SCR脱硝催化剂中毒的研究进展
|
摘要
目前选择性催化还原法(SCR)是烟气脱硝的主要方法,而催化剂的选择则是SCR脱硝技术的关键,直接影响整个处理系统的脱硝效率与脱硝成本。探究催化剂中毒及其机理,将为现有催化剂的优化及新型催化剂的开发提供理论依据。针对脱硝过程中催化剂中毒现象,概述了SCR催化剂在使用过程中碱(土)金属、重金属、H_2O和SO_2中毒的研究进展,总结了催化剂中毒的机理,展望了SCR研究发展方向。
At present,selective catalytic reduction( SCR) is the main method for flue gas denitrification,the catalyst is the most important component of this system,it will directly affect the denitration efficiency and denitrification cost of the whole system. Exploring the catalyst poisoning and its mechanism for the optimization of existing catalysts and the development of new catalysts to provide a theoretical basis. In view of the phenomenon of catalyst poisoning in the process of denitrification,the research progress of alkali( alkali-earth) metal,heavy metal,H_2O and SO_2 poisoning in SCR catalyst was summarized. The mechanism of catalyst poisoning was summarized,and the development direction of SCR was prospected.
At present,selective catalytic reduction( SCR) is the main method for flue gas denitrification,the catalyst is the most important component of this system,it will directly affect the denitration efficiency and denitrification cost of the whole system. Exploring the catalyst poisoning and its mechanism for the optimization of existing catalysts and the development of new catalysts to provide a theoretical basis. In view of the phenomenon of catalyst poisoning in the process of denitrification,the research progress of alkali( alkali-earth) metal,heavy metal,H_2O and SO_2 poisoning in SCR catalyst was summarized. The mechanism of catalyst poisoning was summarized,and the development direction of SCR was prospected.
引文
[1]环境保护部,国家质量监督检验检疫总局.GB/T13223—2011火电厂大气污染物排放标准[S].北京:中国标准出版社,2011.
[2]席文昌,刘清才,魏春梅,等.蜂窝式脱硝催化剂在燃煤电厂中的应用研究[J].材料导报,2008,22(s3):282-284.
[3]贺泓,刘福东,余运波,等.环境友好的选择性催化还原氮氧化物催化剂[J].中国科学:化学,2012,1(4):446-468.
[4]周学荣,张晓鹏.SCR催化剂碱(土)金属中毒的研究进展[J].化学通报,2015,78(7):590-596.
[5]Wang S X,Guo R T,Pan W G,et al.The deactivation of Ce/Ti O2,catalyst for NH3-SCR reaction by alkali metals:TPD and DRIFT studies[J].Catalysis Communications,2017,89:143-147.
[6]Chen L,Li J,Ge M.Promotional effect of Ce-doped V2O5-WO3/Ti O2with low vanadium loadings for selective catalytic reduction of NOxby NH3[J].Journal of Physical Chemistry C,2009,113(50):21177-21184.
[7]Kern P,Klimczak M,Heinzelmann T,et al.High-throughput study of the effects of inorganic additives and poisons on NH3-SCR catalysts.Part II:Fe-zeolite catalysts[J].Applied Catalysis B Environmental,2010,95(1):48-56.
[8]陈新利,周爱奕,盛重义,等.钾盐沉积对Mn-Ce/Ti O2低温SCR催化剂脱硝性能的影响[J].电力科技与环保,2016,32(4):1-4.
[9]Deng L,Liu X,Cao P,et al.A study on deactivation of V2O5-WO3-Ti O2,SCR catalyst by alkali metals during entrained-flow combustion[J].Journal of the Energy Institute,2017,90(5):743-751.
[10]Zhang L,Cui S,Guo H,et al.The poisoning effect of potassium ions doped on Mn Ox/Ti O2catalysts for low-temperature selective catalytic reduction[J].Applied Surface Science,2015,355:1116-1122.
[11]Du X,Yang G,Chen Y,et al.The different poisoning behaviors of various alkali metal containing compounds on SCR catalyst[J].Applied Surface Science,2016,392:162-168.
[12]沈伯雄,卢凤菊,高兰君,等.中温商业SCR催化剂碱和碱土中毒特性研究[J].燃料化学学报,2016,44(4):500-506.
[13]Li X,Li X,Yang R T,et al.The poisoning effects of calcium on V2O5-WO3/Ti O2catalyst for the SCR reaction:Comparison of different forms of calcium[J].Molecular Catalysis,2017,434:16-24.
[14]王春杰.钒钛基SCR脱硝催化剂的制备及碱土金属中毒研究[D].北京:北京化工大学,2015.
[15]T Lei,Q Li,S Chen Z,et al.KCl-induced deactivation of V2O5-WO3/Ti O2catalyst during selective catalytic reduction of NO by NH3:Comparison of poisoning methods[J].Chemical Engineering Journal,2016,296:1-10.
[16]阮东亮.燃煤电厂SCR脱硝催化剂的中毒机理研究[D].广州:华南理工大学,2014.
[17]崔皎.火电厂SCR催化剂中毒机理的研究[D].北京:华北电力大学,2015.
[18]王俊杰,张亚平,王文选,等.商业V2O5-WO3/Ti O2烟气SCR脱硝催化剂Ca SO4中毒机理研究[J].燃料化学学报,2016,44(7):888-896.
[19]郭志敏,袁坚,彭小晋,等.钠盐对V2O5-WO3/Ti O2催化剂NH3-SCR反应活性的影响[J].分子催化,2016,30(6):547-556.
[20]Li X,Li X,Chen J,et al.An efficient novel regeneration method for Ca-poisoning V2O5-WO3/Ti O2,catalyst[J].Catalysis Communications,2016,87:45-48.
[21]赵欣,黄垒,李红蕊,等.过渡金属(Cu,Fe,Mn,Co)改性高分散V2O5/Ti O2作为高效NH3-SCR脱硝催化剂[J].催化学报,2015,36(11):1886-1899.
[22]姚小江,贡营涛,李红丽,等.铈基催化剂用于NH3选择性催化还原NOx的研究进展[J].物理化学学报,2015(5):817-828.
[23]姚小江,李露露,邹伟欣,等.高效Ce O2-Mn Ox-Al2O3催化剂的制备、表征及催化消除NO性能[J].催化学报,2016(8):1369-1380.
[24]杨政.钒钨钛催化剂碱金属中毒规律及抗中毒实验研究[D].重庆:重庆大学,2016.
[25]Cimino S,Lisi L,Tortorelli M.Low temperature SCR on supported Mn Ox,catalysts for marine exhaust gas cleaning:Effect of KCl poisoning[J].Chemical Engineering Journal,2016,283:223-230.
[26]李俊华,李想,彭悦,等.氧化砷对SCR催化剂失活效应与再生研究[C]∥中国化学会第30届学术年会摘要集-第二十六分会:环境化学.北京:中国化学会,2016.
[27]孙克勤,钟秦,于爱华.SCR催化剂的砷中毒研究[J].中国环保产业,2008(1):40-42.
[28]Kong M,Liu Q,Wang X,et al.Performance impact and poisoning mechanism of arsenic over commercial V2O5-WO3/Ti O2,SCR catalyst[J].Catalysis Communications,2015,72:121-126.
[29]王平,钱利科,姚友工.燃煤电厂砷中毒SCR脱硝催化剂再生技术研究[J].四川理工学院学报:自然科学版,2016,29(5):9-13.
[30]Xiang L,Li J,Yue P,et al.Mechanism of arsenic poisoning on SCR catalyst of Ce W/Ti and its novel efficient regenerati on method with hydrogen[J].Applied Catalysis B Environmental,2015,184:246-257.
[31]Peng Y,Si W,Li X,et al.Comparison of Mo O3,and WO3,on arsenic poisoning V2O5/Ti O2,catalyst:DRIFTS and DFT study[J].Applied Catalysis B Environmental,2016,181:692-698.
[32]Li X,Li X,Li J,et al.Identification of the arsenic resistance on Mo O3doped Ce O2/Ti O2catalyst for selective catalytic reduction of NOxwith ammonia[J].Journal of Hazardous Materials,2016,318:615-622.
[33]Yang J,Yang Q,Sun J,et al.Effects of mercury oxidation on V2O5-WO3/Ti O2,catalyst properties in NH3-SCR process[J].Catalysis Communications,2015,59:78-82.
[34]俞晋频.改性SCR催化剂汞氧化试验研究[D].杭州:浙江大学,2015.
[35]Yang Y,Liu J,Zhang B,et al.Experimental and theoretical studies of mercury oxidation over Ce O2-WO3/Ti O2,catalysts in coal-fired flue gas[J].Chemical Engineering Journal,2017,31:758-765.
[36]刘永超.SCR催化剂催化氧化单质汞实验研究[D].北京:华北电力大学,2015.
[37]Zhou Z,Liu X,Liao Z,et al.A novel low temperature catalyst regenerated from deactivated SCR catalyst for Hg0,oxidation[J].Chemical Engineering Journal,2016,304:121-128.
[38]Zhao S,Xu H,Mei J,et al.Ag-Mo modified SCR catalyst for a co-beneficial oxidation of elemental mercury at wide temperature range[J].Fuel,2017,200:236-243.
[39]徐旭.V2O5/Si C催化剂烟气脱硝机理及其反应动力学研究[D].杨州:扬州大学,2015.
[40]闫东杰,刘树军,黄学敏,等.SO2和H2O对Mn-Ce/Ti O2催化剂低温SCR活性的影响[J].安全与环境学报,2016(5):308-312.
[41]刘树军.SO2和H2O对Mn-Ce/Ti O2低温SCR催化剂的影响[D].西安:西安建筑科技大学,2015.
[42]Ma Z,Wu X,Feng Y,et al.Low-temperature SCR activity and SO2deactivation mechanism of Ce-modified V2O5-WO3/Ti O2catalyst[J].Progress in Natural Science:Materials International,2015,25(4):342-352.
[43]罗红成.H2O和SO2对Mn Ox/MWCNTs催化剂低温氨选择性催化还原NOx性能的影响[D].广州:华南理工大学,2012.
[44]杨剑,林凡,陈奎,等.含铈钒基SCR催化剂脱硝性能及SO2失活机理研究[J].燃料化学学报,2016,44(11):1394-1400.
[45]杨瀚.铁铈复合催化剂低温SCR脱硝性能、碱金属中毒机理及成型制备研究[D].南京:东南大学,2016.
[46]李博.选择性催化还原氮氧化物温度依存性及其抗二氧化硫中毒机理研究[D].杭州:浙江大学,2016.
[47]顾婷婷.表面硫改性和Ca掺杂对中低温SCR脱硝催化剂性能影响机理研究[D].杭州:浙江大学,2012.
[48]Xu T,Wu X,Liu X,et al.Effect of barium sulfate modification on the SO2tolerance of V2O5/Ti O2catalyst for NH3-SCR reaction[J].Science Direct,2017,57:110-117.
[49]Xu T,Wu X,Gao Y,et al.Comparative study on sulfur poisoning of V2O5-Sb2O3/Ti O2and V2O5-WO3/Ti O2monolithic catalysts for low-temperature NH3-SCR[J].Catalysis Communications,2017,93:33-36.
[2]席文昌,刘清才,魏春梅,等.蜂窝式脱硝催化剂在燃煤电厂中的应用研究[J].材料导报,2008,22(s3):282-284.
[3]贺泓,刘福东,余运波,等.环境友好的选择性催化还原氮氧化物催化剂[J].中国科学:化学,2012,1(4):446-468.
[4]周学荣,张晓鹏.SCR催化剂碱(土)金属中毒的研究进展[J].化学通报,2015,78(7):590-596.
[5]Wang S X,Guo R T,Pan W G,et al.The deactivation of Ce/Ti O2,catalyst for NH3-SCR reaction by alkali metals:TPD and DRIFT studies[J].Catalysis Communications,2017,89:143-147.
[6]Chen L,Li J,Ge M.Promotional effect of Ce-doped V2O5-WO3/Ti O2with low vanadium loadings for selective catalytic reduction of NOxby NH3[J].Journal of Physical Chemistry C,2009,113(50):21177-21184.
[7]Kern P,Klimczak M,Heinzelmann T,et al.High-throughput study of the effects of inorganic additives and poisons on NH3-SCR catalysts.Part II:Fe-zeolite catalysts[J].Applied Catalysis B Environmental,2010,95(1):48-56.
[8]陈新利,周爱奕,盛重义,等.钾盐沉积对Mn-Ce/Ti O2低温SCR催化剂脱硝性能的影响[J].电力科技与环保,2016,32(4):1-4.
[9]Deng L,Liu X,Cao P,et al.A study on deactivation of V2O5-WO3-Ti O2,SCR catalyst by alkali metals during entrained-flow combustion[J].Journal of the Energy Institute,2017,90(5):743-751.
[10]Zhang L,Cui S,Guo H,et al.The poisoning effect of potassium ions doped on Mn Ox/Ti O2catalysts for low-temperature selective catalytic reduction[J].Applied Surface Science,2015,355:1116-1122.
[11]Du X,Yang G,Chen Y,et al.The different poisoning behaviors of various alkali metal containing compounds on SCR catalyst[J].Applied Surface Science,2016,392:162-168.
[12]沈伯雄,卢凤菊,高兰君,等.中温商业SCR催化剂碱和碱土中毒特性研究[J].燃料化学学报,2016,44(4):500-506.
[13]Li X,Li X,Yang R T,et al.The poisoning effects of calcium on V2O5-WO3/Ti O2catalyst for the SCR reaction:Comparison of different forms of calcium[J].Molecular Catalysis,2017,434:16-24.
[14]王春杰.钒钛基SCR脱硝催化剂的制备及碱土金属中毒研究[D].北京:北京化工大学,2015.
[15]T Lei,Q Li,S Chen Z,et al.KCl-induced deactivation of V2O5-WO3/Ti O2catalyst during selective catalytic reduction of NO by NH3:Comparison of poisoning methods[J].Chemical Engineering Journal,2016,296:1-10.
[16]阮东亮.燃煤电厂SCR脱硝催化剂的中毒机理研究[D].广州:华南理工大学,2014.
[17]崔皎.火电厂SCR催化剂中毒机理的研究[D].北京:华北电力大学,2015.
[18]王俊杰,张亚平,王文选,等.商业V2O5-WO3/Ti O2烟气SCR脱硝催化剂Ca SO4中毒机理研究[J].燃料化学学报,2016,44(7):888-896.
[19]郭志敏,袁坚,彭小晋,等.钠盐对V2O5-WO3/Ti O2催化剂NH3-SCR反应活性的影响[J].分子催化,2016,30(6):547-556.
[20]Li X,Li X,Chen J,et al.An efficient novel regeneration method for Ca-poisoning V2O5-WO3/Ti O2,catalyst[J].Catalysis Communications,2016,87:45-48.
[21]赵欣,黄垒,李红蕊,等.过渡金属(Cu,Fe,Mn,Co)改性高分散V2O5/Ti O2作为高效NH3-SCR脱硝催化剂[J].催化学报,2015,36(11):1886-1899.
[22]姚小江,贡营涛,李红丽,等.铈基催化剂用于NH3选择性催化还原NOx的研究进展[J].物理化学学报,2015(5):817-828.
[23]姚小江,李露露,邹伟欣,等.高效Ce O2-Mn Ox-Al2O3催化剂的制备、表征及催化消除NO性能[J].催化学报,2016(8):1369-1380.
[24]杨政.钒钨钛催化剂碱金属中毒规律及抗中毒实验研究[D].重庆:重庆大学,2016.
[25]Cimino S,Lisi L,Tortorelli M.Low temperature SCR on supported Mn Ox,catalysts for marine exhaust gas cleaning:Effect of KCl poisoning[J].Chemical Engineering Journal,2016,283:223-230.
[26]李俊华,李想,彭悦,等.氧化砷对SCR催化剂失活效应与再生研究[C]∥中国化学会第30届学术年会摘要集-第二十六分会:环境化学.北京:中国化学会,2016.
[27]孙克勤,钟秦,于爱华.SCR催化剂的砷中毒研究[J].中国环保产业,2008(1):40-42.
[28]Kong M,Liu Q,Wang X,et al.Performance impact and poisoning mechanism of arsenic over commercial V2O5-WO3/Ti O2,SCR catalyst[J].Catalysis Communications,2015,72:121-126.
[29]王平,钱利科,姚友工.燃煤电厂砷中毒SCR脱硝催化剂再生技术研究[J].四川理工学院学报:自然科学版,2016,29(5):9-13.
[30]Xiang L,Li J,Yue P,et al.Mechanism of arsenic poisoning on SCR catalyst of Ce W/Ti and its novel efficient regenerati on method with hydrogen[J].Applied Catalysis B Environmental,2015,184:246-257.
[31]Peng Y,Si W,Li X,et al.Comparison of Mo O3,and WO3,on arsenic poisoning V2O5/Ti O2,catalyst:DRIFTS and DFT study[J].Applied Catalysis B Environmental,2016,181:692-698.
[32]Li X,Li X,Li J,et al.Identification of the arsenic resistance on Mo O3doped Ce O2/Ti O2catalyst for selective catalytic reduction of NOxwith ammonia[J].Journal of Hazardous Materials,2016,318:615-622.
[33]Yang J,Yang Q,Sun J,et al.Effects of mercury oxidation on V2O5-WO3/Ti O2,catalyst properties in NH3-SCR process[J].Catalysis Communications,2015,59:78-82.
[34]俞晋频.改性SCR催化剂汞氧化试验研究[D].杭州:浙江大学,2015.
[35]Yang Y,Liu J,Zhang B,et al.Experimental and theoretical studies of mercury oxidation over Ce O2-WO3/Ti O2,catalysts in coal-fired flue gas[J].Chemical Engineering Journal,2017,31:758-765.
[36]刘永超.SCR催化剂催化氧化单质汞实验研究[D].北京:华北电力大学,2015.
[37]Zhou Z,Liu X,Liao Z,et al.A novel low temperature catalyst regenerated from deactivated SCR catalyst for Hg0,oxidation[J].Chemical Engineering Journal,2016,304:121-128.
[38]Zhao S,Xu H,Mei J,et al.Ag-Mo modified SCR catalyst for a co-beneficial oxidation of elemental mercury at wide temperature range[J].Fuel,2017,200:236-243.
[39]徐旭.V2O5/Si C催化剂烟气脱硝机理及其反应动力学研究[D].杨州:扬州大学,2015.
[40]闫东杰,刘树军,黄学敏,等.SO2和H2O对Mn-Ce/Ti O2催化剂低温SCR活性的影响[J].安全与环境学报,2016(5):308-312.
[41]刘树军.SO2和H2O对Mn-Ce/Ti O2低温SCR催化剂的影响[D].西安:西安建筑科技大学,2015.
[42]Ma Z,Wu X,Feng Y,et al.Low-temperature SCR activity and SO2deactivation mechanism of Ce-modified V2O5-WO3/Ti O2catalyst[J].Progress in Natural Science:Materials International,2015,25(4):342-352.
[43]罗红成.H2O和SO2对Mn Ox/MWCNTs催化剂低温氨选择性催化还原NOx性能的影响[D].广州:华南理工大学,2012.
[44]杨剑,林凡,陈奎,等.含铈钒基SCR催化剂脱硝性能及SO2失活机理研究[J].燃料化学学报,2016,44(11):1394-1400.
[45]杨瀚.铁铈复合催化剂低温SCR脱硝性能、碱金属中毒机理及成型制备研究[D].南京:东南大学,2016.
[46]李博.选择性催化还原氮氧化物温度依存性及其抗二氧化硫中毒机理研究[D].杭州:浙江大学,2016.
[47]顾婷婷.表面硫改性和Ca掺杂对中低温SCR脱硝催化剂性能影响机理研究[D].杭州:浙江大学,2012.
[48]Xu T,Wu X,Liu X,et al.Effect of barium sulfate modification on the SO2tolerance of V2O5/Ti O2catalyst for NH3-SCR reaction[J].Science Direct,2017,57:110-117.
[49]Xu T,Wu X,Gao Y,et al.Comparative study on sulfur poisoning of V2O5-Sb2O3/Ti O2and V2O5-WO3/Ti O2monolithic catalysts for low-temperature NH3-SCR[J].Catalysis Communications,2017,93:33-36.