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【目的】氨选择性催化还原被认为是控制电厂尾气主要成分NOx排放的最佳技术之一，其中催化剂是该技术的关键所在。负载型钨铈催化剂是中高温度范围内具有优异脱硝活性的非钒基催化剂，为使该催化剂保持长期高效的脱硝活性，深入研究其SO2中毒失活再生机理具有重要意义。【方法】本研究使用不同气氛(N2、Air-N_2+O2、NH3)对SO2中毒的WO3/CeO2(W/Ce-S)催化剂在400℃下进行热处理，探究SO2中毒WO3/CeO2催化剂的失活再生机理。借助X射线衍射、拉曼光谱、X射线光电子能谱、傅里叶红外光谱、热重分析、氢气程序升温还原等表征手段，探究不同气氛热处理后催化剂再生效果存在差异的具体原因。【结果】研究发现，SO2中毒的WO3/CeO2催化剂经不同气氛热处理后，脱硝活性都可以得到不同程度的恢复。其中，经NH3热处理后，W/Ce-S的脱硝活性恢复至中毒前水平的97.4%。借助多种表征手段发现，这主要是因为经NH3热处理后，W/Ce-S催化剂表面沉积的硫酸铵盐和金属硫酸盐物种得到了最大程度的分解，使其表面活性位点和氧化还原能力得以恢复，促进了其催化活性再生。【结论】研究结果为环保型抗硫催化剂的设计提供了理论依据。
Abstract：[Objective] Ammonia selective catalytic reduction(SCR) is considered to be one of the best technologies for controlling the emission of NOx, the main component of power plant tail gas, in which the catalyst is the core of the technology. The loaded tungsten-cerium catalyst is a non-vanadium based SCR catalyst with excellent denitrification activity in the medium to high temperature range, and it is of great significance to carry out an in-depth study on the regeneration mechanism of its SO2 poisoning deactivation in order to maintain the long-term and efficient denitrification activity of this catalyst. [Methods] In this study, the SO_2-poisoned WO3/CeO2(W/Ce-S) catalyst was heat-treated at 400 ℃ with different atmospheres(N2, Air-N_2+O2, NH3) to investigate the deactivation and regeneration mechanism of SO_2-poisoned WO3/CeO2 catalyst. With the help of characterisation tools such as X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, Fourier infrared spectroscopy, thermogravimetric analysis, and hydrogenprogrammed warming reduction, the reasons for the different regeneration effects were explored. [Results] It was found that the denitrification activity of SO_2-poisoned WO3/CeO2 catalysts could be restored to different degrees after heat treatment with different atmospheres. Among them, the W/Ce-S activity recovered to 97.4% of the pre-poisoning level after NH3 heat treatment. With the help of various characterisation means, it was found that this was mainly due to the fact that the ammonium sulphate and metal sulphate species deposited on the surface of the W/Ce-S catalysts were decomposed to the maximum extent after the NH3 heat treatment, which restored the surface active sites and redox capacity, and promoted the regeneration of its catalytic activity. [Conclusion] The results of the study are conducive to the reduction of denitrification costs in the power industry and provide a theoretical basis for the design of environmentally friendly sulfur-resistant catalysts.
[1]俞颖.全球电力发展现状[J].电力科技与环保，2025,41(1):173.YU Ying. The current situation of global power development[J].Electric Power Technology and Environmental Protection,2025,41(1):173.
[2]杨阳，杨东泰，张超群，等.双碳背景下火电厂低碳化改造技术路径及经济分析[J].电力科技与环保，2025,41(1):13-26.YANG Yang,YANG Dongtai,ZHANG Chaoqun, et al. Techeconomic and carbon emissions analysis of net zero emissions technologies under the background of carbon peaking and carbon neutrality[J]. Electric Power Technology and Environmental Protection,2025,41(1):13-26.
[3]许昌日，朱法华，刘丹丹，等.基于污染物和气象要素的北京市雾霾影响因素分析[J].电力科技与环保，2021,37(1):1-8.XU Changri,ZHU Fahua,LIU Dandan.Analysis of the influencing factors of haze in Beijing based on pollutants and meteorological elements[J].Electric Power Technology and Environmental Protection,2021,37(1):1-8.
[4]ZHAO S H,YANG Y,BI F K,et al. Oxygen vacancies in the catalyst:Efficient degradation of gaseous pollutants[J]. Chemical Engineering Journal,2023,454:140376
[5]吴晶，柴雅欣.应对气候变化的大国担当[N].中国纪检监察报,2023-12-06(004).
[6]任景行，刘程，李炳宏，等.水泥厂烟气超低温NH3-SCR脱硝工艺中试[J].工业催化，2024,32:87-96.REN Jinghang, LIU Cheng, LI Binghong. Pilot test of ultra-low temperature NH3-SCR denitrification processfor cement plant flue gas[J].Industrial Catalysis,2024,32:87-96
[7]陈立志，孙毓霞，郭鹏，等.Cu-MOFs催化剂的合成及NH3-SCR脱硝应用研究[J].安全与环境学报，2025,25(4):1584-1592.CHEN Lizhi,SUN Yuxia,GUO Peng.Synthesis of Cu MOF catalysts and their a pplication in NH3-SCR denitration[J].Journal of Safety and Environment,2025,25(4):1584-1592.
[8]TAN H S,MA S B,ZHAO X Y,et al. Excellent low-temperature NH3-SCR of NO activity and resistance to H2O and SO2 over WaCeOx(a=0.06, 0.12, 0.18, 0.24)atalysts:Key role of acidity derived from tungsten addition[J]. Applied Catalysis A, General,2021, 627:1183374.
[9]HAN S C,RAO W,HU J Y,et al. Direct synthesis of high silica SSZ-16zeolite with extraordinarily superior performance in NH3-SCR reaction[J]. Applied Catalysis B:Environmental, 2023, 332:122746.
[10]TANG C J,ZHANG H L,DONG L. Ceria-based catalysts for lowtemperature selective catalytic reduction of NO with NH3[J].Catalysis Science&Technology, 2016, 6:1248-1264.
[11]Li Y J,DU J P,LIN C X,et al. Improvement of Low-Temperature NH3-SCR Activity over CeVO4 Modiffed by Sm[J]. Industrial&Engineering Chemistry Research, 2024, 63:17824-17835.
[12]QI X F,WANG Q L,WANG H N,et al. Synergistic efect of Ce doping and phosphorylation on optimizing the low temperature NH3-SCR activity of the spent V2O5-WO3/TiO2 catalyst[J]. Waste Disposal&Sustainable Energy,2025,7:73-84.
[13]JI J W,GAO N Z,SONG W,et al. Understanding the temperature-dependent H2O promotion effect on SO2 resistance of Mn O-CeO2 catalyst for SCR denitration[J]. Applied Catalysis B:Environmental, 2023, 324:122263.
[14]XIE H D,CHEN C,HE P W,et al. Promoting H2O/SO2 resistance of Ce-Mn/TiO2 nanostructures by Sb5+/Sb3+addition for Selective catalytic reduction of NO with NH3[J]. Applied Surface Science,2022, 600:154146.
[15]YOON W G, LEE S J, MAENG J B, et al. Improving catalytic performance with sulfur resistance over Co-Cr layered double oxide for low temperature NH3-SCR[J]. Chemical Engineering Journal, 2023, 452:139561.
[16]LI L L, ZHANG L, MA K L, et al. Ultra-low loading of copper modified TiO2/CeO2 catalysts for low-temperature selective catalytic reduction of NO by NH3[J]. Applied Catalysis B:Environmental,2017,207:366-375.
[17]YANG J,FAN S Y,LI X Y,et al. Highly efficient electrocatalysis dechlorination of dichloromethane over single-atom Cu/Co3O4-βspinel nanofibers[J]. Chemical Engineering Journal, 2023, 470:144040.
[18]MA Z X,SHENG L P,WANG X W,et al. Oxide Catalysts with Ultrastrong Resistance to SO2 Deactivation for Removing Nitric Oxide[J]. 2019, 31:1903719.
[19]KONG M,LIAO H P,SONG L J,et al. Insight into SO2 poisoning mechanism of MnOx-CeO2/Ti-bearing blast furnace slag catalyst for low temperature NH3-SCR reaction[J]. Molecular Catalysis,2024, 569:114609.
[20]WANG C Z,GAO F Y,KO S J, et al. Structural control for inhibiting SO2 adsorption in porous MnCe nanowire aerogel catalysts for low-temperature NH3-SCR[J]. Chemical Engineering Journal, 2022, 434:134729.
[21]CHANG H Z,LI J H,Chen X Y,et al. Effect of Sn on MnOx-CeO2catalyst for SCR of NOx by ammonia:Enhancement of activity and remarkable resistance to SO2[J]. Catalysis Communications, 2021,27:54-57.
[22]HAO Z F,JIAO Y L,SHI Q,et al. Improvement of NH3-SCR performance and SO2 resistance over Sn modifed[J].Catalysis Today,2019, 327:37-46.
[23]MA K L,GUO K,LI L L,et al. Cavity size dependent SO2resistance for NH3-SCR of hollow structured CeO2-TiO2 catalysts[J]. Catalysis Communications, 2019,128:105719.
[24]ZHAO Q,HUANG X S,ZHANG G D,et al. Deeply revealing the deactivation and decomposition mechanism of ammonium bisulfate on nanotube structured SCR catalysts for the low-temperature NH3-SCR reaction[J]. Catalysis Science&Technology, 2025,15:903.
[25]MU J C,Li X Y,WANG X Y,et al. New Insight into the effects of NH3 on SO2 Poisoning for in situ removal of metal sulfates in lowtemperature NH3-SCR over an Fe-V Catalyst[J]. The Journal of Physical Chemistry C, 2020, 124:21396-21406.
[26]KIM J S,KIM D H,HA H P,et al. Investigating multi-functional traits of metal-substituted vanadate catalysts in expediting NOx reduction and poison degradation at low temperatures[J].Journal of Hazardous Materials,2020,397:122671.
[27]XU L W,WANG C Z,CHANG H Z,et al. New insight into SO2poisoning and regeneration of CeO2-WO3/TiO2 and V2O5-WO3/TiO2 catalysts for low-temperature NH3-SCR[J]. Environmental Science&Technology,2018,52:7064-7071.
[28]CHANG H Z,LI J H,YUAN J,et al. Ge, Mn-doped CeO2-WO3catalysts for NH3-SCR of NOx:Effects of SO2 and H2 regeneration[J]. Catalysis Today,2013,201:139-144.
[29]ZHANG L,SUN J F,XIONG Y,et al. Catalytic performance of highly dispersed WO3 loaded on CeO2 in the selective catalytic reduction of NO by NH3[J]. Chinese Journal of Catalysis, 2017,38:1749-1758.
[30]杨佳楠，史建强，杨凯鑫，等.SSZ-13分子筛负载MnCeOx催化剂NH3-SCR脱硝及抗硫中毒性能研究[J].现代化工，2025,45:93-99.YANG Jianan, SHI Jianqiang, YANG Kaixin. Study on NH3-SCR denitrification and sulfur poisoning resistance performances of SSZ-13 molecular sieve supported MnCeOx catalysts[J]. Modern Chemical Industry,2025,45:93-99.
[31]HAO Y H,WANG Y,ZHANG T T,et al. Cu docking-activated Nb incorporation in multivariate CuO-Nb2O5/CeO2 catalysts for selective reduction of NOx with NH3[J]. Applied Catalysis B:Environmental,2024,340:123254.
[32]LI L L,JI J W,TAN W,et al. Enhancing low-temperature NH3-SCR performance of Fe-Mn/CeO2 catalyst by Al2O3 modification[J]. Journal of Rare Earths,2022,40:1454-1461.
[33]TAN W,XIE S H,LE D,et al. Fine-tuned local coordination environment of Pt single atoms on ceria controls catalytic reactivity[J]. Nature Communications, 2022, 13:7070.
[34]LI L L,GE C Y,JI J W,et al. Effects of different methods of introducing Mo on denitration performance and anti-SO2poisoning performance of CeO2[J]. Chinese Journal of Catalysis,2021, 42:1488-1499.
[35]GUO M,LIS B M,FORD M E,et al. Effect of redox promoters(CeOx and Cu Ox)and surface sulfates on the selective catalytic reduction(SCR)of NO with NH3 by supported V2O5-WO3/Ti O2 catalysts[J].Applied Catalysis B:Environmental,2022,306:121108.
[36]YU Y X,TAN Wei,AN D Q,et al. Activity enhancement of WO3modified FeTiO catalysts for the selective catalytic reduction of NO by NH3[J]. Catalysis Today, 2021,375:614-622.
[37]ZOU W X,GE C Y,LU M Y,et al. Engineering the NiO/CeO2interface to enhance the catalytic performance for CO oxidation[J].RSC Advances,2015,5:98335-98343.
[38]马恬，朱晨，刘成宝，等.Co修饰CeO2复合材料的晶面调控及其光热催化脱硝性能[J].复合材料学报,2020,37(9):2265-2271.MA Tian,ZHU Chen,LIU Chengbao. Facet control of Comodified CeO2 composite and its thermal-photocatalytic denitration property[J]. Acta Materiae Compositae Sinica,2020,37(9):2265-2271.
[39]YASSER J J,DI W,ASHOK K,et al. SO2 poisoning of the NH3-SCR reaction over Cu-SAPO-34:Effect of ammonium sulfate versus Other S-containing species[J]. ACS Catalysis, 2016,6:6612-6622.
[40]ZHAO W R,JI J W,MA K L,et al. Improved K-resistance of a Cumodified Ti O2/Ce O2 catalyst for SCR of NOx at low temperatures[J].Industrial&Engineering Chemistry Research, 2023,62:5782-5791.
[41]ZHANG J,CHEN L Q,FAN Y X,et al. Unraveling the high catalytic activity of single atom Mo-doped Ti O2 toward NH3-SCR:Synergetic roles of Mo as acid sites and oxygen vacancies as oxidation sites[J]. Chemical Engineering Journal, 2023, 465:142759.
[42]AN D Q,YANG S,ZOU W X,et al. Unraveling the SO2 poisoning effect over the lifetime of MeOx(Me=Ce, Fe, Mn)catalysts in low-temperature NH3-SCR:interaction of reaction atmosphere with surface species[J]. The Journal of Physical Chemistry C,2022, 126:12168-12177.
[43]LIU H,GAO C,CHEN J J,et al. Optimized local geometry and electronic structure of MoO3/CeO2 catalyst by adding copper cations for boosted nitrogen oxide reduction performance[J].Applied Catalysis B:Environmental, 2023, 332:122742.
[44]INOMATA Y,KUBOTA H,HONMATSU Y,et al. Sodium ion intercalation in vanadium oxide promotes low-temperature NH3-SCR activity:Sodium vanadium bronzes(Na0.33V2O5)for NOx removal[J]. Applied Catalysis B:Environmental, 2023, 328:122536.
[45]GUO K,JI J,SONG W,et al. Conquering ammonium bisulfate poison over low-temperature NH3-SCR catalysts:A critical review[J].Applied Catalysis B:Environmental, 2021, 297:120388.
[46]XU Y,WU X,LIN Q,et al. SO2 promoted V2O5-MoO3/TiO2 catalyst for NH3-SCR of NO at low temperatures[J]. Applied Catalysis A:General, 2019, 570:42-50.
[47]YU Y,TAN W,AN D,et al. Insight into the SO2 resistance mechanism on γ-Fe2O3 catalyst in NH3-SCR reaction:A collaborated experimental and DFT study[J]. Applied Catalysis B:Environmental, 2021, 281:119544.
[48]XIE S,TAN W,LI Y,et al. Copper single atom-triggered NiobiaCeria catalyst for efficient low-temperature reduction of nitrogen oxides[J]. ACS Catalysis, 2022, 12:2441-2453.
[49]YANG S,GUO Y,CHANG H,et al. Novel effect of SO2 on the SCR reaction over CeO2:Mechanism and significance[J]. Applied Catalysis B:Environmental, 2013, 136-137:19-28.
基本信息:
DOI：10.19944/j.eptep.1674-8069.2025.05.013
中图分类号:X701
引用信息:
[1]赵文瑞,李佩晓,蒋沛婷,等.不同气氛热处理对SO_2中毒的WO_3/CeO_2催化剂再生活性的影响[J].电力科技与环保,2025,41(05):822-831.DOI:10.19944/j.eptep.1674-8069.2025.05.013.
基金信息:
国家自然科学基金青年项目（22402027）