朱浩峰,孟思彤,段玉梅,张靖,何云刚,段开娇,向明武,贾丽娟

• 1:云南民族大学化学与环境学院
• 2:非常规冶金教育部重点实验室

摘要(Abstract)：

钐改性锰(Sm-Mn)催化剂因低温活性和抗硫性能优越，在非电行业烟气脱硝中展现出独特的优势和重要的研究价值，但水硫杂质共存会大幅降低催化活性，元素掺杂、制备方法、载体选择是提高该催化剂低温脱硝性能的关键技术。首先介绍了Sm-Mn催化剂的低温脱硝性能优势和Sm作用机制，然后阐述了催化剂的脱硝反应路径和抗水抗硫机理，重点围绕催化剂的设计与开发，分别论述了上述3种关键技术对提高Sm-Mn催化剂的低温脱硝性能影响规律及特征，最后对Sm-Mn催化剂未来研究方向提出展望。

关键词(KeyWords)： 低温脱硝;Sm-Mn催化剂;抗水抗硫性;NH_3-SCR反应机理

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金(22266036);; 云南省教育厅科研基金(2023J0597)

作者(Author): 朱浩峰,孟思彤,段玉梅,张靖,何云刚,段开娇,向明武,贾丽娟

参考文献(References)：

• [1]CHEN T,WANG X W,MA S J,et al.Carbon nanomaterial-Sm Mn2O5nanocrystal composites with highly efficient catalytic oxidation of NO[J].Solid State Sciences,2020,108:106425．
• [2]SONG I,LEE H,JEON S W,et al.Simple physical mixing of zeolite prevents sulfur deactivation of vanadia catalysts for NOxremoval[J].Nature communications,2021,12(1):901．
• [3]ZHU N,SHAN W P,SHAN Y L,et al.Effects of alkali and alkaline earth metals on Cu-SSZ-39 catalyst for the selective catalytic reduction of NOxwith NH3[J].Chemical Engineering Journal,2020,388:124250．
• [4]CHEN G R,XU J Q,YU H J,et al.Effect of the non-thermal plasma treatment on the structure and SCR activity of vanadium-based catalysts[J].Chemical Engineering Journal,2020,380:122286．
• [5]高尔豪，赵子龙，朱绍东，等．Mn Cr2O4催化剂的制备方法及其SCR脱硝性能研究[J]．高校化学工程学报，2021,35(2):355-362.GAO E H,ZHAO Z L,ZHU S D,et al.Preparation of Mn Cr2O4catalysts and their NH3-SCR performance[J].Journal of Chemical Engineering of Chinese Universities,2021,35(2):355-362．
• [6]YANG J,REN S,ZHANG T S,et al.Iron doped effects on active sites formation over activated carbon supported Mn-Ce oxide catalysts for low-temperature SCR of NO[J].Chemical Engineering Journal,2020,379:122398．
• [7]TANG J G,WANG X T,LI H J,et al.The resistance of SO2and H2O of Mn-based catalysts for NOxselective catalytic reduction with ammonia:Recent advances and perspectives[J].ACS Omega,2023,8(8):7262-7278．
• [8]YANG J,REN S,ZHOU Y H,et al.In situ IR comparative study on N2O formation pathways over different valence states manganese oxides catalysts during NH3-SCR of NO[J].Chemical Engineering Journal,2020,397:125446．
• [9]WANG Z Y,GUO R T,SHI X,et al.The superior performance of Co Mn Oxcatalyst with ball-flowerlike structure for low-temperature selective catalytic reduction of NOxby NH3[J].Chemical Engineering Journal,2020,381:122753．
• [10]RAJA S,ALPHIN M S,SIVACHANDIRAN L.Promotional effects of modified Ti O2-and carbon-supported V2O5-and Mn Ox-based catalysts for the selective catalytic reduction of NOx:A review[J].Catalysis Science&Technology,2020,10(23):7795-7813．
• [11]SALAEV M A,KULCHAKOVSKAYA E V,LIOTTA L F,et al.Bimetallic Ag-based catalysts for low-temperature SCR:Quo vadis?[J].Applied Catalysis A:General,2022,644:118815．
• [12]CHEN S N,VASILIADES M A,YAN Q H,et al.Remarkable N2-selectivity enhancement of practical NH3-SCR over Co0.5Mn1Fe0.25Al0.75Ox-LDO:The role of Co investigated by transient kinetic and DFT mechanistic studies[J].Applied Catalysis B:Environmental,2020,277:119186．
• [13]LI Y S,LENG X S,MA S B,et al.Effects of Mo addition on the NH3-SCR of NO reaction over MoaMn Ti10Ox(a=0.2,0.4,0.6 and0.8):Synergistic action between redox and acidity[J].Catalysis Today,2020,339:254-264．
• [14]GAO F Y,TANG X L,YI H H,et al.Mn2Ni O4spinel catalyst for high-efficiency selective catalytic reduction of nitrogen oxides with good resistance to H2O and SO2at low temperature[J].Journal of Environmental Sciences,2020,89:145-155．
• [15]SUN P,GUO R T,LIU S M,et al.The enhanced performance of Mn Oxcatalyst for NH3-SCR reaction by the modification with Eu[J].Applied Catalysis A:General,2017,531:129-138．
• [16]CAI M,BIAN X,XIE F,et al.Preparation and performance of cerium-based catalysts for selective catalytic reduction of nitrogen oxides:A critical review[J].Catalysts,2021,11(3):361．
• [17]XU J Q,YU H J,ZHANG C,et al.Development of cerium-based catalysts for selective catalytic reduction of nitrogen oxides:a review[J].New Journal of Chemistry,2019,43(10):3996-4007．
• [18]REN D D,LIN K S,MAO T P,et al.The study of SCR mechanism on La Mn1-xFexO3catalyst surface based DFT[J].Energies,2023,16(22):7609．
• [19]SHI X K,GUO J X,SHEN T,et al.Enhancement of Ce doped La-Mn oxides for the selective catalytic reduction of NOxwith NH3and SO2and/or H2O resistance[J].Chemical Engineering Journal,2021,421:129995．
• [20]WANG F L,WANG P L,LAN T W,et al.Ultralow-temperature NOxreduction over Sm Mn2O5mullite catalysts via modulating the superficial dual-functional active sites[J].ACS Catalysis,2022,12(13):7622-7632．
• [21]GUO R T,QIN B,WEI L G,et al.Recent progress of low-temperature selective catalytic reduction of NOxwith NH3over manganese oxide-based catalysts[J].Physical Chemistry Chemical Physics,2022,24(11):6363-6382．
• [22]MENG D M,ZHAN W C,GUO Y,et al.A highly effective catalyst of Sm-Mn Oxfor the NH3-SCR of NOxat low temperature:Promotional role of Sm and its catalytic performance[J].ACS Catalysis,2015,5(10):5973-5983．
• [23]MENG D M,ZHAN W C,GUO Y,et al.A highly effective catalyst of Sm-Mn mixed oxide for the selective catalytic reduction of NOx with ammonia:Effect of the calcination temperature[J].Journal of Molecular Catalysis A:Chemical,2016,420:272-281．
• [24]杨梅君，马艳娇，涂溶，等．钐掺杂对锰基催化剂的NO分解性能影响[J]．化工进展，2018,37(12):4687-4692.YANG M J,MA Y J,TU R,et al.Effect of Sm-doping on direct NO decomposition over Mn-based catalyst[J].Chemical Industry and Engineering Progress,2018,37(12):4687-4692．
• [25]康天红．Sm-Mn脱硝催化剂及其低温抗硫性研究[D]．武汉:武汉理工大学，2019.KANG T H.Sm-Mn De-NOxcatalyst and its low temperature sulfur resistance study[D].Wuhan:Wuhan University of Technology,2019．
• [26]XIE J L,YE Y L,LI Q L,et al.Denitrification performance and sulfur resistance mechanism of Sm-Mn catalyst for low temperature NH3-SCR[J].Frontiers of Chemical Science and Engineering,2023,17(5):617-633．
• [27]QUE T T,DUAN K J,KOPPALA S,et al.Novel synthesis of reed flower-like Sm Mn Oxcatalyst with enhanced low-temperature activity and SO2resistance for NH3-SCR[J].Environmental Research,2022,215:114231．
• [28]张靖，段玉梅，孟思彤，等．超低温Sm Mn Ox催化剂高效脱硝及抗硫性能研究[J]．现代化工，2024,44(2):103-108.ZHANG J,DUAN Y M,MENG S T,et al.Sm Mn Oxcatalyst for high-efficiency SCR of NOxwith good sulfur resistance at ultralow temperature[J].Modern Chemical Industry,2024,44(2):103-108．
• [29]GAO C,SHI J W,FAN Z Y,et al."Fast SCR"reaction over Sm-modified Mn Ox-Ti O2for promoting reduction of NOxwith NH3[J].Applied Catalysis A:General,2018,564:102-112．
• [30]SALAZAR M,HOFFMANN S,TILLMANN L,et al.Hybrid catalysts for the selective catalytic reduction (SCR) of NO by NH3:Precipitates and physical mixtures[J].Applied Catalysis B:Environmental,2017,218:793-802．
• [31]LU P,YE L M,YAN X H,et al.N2O inhibition by toluene over Mn-Fe spinel SCR catalyst[J].Journal of Hazardous Materials,2021,414:125468．
• [32]HAN L P,CAI S X,GAO M,et al.Selective catalytic reduction of NOxwith NH3by using novel catalysts:State of the art and future prospects[J].Chemical Reviews,2019,119(19):10916-10976．
• [33]CHEN Z C,REN S,XING X D,et al.Unveiling the inductive strategy of different precipitants on Mn Fe Oxcatalyst for low-temperature NH3-SCR reaction[J].Fuel,2023,335:126986．
• [34]WANG J W,XIE H,SHU D B,et al.The promotion of NH3-SCR performance and its mechanism on Sm modified birnessite[J].Fuel,2024,356:129604．
• [35]ZHANG S Y,ZHANG B L,WU B Y,et al.Effect of samarium on the N2selectivity of SmxMn0.3-xTi catalysts during selective catalytic reduction of NOxwith NH3[J].International Journal of Minerals,Metallurgy and Materials,2023,30(4):642-652．
• [36]FENG S,LI Z M,SHEN B X,et al.An overview of the deactivation mechanism and modification methods of the SCR catalysts for denitration from marine engine exhaust[J].Journal of Environmental Management,2022,317:115457．
• [37]SUN C Z,LIU H,CHEN W,et al.Insights into the Sm/Zr co-doping effects on N2selectivity and SO2resistance of a Mn Ox-Ti O2catalyst for the NH3-SCR reaction[J].Chemical Engineering Journal,2018,347:27-40．
• [38]FENG S,KONG W W,WANG Y L,et al.Mechanistic investigation of Sm doping effects on SO2resistance of W-Zr-ZSM-5 catalyst for NH3-SCR[J].Fuel,2023,353:129139．
• [39]CHEN Z C,REN S,WANG M M,et al.Insights into samarium doping effects on catalytic activity and SO2tolerance of Mn Fe Oxcatalyst for low-temperature NH3-SCR reaction[J].Fuel,2022,321:124113．
• [40]LI J,GUO J X,SHI X K,et al.Effect of aluminum on the catalytic performance and reaction mechanism of Mn/MCM-41 for NH3-SCRreaction[J].Applied Surface Science,2020,534:147592．
• [41]QIN Q J,CHEN K A,XIE S Z,et al.Enhanced SO2and H2O resistance of Mn Ti Sn Oycomposite oxide for NH3-SCR through Sm modification[J].Applied Surface Science,2022,583:152478．
• [42]LIU C X,BI Y L,LI J H.Activity enhancement of sulphated Fe2O3supported on Ti O2-Zr O2for the selective catalytic reduction of NO by NH3[J].Applied Surface Science,2020,528:146695．
• [43]YANG J,REN S,SU B X,et al.Understanding the dual-acting of iron and sulfur dioxide over Mn-Fe/AC catalysts for low-temperature SCR of NO[J].Molecular Catalysis,2022,519:112150．
• [44]ZHANG Y,YANG S,ZHU X Y,et al.Effects of sulfation on hematite for selective catalytic reduction of nitrogen oxides with ammonia[J].Journal of Colloid and Interface Science,2022,606:1445-1456．
• [45]XU Q,FANG Z L,CHEN Y Y,et al.Titania-samarium-manganese composite oxide for the low-temperature selective catalytic reduction of NO with NH3[J].Environmental Science&Technology,2020,54(4):2530-2538．
• [46]WANG B,WANG M X,HAN L N,et al.Improved activity and SO2resistance by Sm-modulated redox of Mn Ce Sm Ti Oxmesoporous amorphous oxides for low-temperature NH3-SCR of NO[J].ACS Catalysis,2020,10(16):9034-9045．
• [47]TONG Y M,LI Y S,LI Z B,et al.Influence of Sm on the low temperature NH3-SCR of NO activity and H2O/SO2resistance over the SmaMn Ni2Ti7Ox(a=0.1,0.2,0.3,0.4) catalysts[J].Applied Catalysis A:General,2020,590:117333．
• [48]SUN C Z,CHEN W,JIA X X,et al.Comprehensive understanding of the superior performance of Sm-modified Fe2O3catalysts with regard to NO conversion and H2O/SO2resistance in the NH3-SCR reaction[J].Chinese Journal of Catalysis,2021,42 (3):417-430．
• [49]LIU H,FAN Z X,SUN C Z,et al.Improved activity and significant SO2tolerance of samarium modified Ce O2-Ti O2catalyst for NO selective catalytic reduction with NH3[J].Applied Catalysis B:Environmental,2019,244:671-683．
• [50]YUAN X Y,ZHAO X Y,LI Y Y,et al.Boosting the H2O resistance and NH3-SCR activity over sulfated Fe Ce0.5SmaTi4Ox-S catalysts by Sm modification[J].Journal of Environmental Chemical Engineering,2023,11(3):110010．
• [51]WANG Y H,ZHANG G D,HUANG X S,et al.An effective strategy to enhance the sulfur resistance of Ce-based catalyst for low temperature SCR reaction[J].Fuel,2023,352:129078．
• [52]ZHAO X Y,MA M M,LIU Z,et al.Selective catalytic reductive removal of NOxwith decreased interference from SO2and H2O by use of Sm-modified SmxCo0.05-xCe0.05Ti0.9Oycatalysts[J].Journal of Colloid and Interface Science,2022,611:9-21．
• [53]SUN P,GUO R T,LIU S M,et al.Enhancement of the low-temperature activity of Ce/Ti O2catalyst by Sm modification for selective catalytic reduction of NOxwith NH3[J].Molecular Catalysis,2017,433:224-234．
• [54]DING J B,YANG X W,WANG A Y,et al.Sm-Mn Oxcatalysts for low-temperature selective catalytic reduction of NOxwith NH3:Effect of precipitation agent[J].Journal of Rare Earths,2022,40(8):1199-1210．
• [55]LIU L J,XU K,SU S,et al.Efficient Sm modified Mn/Ti O2catalysts for selective catalytic reduction of NO with NH3at low temperature[J].Applied Catalysis A:General,2020,592:117413．
• [56]HE X,ZHU F J,DONG L L,et al.Sm-Mn Ox/Ti O2-{001}with preferentially exposed anatase{001}facet for selective catalytic reduction of NO with NH3[J].Applied Catalysis A:General,2023,664:119353．
• [57]LI J F,LIU H,QIN Q J,et al.Functional distinction of different components in Sm Ce Mn/Ti catalytic system for NH3-SCR[J].Applied Surface Science,2023,636:157775．
• [58]CHEN L,YANG J,REN S,et al.Effects of Sm modification on biochar supported Mn oxide catalysts for low-temperature NH3-SCR of NO[J].Journal of the Energy Institute,2021,98:234-243．
• [59]QU C S,LIN S,ZHAO D Y,et al.Enhancing SCR activity and anti-poisoning of Mn Ox/m-Zr O2catalysts by metal doping[J].Catalysis Communications,2023,185:106809．
• [60]PE?A D A,UPHADE B S,SMIRNIOTIS P G.Ti O2-supported metal oxide catalysts for low-temperature selective catalytic reduction of NO with NH3:I.Evaluation and characterization of first row transition metals[J].Journal of Catalysis,2004,221(2):421-431.