D].哈尔滨:哈尔滨工程大学, 2014.DuanRR.InfluencesonmodulationoftheV4+/V5+ratioandrateofV4+andV5+redoxandSCRDe NOxactivity[D].Harbin:HarbinEngineering University, 2014.
[23]陈艳萍.1000MW燃煤电厂钒钛系商业催化剂失活原因分析和再生研究[D].杭州:浙江大学, 2015.ChenYP.TheStudyofdeactivationmechanismandregenerationofcommercialV2O5-WO3/Ti O2SCRcatalystsusedin1000MWcoalfired power plant[D]. Hangzhou:Zhejiang University, 2015.