| 34 | 0 | 84 |
| 下载次数 | 被引频次 | 阅读次数 |
【目的】在燃煤机组深度调峰和灵活性运行需求不断增强的背景下，为解决烟气脱硝系统低负荷工况下烟温降低，传统V_2O5-WO3/TiO2(VW/Ti)基选择性催化还原(selective catalytic reduction,SCR)催化剂活性衰减的问题。【方法】本研究围绕提升SCR催化剂的宽温脱硝能力与抗硫性能展开，通过浸渍法引入不同过渡金属元素对催化剂进行掺杂改性，系统探究了不同掺杂元素及其掺杂比例对性能的影响，并结合多种表征手段，从结构特征、表面酸性、氧化还原性能及反应机理等方面进行了深入分析。【结果】研究表明，Nb、Sb、Ce、Nd掺杂均能显著提升催化剂在160～240℃低温区的脱硝活性，其中Ce掺杂效果最为显著，而Ho和Sm掺杂后性能反而下降。V_2O5-WO3-5CeO2/TiO2(VW5Ce/Ti)催化剂高效脱硝温度窗口拓宽至220～400℃，能够更好地适应燃煤电厂深度调峰运行条件。在含H_2O和SO2的模拟烟气条件下，VW5Ce/Ti催化剂活性衰减幅度明显低于未掺杂的VW/Ti催化剂，表现出优异的抗水抗硫性能。通过X射线衍射、比表面积分析、氢气程序升温还原、氨气程序升温脱附及原位红外光谱(diffuse reflectance infrared fourier transform spectroscopy,DRIFTS)等表征手段分析发现，Ce掺杂未明显改变TiO2载体晶型结构，但增加了催化剂表面酸性位点数量并提升氧化还原能力，促进了NH3与NOx的吸附与反应。原位DRIFTS实验进一步证实，VW5Ce/Ti催化剂表面同时存在Lewis酸和Brønsted酸位点，反应遵循L-H和E-R机理。【结论】Ce掺杂是一种提升VW/Ti基SCR催化剂宽温脱硝性能和抗硫稳定性的有效途径，本研究可为燃煤电厂在深度调峰和超低排放条件下SCR催化剂的优化设计与工程应用提供理论依据和技术参考。
Abstract：[Objective]Under the increasing demand for deep peak regulation and flexible operation of coal-fired units, to address the decline in catalyst activity of conventional V_2O5-WO3/TiO2(VW/Ti)-based selective catalytic reduction(SCR) catalysts caused by reduced flue gas temperature at low loads. [Methods]In this study, efforts were devoted to improving the wide-temperature denitrification performance and sulfur resistance of SCR catalysts. Different transition metal elements were introduced via an impregnation method to modify the catalysts, and the effects of dopant species and doping ratios on catalytic performance were systematically investigated. Structural properties, surface acidity, redox behavior, and reaction mechanisms were comprehensively analyzed using multiple characterization techniques. [Results]The results showed that Nb, Sb, Ce and Nd doped catalysts exhibit significantly enhanced low-temperature DeNOx activity in the range of 160-240 ℃, with Ce doping showing the most pronounced improvement,while doping with Ho and Sm leads to a decline in performance. The effective denitrification temperature window of the V2 O5-WO3-5 CeO2/TiO2(VW5 Ce/Ti) catalyst was broadened to 220-400 ℃, indicating improved adaptability to deep peak shaving operation conditions. Under simulated flue gas conditions containing H_2O and SO2, the VW5 Ce/Ti catalyst exhibited a markedly lower activity decay than the undoped VW/Ti catalyst, demonstrating superior resistance to water vapor and sulfur poisoning. Characterization results obtained from X-ray diffraction, brunauer-emmett-teller, hydrogen temperatureprogrammed reduction, ammonia temperature-programmed desorption, and in situ diffuse reflectance infrared fourier transform spectroscopy(DRIFTS) indicate that Ce doping does not significantly alter the crystalline structure of the TiO2 support but increases the number of surface acidic sites and enhances the redox capability of the catalyst, thereby facilitating the adsorption and reaction of NH3 and NOx species. Furthermore, in situ DRIFTS analysis confirmed that both Lewis and Brønsted acid sites coexist on the surface of the VW5 Ce/Ti catalyst, and the SCR reaction follows a combination of Langmuir-Hinshelwood and Eley-Rideal mechanisms. [Conclusion]Ce doping is demonstrated to be an effective approach for enhancing the wide-temperature denitrification performance and sulfur resistance of VW/Ti based SCR catalysts. The study provide theoretical support for catalyst design and engineering applications under deep peak shaving and ultra-low emission conditions.
[1]蒙毅,刘逸芸,宋士林,等.燃煤电厂碳酸氢铵固体热解制氨系统研究[J].热力发电, 2025, 54(11):76-82.MENG Yi, LIU Yiyun, SONG Shilin, et al. Study on ammonium bicarbonate solid pyrolysis system for ammonia production in coalfired power plants[J]. Thermal Power Generation, 2025, 54(11):76-82.
[2]赵勇刚,蔡彦迪,杜顺鑫,等.Mo/CexZr1-xO2催化剂的协同调控及其低温NH3-SCR活性及抗中毒性能研究[J].电力科技与环保,2025, 41(5):803-810.ZHAO Yonggang, CAI Yandi, DU Shunxin, et al. Study on synergistic regulation of Mo/CexZr1-xO2 catalysts and their low-temperature NH3-SCR activity and poisoning resistance[J]. Electric Power Technology and Environmental Protection, 2025, 41(5):803-810.
[3]WANG J, ZHENG K L, SINGH R, et al. Numerical simulation and cold experimental research of a low-NOx combustion technology for pulverized low-volatile coal[J]. Applied Thermal Engineering,2017, 114:498-510.
[4]LOCCI C, VERVISCH L, FARCY B, et al. Selective non-catalytic reduction(SNCR)of nitrogen oxide emissions:A perspective from numerical modeling[J]. Flow, Turbulence and Combustion, 2018,100(2):301-340.
[5]周会成,王峰,武洁,等.燃煤电厂深度调峰下宽负荷脱硝技术研究进展[J].现代化工, 2025, 45(3):45-49+55.ZHOU Huicheng, WANG Feng, WU Jie, et al. A review on wide-load denitrification technology under deep peak shaving in coal-fired power plants[J]. Modern Chemical Industry, 2025, 45(3):45-49+55.
[6]吴荫南.燃煤烟气NH3-SCR催化剂研究进展[J].现代化工,2025,45(S1):29-35.WU Yinnan. Research progress in NH3-SCR catalysts for coalfired flue gas[J]. Modern Chemical Industry, 2025,45(S1):29-35.
[7]岳彦伟,黄力,王素芹,等.煅烧气氛对高V2O5含量V2O5-MoO3/TiO2脱硝催化剂性能的影响[J].化工环保, 2024,44(2):257-264.YUE Yanwei,HUANG Li,WANG Suqin, et al. Effect of calcination atmosphere on performance of V2O5-Mo O3/Ti O2 denitration catalyst with high V2O5 content[J]. Environmental Protection of Chemical Industry, 2024,44(2):257-264.
[8]赵欣,黄垒,李红蕊,等.过渡金属（Cu, Fe, Mn, Co）改性高分散V2O5/TiO2作为高效NH3-SCR脱硝催化剂[J].催化学报, 2015,58(11):1886-1899.ZHAO Xin, HUANG Lei, LI Hongrui, et al. Highly dispersed V2O5/TiO2 modified with transition metals(Cu, Fe, Mn, Co)as efficient catalysts for the selective reduction of NO with NH3[J]. Chinese Journal of Catalysis, 2015, 58(11):1886-1899.
[9]NI K W, PENG Y W, DAI G Y, et al. Ceria accelerates ammonium bisulfate decomposition for improved SO2 resistance on a V2O5-WO3/TiO2 catalyst in low-temperature NH3-SCR[J]. Journal of the Taiwan Institute of Chemical Engineers, 2022, 140:104555.
[10]JUNG M G, SHIN J H, KWON D W, et al. Promotional effects of Me(Sb, La, Ce, Mo)additives on the NH3-SCR activity and SO2durability of V2O5-WO3/TiO2 catalysts[J]. Process Safety and Environmental Protection, 2024, 183:911-924.
[11]ZHU Y, SHAN W P, LIAN Z H, et al. Effects of impregnation sequence on the NH3-SCR activity and hydrothermal stability of a CeNb/Sn O2 catalyst[J]. Journal of Environmental Sciences, 2024, 138:450-457.
[12]ZHAO T, HUANG X S, CUI R J, et al. Unveiling a remarkable enhancement role by designing a confined structure HoTNTs@Mn catalyst for low-temperature NH3-SCR reaction[J].Nanoscale, 2023, 15(30):12540-12557.
[13]田春雨,董浩,迟姚玲,等.Mn-Fe-Ce-O催化剂对助燃脱硝性能的影响[J].石油化工, 2024,53(11):1552-1559.TIAN Chunyu,DONG Hao,CHI Yaoling, et al. Effect of Mn-Fe-CeO catalysts on combustion-supporting denitration performance[J].Petrochemical Technology, 2024,53(11):1552-1559.
[14]陈佳音,宁淑英,付维,等.CuCoCe-LDH催化剂的C3H6-SCR脱硝特性[J].燃料化学学报(中英文), 2024,52(3):373-383.CHEN Jiayin,NING Shuying,FU Wei, et al. C3H6-SCR denitration characteristics of CuCoCe-LDH catalysts[J]. Journal of Fuel Chemistry and Technology, 2024,52(3):373-383.
[15]LIU W Y, WANG X P, QU C, et al. Rare earth metal(La, Ce, Nd, Eu)doped Cu/Zr-PILC catalysts for the efficient NH3-SCR at low temperature[J]. Combustion Science and Technology, 2025, 197(8):1901-1919.
[16]XU J Q, ZHEN F T, ZOU X L, et al. The facilitating effect of sulfide treatment coupled sol-gel method on NH3-SCR activity of Fe-Mn/Ti O2 catalysts[J]. Journal of the Energy Institute, 2024, 112:101458.
[17]KWON D W, NAM K B, HONG S C. Influence of tungsten on the activity of a Mn/Ce/W/Ti catalyst for the selective catalytic reduction of NO with NH3 at low temperatures[J]. Applied Catalysis A:General, 2015, 497:160-166.
[18]DANH H T, KUMAR P A, JEONG Y E, et al. Enhanced NH3-SCR activity of Sb-V/CeO2-TiO2 catalyst at low temperatures by synthesis modification[J]. Research on Chemical Intermediates,2016, 42(1):155-169.
[19]费亦凡,仲兆平,周峻伍,等.Ce(SO4)2改性对V-W/Ti催化剂抗碱土中毒性能提升的影响[J].现代化工, 2025, 45(4):153-159.FEI Yifan, ZHONG Zhaoping, ZHOU Junwu, et al. Ce(SO4)2modification of V-W/Ti catalyst for improving its resistance to alkaline-earth metals poisoning[J]. Modern Chemical Industry,2025, 45(4):153-159.
[20]ZHANG X L, JIN S, LIU S W, et al. Low-temperature NH3-SCR over hierarchical MnOx supported on montmorillonite prepared by different methods[J]. ACS Omega, 2023, 8(14):13384-13395.
[21]HAN X Y, BIAN M Y, LIU K J, et al. Influence of Particle Size of Ce O2 Nanospheres Encapsulated in SBA-15 Eesopores on SO2Tolerance during NH3-SCR Reaction[J]. Catalysts, 2024, 14(2):151.
[22]LI X L, NIU Y F, LI J, et al. Trace Co doping improves NH3-SCR performance and poisoning resistance of Ce-Mn-based catalysts[J].Chemical Engineering Journal, 2023, 454:140180.
[23]SHI M M, YE S, QU H X, et al. Synergistic effect of Cu2+doping and sulfation in Cu-Ce-S, tolerance to H2O and SO2 and decomposition behaviors of ammonia salts[J]. Molecular Catalysis, 2018, 459:135-140.
[24]LIU Z M, ZHANG S X, LI J H, et al. Promoting effect of MoO3 on the NOx reduction by NH3 over CeO2/Ti O2 catalyst studied with in situ DRIFTS[J]. Applied Catalysis B:Environmental, 2014, 144:90-95.
[25]XUE H Y, GUO X M, MENG T, et al. NH3-SCR of NO over M/ZSM-5(M=Mn, Co, Cu)catalysts:An in-situ DRIFTS study[J].Surfaces and Interfaces, 2022, 29:101722.
[26]WANG X Q, SHI A J, DUAN Y F, et al. Catalytic performance and hydrothermal durability of Ce O2-V2O5-Zr O2/WO3-Ti O2 based NH3-SCR catalysts[J]. Catalysis Science&Technology, 2012, 2(7):1386.
[27]WANG H, QU Z P, LIU L L, et al. Promotion of NH3-SCR activity by sulfate-modification over mesoporous Fe doped CeO2 catalyst:Structure and mechanism[J]. Journal of Hazardous Materials,2021, 414:125565.
[28]TANG X L, SHI Y R, GAO F Y, et al. Promotional role of Mo on Ce0.3Fe Ox catalyst towards enhanced NH3-SCR catalytic performance and SO2 resistance[J]. Chemical Engineering Journal,2020, 398:125619.
[29]SONG K L, SHI J W, ZHOU X Y, et al. Design of dual-ligand coordination in metal organic frameworks for breaking the seesaw effect between de-NOx activity and N2 selectivity[J]. Applied Catalysis B:Environment and Energy, 2024, 354:124131.
[30]GUI R, ZHANG C, GAO Y S, et al. Unravelling the multiple effects of H2O on the NH3-SCR over Mn2Cu1Al1Ox-LDO by transient kinetics and in situ DRIFTS[J]. Applied Catalysis B:Environment and Energy, 2025, 361:124611.
[31]WANG L, WANG J B, CHENG H P, et al. Ce1-xMnxVO4 with improved activity for low-temperature catalytic reduction of NO with NH3[J]. Chemistry-An Asian Journal, 2025, 20(6):e202401341.
[32]WANG S X, GUO R T, PAN W G, et al. The deactivation of Ce/TiO2 catalyst for NH3-SCR reaction by alkalimetals:TPD and DRIFT studies[J]. Catalysis Communications, 2017, 89:143-147.
基本信息:
DOI：10.19944/j.eptep.1674-8069.2026.03.006
中图分类号:O643.36;X773
引用信息:
[1]杜昌飞,张博雅,程节兵,等.元素掺杂对VW/Ti基SCR催化剂宽温脱硝及抗硫性能的影响与反应机理研究[J].电力科技与环保,2026,42(03):404-412.DOI:10.19944/j.eptep.1674-8069.2026.03.006.
基金信息:
国家重点研发计划项目（2023YFB4102903）
2026-06-15
2026-06-15