| 15 | 0 | 56 |
| 下载次数 | 被引频次 | 阅读次数 |
【目的】为实现火电行业烟气中氮氧化物(NOx)与挥发性有机物(VOCs)的协同控制，筛选高效催化剂，并探究不同制备方法对催化剂性能的影响。【方法】本研究通过溶胶凝胶法、水热法、共沉淀法和浸渍法在TiO2上负载Ce和Mn制备了一系列同时去除NO和甲苯(PhCH3)的催化剂，分别记作MnCe/Ti(S)、MnCe/Ti(H)、MnCe/Ti(C)和MnCe/Ti(I)，并系统评价其在200～450℃温度范围内的脱硝与甲苯氧化性能。采用扫描电子显微镜、X射线衍射、X射线光电子能谱、氢气程序升温还原和氨气程序升温脱附等表征技术，分析了不同制备方法对催化剂理化性能的影响。【结果】研究表明，4种催化剂的单独脱硝活性顺序为：MnCe/Ti(S)>MnCe/Ti(H)>MnCe/Ti(I)>MnCe/Ti(C),MnCe/Ti(S)和MnCe/Ti(H)催化剂在测试范围内的NO转化率都在90%以上，而MnCe/Ti(I)和MnCe/Ti(C)催化剂的转化率直到300℃都没有达到90%。当反应温度为200℃时，MnCe/Ti(S)催化剂对NO的去除率为97.6%，温度为250℃时，该催化剂对甲苯的去除率达80%。在250～350℃时，MnCe/Ti(S)催化剂对两种污染物的去除效果最好。发现相比于其他3种方法制备的MnCe/Ti催化剂，MnCe/Ti(S)催化剂表面颗粒更均匀，元素分散性更好，其表面有利于NO氧化的Mn3+浓度占比为83.98%，远远高于其他催化剂，同时MnCe/Ti(S)催化剂的酸量以及酸强度明显更大，低温氧化还原性能更优。【结论】本研究为电力、钢铁等行业烟气中NOx与VOCs的协同治理提供了高效催化剂筛选依据，也为锰基催化剂的制备方法优化提供了理论支持。
Abstract：[Objective]To achieve the synergistic control of nitrogen oxides(NOx) and volatile organic compounds(VOCs) in flue gas from the thermal power industry, screen high-performance catalysts, and investigate the influence of different preparation methods on their performance. [Methods]Here, Ce-and Mn-loaded TiO2 catalysts for concurrent NO and toluene(PhCH3) removal were prepared by sol-gel, hydrothermal, co-precipitation and impregnation routes, and their performance was evaluated between 200 ℃ and 450 ℃. The effects of different preparation methods on the physicochemical properties of the catalysts were analyzed using characterization techniques such as scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, ammonia temperature-programmed desorption, and hydrogen temperature-programmed reduction.[Results] The results indicate that the standalone DeNOx activity of the four catalysts follows the order: MnCe/Ti(S) > MnCe/Ti(H) > MnCe/Ti(I) > MnCe/Ti(C),the NO conversion rates of both MnCe/Ti(S) and MnCe/Ti(H) catalysts remained above 90% within the test range, whereas MnCe/Ti(I) and MnCe/Ti(C) catalysts failed to reach 90% even at 300 ℃. At a reaction temperature of 200 ℃, the MnCe/Ti(S) catalyst achieved a 97.6% removal rate for NO. At 250 ℃, the catalyst demonstrated an 80% removal rate for toluene. When the temperature is between 250 and 350 ℃, Mn Ce/Ti(S) exhibited the most effective removal performance for both pollutants. Compared to MnCe/Ti catalysts prepared by the other three methods, the Mn Ce/Ti(S) catalyst exhibited more uniform surface particles and superior elemental dispersion. Furthermore, the Mn3+ concentration in MnCe/Ti(S) catalysts, which is beneficial for NO oxidation, accounted for 83.98%, significantly higher than that in MnCe/Ti(H) and other catalysts. Additionally, MnCe/Ti(S) catalysts exhibited markedly higher acid content and acid strength, along with superior low-temperature De NOx performance. [Conclusion]The work provides an efficient catalyst option for simultaneous NOx and VOCs abatement in power-plant and steel-industry flue gases and offers theoretical guidance for optimising Mn-based catalyst synthesis.
[1]ZENG W L, LIU T, DU Q F, et al. The interplay of haze characteristics on mortality in the Pearl River Delta of China[J].Environmental Research, 2020:109279.
[2]MCFIGGANS G, MENTEL T F, WILDT J, et al. Secondary organic aerosol reduced by mixture of atmospheric vapours[J]. Nature,2019, 565(7741):587-593.
[3]TIAN D S, NIU S L. A global analysis of soil acidification caused by nitrogen addition[J]. Environmental Research Letters, 2015, 10(2):024019.
[4]LI T, YANG H L, XU L T, et al. Comprehensive treatment strategy for diesel truck exhaust[J]. Environmental Science and Pollution Research, 2023, 30(19):54324-54332.
[5]LI H R, MIAO J F, SU Q F, et al. Improvement in alkali metal resistance of commercial V2O5-WO3/TiO2 SCR catalysts modified by Ce and Cu[J]. Journal of Materials Science, 2019, 54(24):14707-14719.
[6]SUN X Y, LIU Q J, LIU S, et al. Improvement of low-temperature NH3-SCR catalytic performance over nitrogen-doped MOx-Cr2O3-La2O3/TiO2-N(M=Cu, Fe, Ce)catalysts[J]. RSC Advances, 2021,11(37):22780-22788.
[7]FANG D, LI D, HE F, et al. Experimental and DFT study of the adsorption and activation of NH3 and NO on Mn-based spinels supported on TiO2 catalysts for SCR of NOx[J]. Computational Materials Science, 2019, 160:374-381.
[8]WU Z B, JIANG B Q, LIU Y, et al. Experimental study on a lowtemperature SCR catalyst based on MnOx/TiO2 prepared by sol-gel method[J]. Journal of Hazardous Materials, 2007, 145(3):488-494.
[9]LU X X, DANG Y L, LI M L, et al. Synergistic promotion of transition metal ion-exchange in TiO2 nanoarray-based monolithic catalysts for the selective catalytic reduction of NOx with NH3[J].Catalysis Science&Technology, 2022, 12(17):5397-5407.
[10]CHEN L Q, YUAN F L, LI Z B, et al. Synergistic effect between the redox property and acidity on enhancing the low temperature NH3-SCR activity for NOx removal over the Co0.2CexMn0.8-xTi10(x=0-0.40)oxides catalysts[J]. Chemical Engineering Journal,2018, 354:393-406.
[11]ZHANG N Q, LI L C, GUO Y Z, et al. A MnO2-based catalyst with H2O resistance for NH3-SCR:Study of catalytic activity and reactants-H2O competitive adsorption[J]. Applied Catalysis B:Environmental, 2020, 270:118860.
[12]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)catalysts:Key role of acidity derived from tungsten addition[J]. Applied Catalysis A:General,2021, 627:118374.
[13]XIE S Z, LI L, JIN L J, et al. Low temperature high activity of M(M=Ce, Fe, Co, Ni)doped M-Mn/TiO2 catalysts for NH3-SCR and in situ DRIFTS for investigating the reaction mechanism[J].Applied Surface Science, 2020, 515:146014.
[14]LIU R Y, ZHOU B, LIU L Z, et al. Enhanced catalytic oxidation of VOCs over porous Mn-based mullite synthesized by in-situ dismutation[J]. Journal of Colloid and Interface Science, 2021,585:302-311.
[15]廖伟平,杨柳,王飞,等.不同制备方法的Mn-Ce催化剂低温SCR性能研究[J].化学学报, 2011, 69(22):2723-2728.LIAO Weiping, YANG Liu, WANG Fei, et al. Performance study for low-temperature SCR catalysts based on Mn-Ce prepared by different methods[J]. Acta Chimica Sinica, 2011, 69(22):2723-2728.
[16]CHEN L, LIAO Y F, CHEN Y, et al. Performance of Ce-modified V-W-Ti type catalyst on simultaneous control of NO and typical VOCs[J]. Fuel Processing Technology, 2020, 207:106483.
[17]CHEN Y, LIAO Y F, CHEN L, et al. Performance of transition metal(Cu, Fe and Co)modified SCR catalysts for simultaneous removal of NO and volatile organic compounds(VOCs)from coalfired power plant flue gas[J]. Fuel, 2021, 289:119849.
[18]LU X N, SONG C Y, JIA S H, et al. Low-temperature selective catalytic reduction of NOx with NH3 over cerium and manganese oxides supported on TiO2-graphene[J]. Chemical Engineering Journal, 2015, 260:776-784.
[19]LI T Y, SUN L C, WEY M Y. Redox ability dependent SO2 tolerance for low-temperature NH3-SCR of MnO2@MeOx(Me=Ti, Ce, Cu)catalysts[J]. Chemical Engineering Journal, 2024, 500:157395.
[20]AN Z Y, ZHOU Y, XU Q C, et al. Influence of the TiO2 crystalline phase of MnOx/TiO2 catalysts for NO oxidation[J]. Chinese Journal of Catalysis, 2014, 35(1):120-126.
[21]Atribak I, Bueno-López A, García-García A, et al. Catalytic activity for soot combustion of birnessite and cryptomelane[J].Applied Catalysis B:Environmental, 2010, 93(3):267-273.
[22]Cimino A, Indovina V. Catalytic activity of Mn3+and Mn4+ions dispersed in MgO for CO oxidation[J]. Journal of Catalysis, 1974,33(3):493-496.
[23]JIANG F, WANG S, LIU B, et al. Insights into the influence of CeO2 crystal facet on CO2 hydrogenation to methanol over Pd/CeO2 catalysts[J]. ACS Catalysis, 2020, 10(19):11493-11509.
[24]ZHU Y J, SUN Y Q, NIU X Y, et al. Preparation of La-Mn-O perovskite catalyst by microwave irradiation method and its application to methane combustion[J]. Catalysis Letters, 2010, 135(1):152-158.
[25]HUANG B F, SHI Z, YANG Z Y, et al. Mechanism of CO selective catalytic reduction denitration on Fe-Mn/AC catalysts at medium and low temperatures under oxygen atmosphere[J].Chemical Engineering Journal, 2022, 446:137412.
[26]ETTIREDDY P R, ETTIREDDY N, MAMEDOV S, et al. Surface characterization studies of TiO2 supported manganese oxide catalysts for low temperature SCR of NO with NH3[J]. Applied Catalysis B:Environmental, 2007, 76(1):123-134.
[27]CHEN L, REN S, JIANG Y H, et al. Effect of Mn and Ce oxides on low-temperature NH3-SCR performance over blast furnace slag-derived zeolite X supported catalysts[J]. Fuel, 2022, 320:123969.
[28]吴大旺,张秋林,林涛,等. Fe对Mn/CeO2-Ti O2催化剂低温NH3选择性催化还原NO的影响[J].无机材料学报, 2012, 27(5):495-500.WU Dawang, ZHANG Qiulin, LIN Tao, et al. Effect of Fe on the selective catalytic reduction of NO by NH3 at low temperature over Mn/CeO2-TiO2 catalyst[J]. Journal of Inorganic Materials,2012, 27(5):495-500.
[29]LIN X T, LI S J, HE H, et al. Evolution of oxygen vacancies in MnOx-CeO2 mixed oxides for soot oxidation[J]. Applied Catalysis B:Environmental, 2018, 223:91-102.
[30]FAN X X, HAO L F, GU X Y, et al. Low-temperature selective catalytic reduction of NO with NH3 over a biochar-supported perovskite oxide catalyst[J]. Energy&Fuels, 2023, 37(10):7339-7352.
基本信息:
DOI：10.19944/j.eptep.1674-8069.2026.03.007
中图分类号:TQ426;X773
引用信息:
[1]黄硕,储欣悦,张耀宇,等.不同制备方法对锰基催化剂脱除NO及甲苯的性能影响[J].电力科技与环保,2026,42(03):413-421.DOI:10.19944/j.eptep.1674-8069.2026.03.007.
基金信息:
国家自然科学基金项目(52470121); 江苏省研究生科研与实践创新计划项目(KYCX24＿1885)
2025-09-04
2025
2025-10-13
2025-10-15
2025
1
2026-06-15
2026-06-15