助剂添加对CuO/TiO<sub>2</sub>催化剂NH<sub>3</sub>-SCO性能的影响研究

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摘要采用浸渍法制备了一系列CuO-MO_x/TiO₂ （M=W， Zr， La）催化剂用于NH₃选择性催化氧化（NH₃-SCO），同时探究了SO₂中毒对NH₃氧化性能的影响.结果表明，过渡金属氧化物的添加使Cu/TiO₂催化剂NH₃转化率降低，但显著提高N₂选择性.其中，WO₃具有最好的促进效果，在300℃下催化剂N₂选择性提高了36%.通过H₂-TPR和NH₃-TPD表征发现，WO₃的添加增加了Cu/TiO₂催化剂表面酸性位点的数量，促进NH₃的吸附，但降低催化剂氧化还原性能，抑制NH₃氧化为NO_x.经SO₂中毒处理后，CuO-MO_x/TiO₂催化剂N₂选择性进一步提高，表征结果表明，酸性位点的增加和氧化氧化还原性的降低是提高催化剂N₂选择性的关键.

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	陈浩辉
	王亚洲
	余杰
	邱磊
	尹一萌
	王驰中
	常化振

关键词 ： Cu/Ti基催化剂, NH₃选择性催化氧化, 金属氧化物添加, SO₂中毒

Abstract：A series of CuO-MO_x/TiO₂ (M=W, Zr, La) catalysts were prepared by impregnation method for the selective catalytic oxidation of NH₃, and the effects of SO₂ poisoning on the oxidation of NH₃ over Cu/Ti-based catalysts were investigated. The results show that adding of transition metal oxides decreased the NH₃ conversion efficiency of Cu/Ti catalyst slightly, but significantly improved the N₂ selectivity. WO₃ was the best promoter among those additives, with an increase of N₂ selectivity by 36% at 300℃ in comparison to Cu/Ti catalyst. The H₂-TPR and NH₃-TPD results indicate that adding of WO₃ significantly increased the number of acid sites on the surface of Cu/Ti catalyst, and promoted the adsorption of NH₃. But it affected the redox performance of the catalyst and inhibited the oxidation of NH₃ to NO_x. After SO₂ poisoning, the N₂ selectivity of CuO-MO_x/TiO₂ catalyst was further improved. The characterization results shows that the increase of acid sites and the reduction of redox performance are the key factors to improve the N₂ selectivity.

Key words： Cu/Ti-based catalysts NH₃ selective catalytic oxidation metal oxide adding SO₂ poisoning

收稿日期: 2023-03-17

PACS:

X511

基金资助:国家自然科学基金资助项目（22176217）

通讯作者: 常化振,教授,chz@ruc.edu.cn E-mail: chz@ruc.edu.cn

作者简介: 陈浩辉(1999-),男,河南驻马店人,中国人民大学硕士研究生,研究方向为大气污染控制.1020878834@qq.com.

引用本文:

陈浩辉, 王亚洲, 余杰, 邱磊, 尹一萌, 王驰中, 常化振. 助剂添加对CuO/TiO₂催化剂NH₃-SCO性能的影响研究[J]. 中国环境科学, 2023, 43(10): 5123-5130. CHEN Hao-hui, WANG Ya-zhou, YU Jie, QIU Lei, YIN Yi-meng, WANG Chi-zhong, CHANG Hua-zhen. Effect of additives and SO₂ on selective catalytic oxidation of NH₃ over CuO/TiO₂ catalysts. CHINA ENVIRONMENTAL SCIENCECE, 2023, 43(10): 5123-5130.

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http://www.zghjkx.com.cn/CN/ 或 http://www.zghjkx.com.cn/CN/Y2023/V43/I10/5123

[1]	Fujii H, Managi S. Economic development and multiple air pollutant emissions from the industrial sector[J]. Environmental Science and Pollution Research, 2016,23(3):2802-2812.
[2]	Jablonska M, Molla Robles A. A comparative mini-review on transition metal oxides applied for the selective satalytic ammonia oxidation (NH3-SCO)[J]. Materials, 2022,15(14):4770.
[3]	Gu B, Zhang L, ingenen R V, et al. Abating ammonia is more cost-effective than nitrogen oxides for mitigating PM2.5 air pollution[J]. Science, 2021,374(6568):758-762.
[4]	陈莉,樊星,李佳等.制备方法对SSZ-13负载Cu催化剂NH3-SCO性能的影响[J]. 中国环境科学, 2023,43(7):3378-3386. Chen L, Fan X, Li J, et al. Effect of preparation methods on NH3-SCO performance of SSZ-13 supported Cu catalysts[J]. China Environmental Science, 2023,43(7):3378-3386.
[5]	Bai Z, Winiwarter W, Klimont Z, et al. Further improvement of air quality in China needs clear ammonia mitigation target[J]. Environmental Science & Technology, 2019,53(18):10542-10544.
[6]	Wang F, Ma J, He G, et al. Nanosize effect of Al2O3 in Ag/Al2O3 catalyst for the selective catalytic oxidation of ammonia[J]. ACS Catalysis, 2018,8(4):2670-2682.
[7]	Bao Z, Xu H, Li K, et al. Effects of NH3 on secondary aerosol formation from toluene/NOx photo-oxidation in different O3 formation regimes[J]. Atmospheric Environment, 2021,261:118603.
[8]	Lan T, Deng J, Zhang F, et al. Unraveling the promotion effects of dynamically constructed CuOx-OH interfacial sites in the selective catalytic oxidation of ammonia[J]. ACS Catalysis, 2022,12(7):3955-3964.
[9]	Peng L, Guo A, Chen P, et al. Ammonia abatement via selective oxidation over electron-deficient copper catalysts[J]. Environmental Science & Technology, 2022,56(19):14008-14018.
[10]	Jabłońska M, R Palkovits. Copper based catalysts for the selective ammonia oxidation into nitrogen and water vapour-Recent trends and open challenges[J]. Applied Catalysis B:Environmental, 2016, 181:332-351.
[11]	Ge S, Liu X, Liu J, et al. Synthesis of TixSn1-xO2 mixed metal oxide for copper catalysts as high-efficiency NH3 selective catalytic oxidation[J]. Fuel, 2022,314:123061.
[12]	Decarolis D, Clark A H, Pellegrinelli T, et al. Spatial profiling of a Pd/Al2O3 catalyst during selective ammonia oxidation[J]. ACS Catalysis, 2021,11(4):2141-2149.
[13]	Wang F, He G, Zhang M, et al. Insights into the activation effect of H2 pretreatment on Ag/Al2O3 catalyst for the selective oxidation of ammonia[J]. ACS Catalysis, 2019,9(2):1437-1445.
[14]	Gong J L, Ojifinni R A, Kim T S, et al. Selective catalytic oxidation of ammonia to Nitrogen on atomic oxygen precovered Au(111)[J]. Journal of American Chemical Society, 2006,128:9012-9013.
[15]	Cui X, Chen L, Wang Y, et al. Fabrication of hierarchically porous RuO2-CuO/Al-ZrO2 composite as highly efficient catalyst for ammonia-selective catalytic oxidation[J]. ACS Catalysis, 2014,4(7):2195-2206.
[16]	Zhang Q, Zhang T, Xia F, et al. Promoting effects of acid enhancing on N2 selectivity for selectivity catalytic oxidation of NH3 over RuO/TiO2:The mechanism study[J]. Applied Surface Science, 2020,500:144044.
[17]	Svintsitskiy D A, Slavinskaya E M, Stonkus O A, et al. The state of platinum and structural features of Pt/Al2O3 catalysts in the reaction of NH3oxidation[J]. Journal of Structural Chemistry, 2019,60(6):919-931.
[18]	Lan T, Zhao Y, Deng J, et al. Selective catalytic oxidation of NH3 over noble metal-based catalysts:state of the art and future prospects[J]. Catalysis Science & Technology, 2020,10(17):5792-5810.
[19]	Long R Q, Yang R T, Selective catalytic oxidation of ammonia to nitrogen over Fe2O3-TiO2 prepared with a sol-gel method[J]. Journal of Catalysis, 2002,207(2):158-165.
[20]	Wang Z, Qu Z, Quan X, et al. Selective catalytic oxidation of ammonia to nitrogen over ceria-zirconia mixed oxides[J]. Applied Catalysis A:General, 2012,411-412:131-138.
[21]	Kwon D W, Lee S M, Hong S C. Influence of attrition milling on V/Ti catalysts for the selective oxidation of ammonia[J]. Applied Catalysis A:General, 2015,505:557-565.
[22]	Wang H, Zhang Q, Zhang T, et al. Structural tuning and NH3-SCO performance optimization of CuO-Fe2O3 catalysts by impact of thermal treatment[J]. Applied Surface Science, 2019,485:81-91.
[23]	Shojaee K, Haynes B S, Montoya A. The catalytic oxidation of NH3 on Co3O4(110):A theoretical study[J]. Proceedings of the Combustion Institute, 2017,36(3):4365-4373.
[24]	Fung W K, Ledwaba L, Modiba N, et al. Choosing a suitable support for Co3O4 as an NH3 oxidation catalyst[J]. Catalysis Science & Technology, 2013,3(8):1905-1909.
[25]	Qu Z, Fan R, Wang Z, et al. Selective catalytic oxidation of ammonia to nitrogen over MnO2 prepared by urea-assisted hydrothermal method[J]. Applied Surface Science, 2015,351:573-579.
[26]	Kim M S, Lee D W, Chung S H, et al. Oxidation of ammonia to nitrogen over Pt/Fe/ZSM5 catalyst:Influence of catalyst support on the low temperature activity[J]. J. Hazardous Materials, 2012,237-238:153-160.
[27]	Jabłońska M, Król A, Kukulska-Zajac E, et al. Zeolite Y modified with palladium as effective catalyst for selective catalytic oxidation of ammonia to nitrogen[J]. J. Catalysis, 2014,316:36-46.
[28]	Boroń P, Chmielarz L, Gurgul J, et al. The influence of the preparation procedures on the catalytic activity of Fe-BEA zeolites in SCR of NO with ammonia and N2O decomposition[J]. Catalysis Today, 2014,235:210-225.
[29]	Akah A C, Nkeng G, Garforth A A. The role of Al and strong acidity in the selective catalytic oxidation of NH3over Fe-ZSM-5[J]. Applied Catalysis B:Environmental, 2007,74(1/2):34-39.
[30]	Gang L, Grondelle J V, Anderson B G, et al. Selective low temperature NH3oxidation to N2on coppe-based catalysts[J]. J. Cayalysis, 1999, 186:100-109.
[31]	Jablonska M. Progress on noble metal-based catalysts dedicated to the selective catalytic ammonia oxidation into nitrogen and water vapor (NH3-SCO)[J]. Molecules, 2021,26(21):6461.
[32]	Il'chenko N I, Golodets G I. Catalytic oxidation of ammonia I. Reaction kinetics and Mechanism[J]. Journal of catalysis, 1975,39:57-72.
[33]	Jabłońska M, Wolkenar B, Beale A M, et al. Comparison of Cu-Mg-Al-Ox and Cu/Al2O3 in selective catalytic oxidation of ammonia (NH3-SCO)[J]. Catalysis Communications, 2018,110:5-9.
[34]	Yang M, Wu C, Zhang C, et al. Selective oxidation of ammonia over copper-silver-based catalysts[J]. Catalysis Today, 2004,90(3/4):263-267.
[35]	Liang C, Li X, Qu Z, et al. The role of copper species on Cu/γ-Al2O3 catalysts for NH3-SCO reaction[J]. Applied Surface Science, 2012,258(8):3738-3743.
[36]	Bagnasco G, Peluso G, Russo G, et al. Ammonia oxidation over CuO/TiO2 catalyst:selectivity and mechanistic study[J].3rd World Congress on oxidation catalysis, 1997,110:643-652.
[37]	He S, Zhang C, Yang Y, et al. Selective catalytic oxidation of ammonia from MAP decomposition[J]. Separation and Purification Technology, 2007,58(1):173-178.
[38]	Sun H, Wang H, Qu Z. Construction of CuO/CeO2catalysts via the ceria shape effect for selective catalytic oxidation of ammonia[J]. ACS Catalysis, 2023,13(2):1077-1088.
[39]	Yang X, Li N, Zhang Y, et al. Insight into the role of WO3 on catalytic performance over CuO-CeO2 catalyst for NH3selective catalytic oxidation reaction[J]. Journal of Environmental Chemical Engineering, 2021,9(6):106621.
[40]	Xie J, Jin Q, Fang D, et al., Effect of La/Ce modification over Cu based Y zeolite catalysts on high temperature selectivity for selective catalytic reduction with ammonia[J]. J. Cleaner Production, 2022, 362:132255.
[41]	Zhang Q, Wang H, Ning P, et al. In situ DRIFTS studies on CuO-Fe2O3catalysts for low temperature selective catalytic oxidation of ammonia to nitrogen[J]. Applied Surface Science, 2017,419:733-743.
[42]	Boer M D, Huisman H M, Mos R J M, et al. Selective oxidation of ammonia to nitrogen over SiO2-supported MoO3 catalysts[J]. Catalysis Today, 1993,17:198-200.
[43]	Wang Y, Yi W, Yu J, et al. Novel methods for assessing the SO2poisoning effect and thermal regeneration possibility of MOx-WO3/TiO2 (M=Fe, Mn, Cu and V) Catalysts for NH3-SCR[J]. Environmental Science & Technology, 2020,54(19):12612-12620.
[44]	Karthikeyan S, Raj A D, Irudayaraj A A, et al. Effect of temperature on the properties of La2O3 nanostructures[J]. Materials Today:Proceedings, 2015,2(3):1021-1025.
[45]	Cumbrera F L, Sponchia G, Benedetti A, et al. Some crystallographic considerations on the novel orthorhombic ZrO2 stabilized with Ta doping[J]. Ceramics International. 2018,14:10362-10366.
[46]	Adhikari S, Sarkar D, Maiti H S. Synthesis and characterization of WO3spherical nanoparticles and nanorods[J]. Materials Research Bulletin, 2014,49:325-330.
[47]	Liu W, Long Y, Tong X, et al. Transition metals modified commercial SCR catalysts as efficient catalysts in NH3-SCO and NH3-SCR reactions[J]. Molecular Catalysis, 2021,515:111888.
[48]	Yu L, Zhong Q, Zhang S, et al. A CuO-V2O5/TiO2 catalyst for the selectibe catalytic reduction of NO with NH3[J]. Combustion Science and Technology, 2015,187(6):925-936.
[49]	Nam K B, Lee S H, Hong S C. The role of copper in the enhanced performance of W/Ti catalysts for low-temperature selective catalytic reduction[J]. Applied Surface Science, 2021,544:148643.
[50]	Liu T, Wei L, Yao Y, et al. La promoted CuO-MnOx catalysts for optimizing SCR performance of NO with CO[J]. Applied Surface Science, 2021,546:148971.
[51]	Wang T, Li C, Zhao L, et al. The catalytic performance and characterization of ZrO2 support modification on CuO-CeO2/TiO2 catalyst for the simultaneous removal of Hg0and NO[J]. Applied Surface Science, 2017,400:227-237.
[52]	Xiong Z, Wang W, Li J, et al. The synergistic promotional effect of W doping and sulfate modification on the NH3-SCR activity of CeO2 catalyst[J]. Molecular Catalysis, 2022,522.
[53]	Ye D, Wang X, Liu H, et al. Insights into the effects of sulfate species on CuO/TiO2 catalysts for NH3-SCR reactions[J]. Molecular Catalysis, 2020,496.
[54]	Kušar H M J, Ersson A G, Vosecký M, et al. Selective catalytic oxidation of NH3 to N2for catalytic combustion of low heating value gas under lean/rich conditions[J]. Applied Catalysis B:Environmental, 2005,58(1/2):25-32.
[55]	Poston J A, Siriwardane R V, Fisher E P, et al. Thermal decomposition of the rare earth sulfates of cerium(III), cerium(IV), lanthanum(III) and samarium(III)[J]. Applied Surface Science, 2003,214(1-4):83-102.
[56]	Ahmed M A K, Fjellvag H, Kiekshus A. Synthesis and characterization of zirconium and hafnium sulfates, hydroxide sulfates and oxide sulfates[J]. Acta Chemica Scandinavica, 1999,53:24-33.
[57]	Xu L, Wang C, Chang H, et al. New insight into SO2 poisoning and regeneration of CeO2-WO3/TiO2 and V2O5-WO3/TiO2 catalysts for low-temperature NH3-SCR[J]. Environmental Science & Technology, 2018,52(12):7064-7071.