Preparation and NH3-SCR catalytic performance of CeTiOx catalysts with different pore structures

TAN Chenchen; HAN Yuxuan; HU Yaqin; SHEN Kai; DING Shipeng; ZHANG Yaping

doi:10.1016/S1872-5813(23)60369-X

Volume 52 Issue 1

Jan. 2024

Turn off MathJax

Article Contents

Article Navigation > Journal of Fuel Chemistry and Technology > 2024 > 52(1): 65-75

TAN Chenchen, HAN Yuxuan, HU Yaqin, SHEN Kai, DING Shipeng, ZHANG Yaping. Preparation and NH3-SCR catalytic performance of CeTiOx catalysts with different pore structures[J]. Journal of Fuel Chemistry and Technology, 2024, 52(1): 65-75. doi: 10.1016/S1872-5813(23)60369-X

Citation:

TAN Chenchen, HAN Yuxuan, HU Yaqin, SHEN Kai, DING Shipeng, ZHANG Yaping. Preparation and NH₃-SCR catalytic performance of CeTiO_x catalysts with different pore structures[J]. Journal of Fuel Chemistry and Technology, 2024, 52(1): 65-75. doi: 10.1016/S1872-5813(23)60369-X

Citation:

PDF( 2715 KB)

Preparation and NH₃-SCR catalytic performance of CeTiO_x catalysts with different pore structures

doi: 10.1016/S1872-5813(23)60369-X

Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096, China

Funds: The project was supported by National Key Research and Development Program of China (2021YFB3500604)

Received Date: 2023-04-16
Accepted Date: 2023-05-05
Rev Recd Date: 2023-04-28

Available Online: 2023-05-17

Publish Date: 2024-01-09

Abstract

Abstract

To investigate the influence of pore structure on the catalytic activity of catalysts, four catalysts including three-dimensionally ordered macroporous-mesoporous (3DOM-m) CeTiO_x, three-dimensionally ordered macroporous (3DOM) CeTiO_x, three-dimensionally ordered mesoporous (3DOm) CeTiO_xand disordered mesoporous (DM) CeTiO_x were synthesized by the sol-gel method. The NH₃-SCR denitration testing results show that the performance of the catalysts with different pore structures follows the sequence of 3DOM-m CeTiO_x>3DOm CeTiO_x>3DOM CeTiO_x>DM CeTiO_x, and the 3DOM-m CeTiO_x shows an excellent catalytic activity, with more than 90% NO conversion in the range of 250–400 ℃ at a GHSV of 60000 h⁻¹. The characterization of catalysts by XRD, SEM, BET, NH₃-TPD and in-situ DRIFTS indicates that the surface area is not the dominant factor determining the catalytic activity of CeTiO_x. 3DOM-m CeTiO_x has a highly ordered macroporous-mesoporous structure and abundant Bronsted acidic sites, thereby improving the denitrification activity. The NH₃-SCR reaction over the 3DOM-m CeTiO_x mainly follows the L-H and E-R mechanisms.
- CeTiO_x,
- 3DOM structure,
- ordered mesoporous structure,
- NH₃-SCR

FullText(HTML)

References(54)

References

[1]	YAN L J, LIU Y Y, LIU Y Y, et al. Scale-activity relationship of MnO_x-FeO_y nanocage catalysts derived from prussian blue analogues for low-temperature NO reduction: Experimental and DFT studies[J]. ACS Appl Mater Inter,2017,9(3):2581−2593. doi: 10.1021/acsami.6b15527
[2]	LIU Z, SUN G X, CHEN C, et al. Fe-doped Mn₃O₄ spinel nanoparticles with highly exposed Feoct-O-Mntet sites for efficient selective catalytic reduction(SCR) of NO with ammonia at low temperatures[J]. ACS Catal,2020,10(12):6803−6809. doi: 10.1021/acscatal.0c01284
[3]	FANG X, LIU Y J, CHENG Y, et al. Mechanism of Ce-modified birnessite-MnO₂ in promoting SO₂ poisoning resistance for low-temperature NH₃-SCR[J]. ACS Catal,2021,11(7):4125−4135. doi: 10.1021/acscatal.0c05697
[4]	CHEN Z C, REN S, WANG M M, et al. Insights into samarium doping effects on catalytic activity and SO₂ tolerance of MnFeO catalyst for low-temperature NH₃-SCR reaction[J]. Fuel,2022,321:124113−1124113. doi: 10.1016/j.fuel.2022.124113
[5]	PAN Y J, SHEN B X, LIU L J, et al. Develop high efficient of NH₃-SCR catalysts with wide temperature range by ball-milled method[J]. Fuel,2020,282:118834. doi: 10.1016/j.fuel.2020.118834
[6]	YI X F, WANG J X, LIU Y Q, et al. Promotional effect of Fe and Ce co-doping on a V₂O₅-WO₃/TiO₂ catalyst for SCR of NO_x with high K and Pb resistance[J]. Catal Sci Technol,2022,12(13):4169−4180. doi: 10.1039/D2CY00818A
[7]	梁彦正, 王学涛, 张乾蔚, 等. 双金属Ce-Mn/ZSM-5催化剂的制备及NH₃-SCR脱硝性能研究[J]. 燃料化学学报,2020,48(2):205−212. LIANG Yanzheng, WANG Xuetao, ZHANG Qianwei, et al. Performance of the modified Cu-Mn/SAPO-34 catalysts in selective catalytic reduction of NO_x by NH₃[J]. J Fuel Chem Technol,2020,48(2):205−212.
[8]	杨洋, 胡准, 米容立, 等. Mn负载量对nMnO_x/TiO₂催化剂NH₃-SCR催化性能的影响[J]. 分子催化,2020,34(4):313−325. YANG Yang, HU Zhun, MI Rongli, et al. Effect of Mn loading on catalytic performance of nMnO_x/TiO₂ in NH₃-SCR reaction[J]. J Mol Catal,2020,34(4):313−325.
[9]	纪生晓, 张玮坚, 郑玉婴, 等. 低温燃烧法制备Mn-CeO_x催化剂及其NH₃-SCR脱硝性能[J]. 燃料化学学报,2019,47(2):224−232. JI Shengxiao, ZHANG Yijian, ZHENG Yuying, et al. Low-temperature combustion synthesis of the Mn-CeO_x catalyst and its performance in the selective catalytic reduction of NO_x by NH₃[J]. J Fuel Chem Technol,2019,47(2):224−232.
[10]	于飞, 马江丽, 任德志, 等. 铁基分子筛活性位点的制备控制及对NH₃-SCR活性的影响[J]. 分子催化,2022,36(4):321−329. YU Fei, MA Jiangli, REN Dezhi, et al. Effect of Iron sites and synthesis procedure of Fe-beta catalysts on NH₃-SCR performance[J]. J Mol Catal,2022,36(4):321−329.
[11]	CHEN W, YANG S, LIU H, et al. Single-atom Ce-modified alpha-Fe₂O₃ for selective catalytic reduction of NO with NH₃[J]. Environ Sci Technol,2022,56:10442−10453. doi: 10.1021/acs.est.2c02916
[12]	刘崇飞, 王学涛, 邢利益, 等. 双金属Cu-Ce/SAPO-34催化剂的制备及其NH₃-SCR脱硝性能研究[J]. 燃料化学学报,2022,50(10):1316−1323. LIU Chongfei, WANG Xuetao, XING Liyi, et al. Study on preparation and denitrification performance of NH₃-SCR of bimetallic Cu-Ce/SAPO-34 catalyst[J]. J Fuel Chem Technol,2022,50(10):1316−1323.
[13]	WANG J, FAN D Q, YU T, et al. Improvement of low-temperature hydrothermal stability of Cu/SAPO-34 catalysts by Cu²⁺ species[J]. J Catal,2015,322:84−90. doi: 10.1016/j.jcat.2014.11.010
[14]	LIU C X, CHEN L, LI J H, et al. Enhancement of activity and sulfur resistance of CeO₂ supported on TiO₂-SiO₂ for the selective catalytic reduction of NO by NH₃[J]. Environ Sci Technol,2012,46(11):6182−6189. doi: 10.1021/es3001773
[15]	周国民, 李明圆, 付在国, 等. 碱金属对NH₃-SCR脱硝催化剂Ce/TiO₂的毒化研究[J]. 应用化工,2018,47(12):2616−2619. ZHOU Guomin, LI Mingyuan, FU Zaiguo, et al. Influence of alkali metals on Ce/TiO₂ catalyst for selective catalytic reduction of no with NH₃[J]. Appl Chem Ind,2018,47(12):2616−2619.
[16]	耿新泽, 段钰锋, 胡鹏, 等. SCR气氛下Ce-W/TiO₂催化剂的脱硝协同脱汞特性[J]. 中国环境科学,2019,39(4):1419−1426. GENG Xinze, DUAN Yufeng, HU Peng, et al. Characteristics of denitrification and mercury removal of Ce-W/TiO₂ catalysts in SCR atmosphere[J]. China Environ Sci,2019,39(4):1419−1426.
[17]	康海彦, 莫杜娟, 张学军, 等. CeO₂-WO₃催化剂表面酸性和氧化还原性能在脱硝反应中的研究[J/OL]. 燃料化学学报 (中英文), 2023, 51(6): 814–824. KANG Haiyan, MO Dujuan, ZHANG Xuejun, et al. Investigation of the surface acidity and redox on the CeO₂-WO₃ catalyst for selective catalytic reduction with NH₃[J/OL]. J Fuel Chem Technol, 2023, 51(6): 814–824.
[18]	LI Q, LI X, LI W, et al. Effect of preferential exposure of anatase TiO₂ {0 0 1} facets on the performance of Mn-Ce/TiO₂ catalysts for low-temperature selective catalytic reduction of NO_x with NH₃[J]. Chem Eng J,2019,369:26−34. doi: 10.1016/j.cej.2019.03.054
[19]	赵海, 张德祥, 高晋生. 稀土掺杂铁锰脱硝催化剂的制备及其性能研究[J]. 煤炭转化,2011,34(4):72−74 + 78. ZHAO Hai, ZHANG Dexiang, GAO Jinsheng. Selective catalytic reduction of NO_x with NH₃ over Fe-Mn-O catalyst promoted by CeO₂[J]. Coal Conversion,2011,34(4):72−74 + 78.
[20]	周超, 赵阳, 徐佳, 等. pH值对浸渍法制备的铈钨钛脱硝催化剂的影响[J]. 稀土,2020,41(5):59−69. ZHOU Chao, ZHAO Yang, XU Jia, et al. Effect of pH on denitration performance of CeWTi catalyst[J]. Chin Rare Earths,2020,41(5):59−69.
[21]	安志强. 二氧化钛载体制备及性能研究[D]. 南京: 南京工业大学, 2005. AN Zhiqiang. Studies on the preparation and performance of TiO₂ supports[D]. Nanjing: Nanjing University of Technology, 2005.
[22]	ZHANG Z P, LI R M, WANG M J, et al. Two steps synthesis of CeTiO_x oxides nanotube catalyst: Enhanced activity, resistance of SO₂ and H₂O for low temperature NH₃-SCR of NO_x[J]. Appl Catal B: Environ,2021,282:119542. doi: 10.1016/j.apcatb.2020.119542
[23]	ZHANG Z P, CHEN L Q, LI Z B, et al. Activity and SO₂ resistance of amorphous Ce_aTiO_x catalysts for the selective catalytic reduction of NO with NH₃: in situ DRIFT studies[J]. Catal Sci Technol,2016,6(19):7151−7162. doi: 10.1039/C6CY00475J
[24]	FEI Z Y, YANG Y R, WANG M H, et al. Precisely fabricating Ce-O-Ti structure to enhance performance of Ce-Ti based catalysts for selective catalytic reduction of NO with NH₃[J]. Chem Eng J,2018,353:930−939. doi: 10.1016/j.cej.2018.07.198
[25]	HUANG B J, YU D Q, SHENG Z Y, et al. Novel CeO₂@TiO₂ core-shell nanostructure catalyst for selective catalytic reduction of NO_xwith NH₃[J]. J Environ Sci,2017,55(5):129−136.
[26]	MA K L, GUO K, LI L L, et al. Cavity size dependent SO₂ resistance for NH₃-SCR of hollow structured CeO₂-TiO₂ catalysts[J]. Catal Commun,2019,128:105719. doi: 10.1016/j.catcom.2019.105719
[27]	李丹, 王慧, 陈留平, 等. 一种无定形有序的Ce-Ti催化膜用于同时去除粉尘和氮氧化物(英文)[J]. 无机化学学报,2020,36(11):2189−2196. LI Dan, WANG Hui, CHEN Liuping, et al. Ordered mesoporous and complete amorphous Ce-Ti catalytic filter for particle separation and NO_x removal[J]. Chin J Inorg Chem,2020,36(11):2189−2196.
[28]	HONG H, LIU J L, HUANG H W, et al. Ordered macro-microporous metal-organic framework single crystals and their derivatives for rechargeable aluminum-ion batteries[J]. J Am Chem Soc,2019,141:14764−14771. doi: 10.1021/jacs.9b06957
[29]	YANG G C, PAN Q Y, YANG P, et al. Heteropolyacids supported on hierarchically macro/mesoporous TiO₂: Efficient catalyst for deep oxidative desulfurization of fuel[J]. Tungsten,2022,4(1):28−37. doi: 10.1007/s42864-021-00125-2
[30]	ZHOU Z M, ZENG T Y, CHENG Z M, et al. Preparation and characterization of titania-alumina mixed oxides with hierarchically macro-mesoporous structures[J]. Ind Eng Chem Res,2011,50(2):883−890. doi: 10.1021/ie101697t
[31]	ZHOU Z M, ZENG T Y, CHENG Z M, et al. Preparation of a catalyst for selective hydrogenation of pyrolysis gasoline[J]. Ind Eng Chem Res,2010,49:11112−11118. doi: 10.1021/ie1003043
[32]	ZHOU Z M, ZENG T Y, CHENG Z M, et al. Diffusion-enhanced hierarchically macro-mesoporous catalyst for selective hydrogenation of pyrolysis gasoline[J]. AICHE J,2011,57(8):2198−2206. doi: 10.1002/aic.12421
[33]	邓权政, 毛文婷, 韩璐. 介观尺度多孔材料的电子显微学结构解析[J]. 化学学报,2022,80(8):1203−1216. doi: 10.6023/A22030136 DENG Quanzheng, MAO Wenting, HAN Lu. Structural solution of porous materials on the mesostructural scale by electron microscopy[J]. Acta Chim Sin,2022,80(8):1203−1216. doi: 10.6023/A22030136
[34]	WANG L Y, REN Y, YU X H, et al. Novel preparation method, catalytic performance and reaction mechanisms of Pr_xMn_1-xO_d/3DOM ZSM-5 catalysts for the simultaneous removal of soot and NO_x[J]. J Catal,2023,417:226−247. doi: 10.1016/j.jcat.2022.12.004
[35]	LI Y L, LI W M, YAN R, et al. Hierarchical three-dimensionally ordered macroporous Fe-V binary metal oxide catalyst for low temperature selective catalytic reduction of NO_x from marine diesel engine exhaust[J]. Appl Catal B: Environ,2020,268:118455. doi: 10.1016/j.apcatb.2019.118455
[36]	宋丽云, 邓世林, 周宜芸, 等. V₂O₅-MoO₃/TiO₂催化剂的NH₃-SCR性能: 载体的影响[J]. 材料导报,2023,37(6):71−76. SONG Liyun, DENG Shilin, ZHOU Yiyun, et al. NH₃-SCR performance of V₂O₅-MoO₃/TiO₂ catalyst: Effect of support[J]. Mater Rep,2023,37(6):71−76.
[37]	ZHANG X L, HU X R, LIU S W, et al. MnO_x-pillared rectorite prepared by in-situ deposition as efficient catalysts for low-temperature NH₃-SCR: The influences of manganese (II) precursors[J]. J Environ Chem Eng,2022,10(2):105719.
[38]	PAN J H, ZHAO X S, LEE W I. Block copolymer-templated synthesis of highly organized mesoporous TiO₂-based films and their photoelectrochemical applications[J]. Chem Eng J,2011,170(2-3):363−380. doi: 10.1016/j.cej.2010.11.040
[39]	MU Y B, HUANG X S, TANG Z C, et al. Ordered mesoporous TiO₂ framework confined CeSn catalyst exhibiting excellent high activity for selective catalytic reduction of NO with NH₃ at low temperature[J]. Chem Eng J,2023,454:140−181.
[40]	梅雪垒, 熊靖, 韦岳长, 等. 三维有序大孔钙钛矿型La_1−xK_xNiO₃催化剂提高炭烟催化燃烧活性: K取代的作用(英文)[J]. 催化学报,2019,40(5):722−732. doi: 10.1016/S1872-2067(18)63269-9 MEI Xuelei, XIONG Jing, WEI Yuechang, et al. Three-dimensional ordered macroporous perovskite-type La_1−xK_xNiO₃ catalysts with enhanced catalytic activity for soot combustion: the Effect of K-substitution[J]. Chin J Catal,2019,40(5):722−732. doi: 10.1016/S1872-2067(18)63269-9
[41]	王艳, 李兆强, 赵文怡, 等. 有序介孔CeO₂基催化剂用于富H₂中CO优先氧化的研究[J]. 稀土,2018,39(1):1−10. WANG Yan, LI Zhaoqiang, ZHAO Wenyi, et al. Modified highly ordered mesoporous ceria-based catalysts employed for CO preferential oxidation in H₂-rich stream[J]. Chin Rare Earth,2018,39(1):1−10.
[42]	ZHONG Y K, CHANG S, DONG G J. Preparation and characterization of a novel double-walled Na₂(TiO)SiO₄ nanotube by hydrothermal process with CTAB as an assistant[J]. Microporous Mesoporous Mater,2017,239:70−77.
[43]	XU Y, ZHOU M L, CHEN M T, et al. Simultaneous removal of NO and elemental mercury from coal-fired flue gas using natural ferruginous manganese ore at low temperature[J]. Fuel,2022,326:125118.
[44]	WANTANABE S G, MA X L, SONG C S. Characterization of structural and surface properties of nanocrystalline TiO₂-CeO₂ mixed oxides by XRD, XPS, TPR, and TPD[J]. J Phys Chem C,2009,113(32):14249−21425. doi: 10.1021/jp8110309
[45]	LIU B, LIU J, MA S C, et al. Mechanistic study of selective catalytic reduction of NO with NH₃ on W-Doped CeO₂ catalysts: Unraveling the catalytic cycle the role of oxygen vacancy[J]. J Phys Chem C,2016,120(4):2271−2283. doi: 10.1021/acs.jpcc.5b11355
[46]	WU Z B, JIANG B Q, LIU Y, et al. DRIFT study of manganese/titania-based catalysts for low-temperature selective catalytic reduction of NO with NH₃[J]. Environ Sci Technol,2007,41(16):5812−5817. doi: 10.1021/es0700350
[47]	LIU F D, ASAKURA K, HE H, et al. Influence of calcination temperature on iron titanate catalyst for the selective catalytic reduction of NO_x with NH₃[J]. Catal Today,2011,164(1):520−527. doi: 10.1016/j.cattod.2010.10.008
[48]	陈宜华, 王攀, 孟凡禹, 等. VPO/TiO₂催化剂表面酸性位调控及低温NH₃-SCR脱硝性能研究[J]. 中国环境科学,2023,43(4):1558−1566. CHEN Yihua, WANG Pan, MENG Fanyu, et al. The optimization of surface acidity VPO/TiO, catalyst and its low-temperature NH₃-SCR denitration performance[J]. China Environ Sci,2023,43(4):1558−1566.
[49]	SHAN W, LIU F, HONG H, et al. A superior Ce-W-Ti mixed oxide catalyst for the selective catalytic reduction of NO_x with NH₃[J]. Appl Catal B: Environ,2012,115−116:100−106. doi: 10.1016/j.apcatb.2011.12.019
[50]	CHEN L, LI J, GE M F. DRIFT study on cerium-tungsten/titiania catalyst for selective catalytic reduction of NO_x with NH₃[J]. Environ Sci Technol,2010,44:9590−9596. doi: 10.1021/es102692b
[51]	LIU Z M, ZHANG S X, LI J H, et al. Promoting effect of MoO₃ on the NO_x reduction by NH₃ over CeO₂/TiO₂ catalyst studied with in situ DRIFTS[J]. Appl Catal B: Environ,2014,144:90−95. doi: 10.1016/j.apcatb.2013.06.036
[52]	SHU Y, SUN H, QUAN X, et al. Enhancement of catalytic activity over the iron-modified Ce/TiO₂ catalyst for selective catalytic reduction of NO_x with ammonia[J]. J Phys Chem C,2012,116(48):25319−25327. doi: 10.1021/jp307038q
[53]	LIU Z, LIU Y, CHEN B, et al. Novel Fe-Ce-Ti catalyst with remarkable performance for the selective catalytic reduction of NO_x by NH₃[J]. Catal Sci Technol,2016,6:6688−6696. doi: 10.1039/C5CY02278A
[54]	CHEN W M, MA Y P, QU Z, et al. Mechanism of the selective catalytic oxidation of slip ammonia over Ru-modified Ce-Zr complexes determined by in situ diffuse reflectance infrared fourier transform spectroscopy[J]. Environ Sci Technol,2014,48(20):12199−12205. doi: 10.1021/es502369f