SCR脱硝金属氧化物催化剂研究进展

摘要/Abstract

摘要： 氮氧化物是大气主要污染物之一,选择性催化还原(SCR)是国内外工业锅炉(窑炉)烟气脱硝的主要技术途径。脱硝催化剂是SCR技术的核心,近几十年来为人们所关注和广泛研究。金属氧化物催化剂材料来源广泛,制备简单,脱硝效率稳定,在工业锅炉(窑炉)烟气脱硝中具有广阔的应用前景,因而成为人们研究关注的重点。本文基于SCR烟气脱硝理论现状,归纳了金属氧化物催化剂优化设计的关键与重要基础,同时,梳理了目前备受研究关注的钒基、锰基、铈基、铁基等四种典型金属氧化物催化剂的研究进展,系统介绍了不同氧化物催化剂的脱硝机理、本质特征、元素改良、结构和形貌设计,以及存在的问题等,并展望了今后金属氧化物催化剂研究的发展趋势,为今后工业锅炉(窑炉)烟气高效脱硝催化剂的研发提供参考借鉴。

关键词: 氮氧化物, 选择性催化还原, 机理, 烟气脱硝, 金属氧化物, 催化剂

Abstract: Nitrogen oxides are the one of major air pollution. Selective catalytic reduction (SCR) is the main technical way of high-efficiency DeNO_x of industrial boiler (kiln) flue gas at home and abroad. The DeNO_x catalyst is the core of SCR technology, which has been concerned and widely studied in recent decades. Metal oxide catalyst has a broad application prospect in industrial boiler (kiln) flue gas DeNO_x, wide range of material sources, simple preparation and stable DeNO_x efficiency, and it becomes the focus of research attention. Based on the current situation of SCR flue gas DeNO_x theory, the key and important basis for the optimal design of metal oxide catalysts were summarized. At the same time, the research progress of four typical metal oxide catalysts, such as vanadium, manganese, cerium and iron, was reviewed. The DeNO_x mechanism, essential characteristics, element improvement, structure and morphology design and existing problems of different oxide catalysts were introduced systematically, and the development trend of metal oxide catalysts in the future was prospected. It would provide reference for the research of efficient DeNO_x catalyst for industrial boiler (kiln) flue gas.

Key words: nitrogen oxide, selective catalytic reduction, mechanism, flue gas DeNO_x, metal oxide, catalyst

中图分类号:

TQ172

王昕, 张金山, 汪澜. SCR脱硝金属氧化物催化剂研究进展[J]. 硅酸盐通报, 2023, 42(2): 509-519.

WANG Xin, ZHANG Jinshan, WANG Lan. Research Progress on SCR DeNO_x Metallic Oxide Catalysts[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2023, 42(2): 509-519.

参考文献

[1] HUANG R J, ZHANG Y L, BOZZETTI C, et al. High secondary aerosol contribution to particulate pollution during haze events in China[J]. Nature, 2014, 514(7521): 218-222.
[2] 苏士焜, 宗保宁, 荣峻峰. 金属氧化物催化剂用于NO催化氧化的研究进展[J]. 化工环保, 2022, 42(3): 249-254.
SU S K, ZONG B N, RONG J F. Research progress of metal oxide catalysts for catalytic oxidation of NO[J]. Environmental Protection of Chemical Industry, 2022, 42(3): 249-254 (in Chinese).
[3] 王金玉. 掺杂Ce对Mn基脱硝催化剂抗水抗硫性的实验研究和模拟分析[D]. 青岛: 青岛大学, 2020.
WANG J Y. Experimental study and simulation analysis of water resistance and sulfur resistance of Mn-based denitration catalyst doped with Ce[D]. Qingdao: Qingdao University, 2020 (in Chinese).
[4] HAN L P, CAI S, GAO M, et al. Selective catalytic reduction of NO_x with NH₃ by using novel catalysts: state of the art and future prospects[J]. Chemical Reviews, 2019, 119: 10916-10976.
[5] CAO L, CHEN L, WU X D, et al. TRA and DRIFTS studies of the fast SCR reaction over CeO₂/TiO₂ catalyst at low temperatures[J]. Applied Catalysis A: General, 2018, 557: 46-54.
[6] YUAN H Y, CHEN J F, WANG H F, et al. Activity trend for low-concentration NO oxidation at room temperature on rutile-type metal oxides[J]. ACS Catalysis, 2018, 8(11): 10864-10870.
[7] GILLOT S, TRICOT G, VEZIN H, et al. Development of stable and efficient CeVO₄ systems for the selective reduction of NO_x by ammonia: structure-activity relationship[J]. Applied Catalysis B: Environmental, 2017, 218: 338-348.
[8] 张洪亮, 龙红明, 李家新, 等. 铁基催化剂用于氨选择性催化还原氮氧化物研究进展[J]. 无机化学学报, 2019, 35(5): 753-768.
ZHANG H L, LONG H M, LI J X, et al. Research progress in iron-based catalysts for the selective catalytic reduction of NO_x by NH₃[J]. Chinese Journal of Inorganic Chemistry, 2019, 35(5): 753-768 (in Chinese).
[9] QI G, YANG R T, CHANG R. MnO_x-CeO₂ mixed oxides prepared by co-precipitation for selective catalytic reduction of NO with NH₃ at low temperatures[J]. Applied Catalysis B: Environmental, 2004, 51(2): 93-106.
[10] CAO F, XIANG J, SU S, et al. Ag modified Mn-Ce/γ-Al₂O₃ catalyst for selective catalytic reduction of NO with NH₃ at low-temperature[J]. Fuel Processing Technology, 2015, 135: 66-72.
[11] 陈靓. 基于酸性位强化的铈基催化剂结构调控及NH₃-SCR反应机制[D]. 杭州: 浙江大学, 2020.
CHEN L. Design of acid-site strengthened cerium-based catalyst and its NH₃-SCR mechanism investigation[D]. Hangzhou: Zhejiang University, 2020 (in Chinese).
[12] DAMMA D, ETTIREDDY P, REDDY B, et al. A review of low temperature NH₃-SCR for removal of NO_x[J]. Catalysts, 2019, 9(4): 349.
[13] 云军阁, 胡晓玫, 赵成, 等. 中低温NH₃-SCR催化剂抗中毒研究进展[J]. 环境科学与技术, 2021, 44(1): 141-150.
YUN J G, HU X M, ZHAO C, et al. Research progress on anti-poisoning of NH₃-SCR catalysts at medium and low temperature[J]. Environmental Science & Technology, 2021, 44(1): 141-150 (in Chinese).
[14] LIU H Z, YOU C F, WANG H M. Time-resolved in situ IR and DFT study: NH₃ adsorption and redox cycle of acid site on vanadium-based catalysts for NO abatement via selective catalytic reduction[J]. Chemical Engineering Journal, 2020, 382: 122756.
[15] KE Y, HUANG W J, LI S C, et al. Surface acidity enhancement of CeO₂ catalysts via modification with a heteropoly acid for the selective catalytic reduction of NO with ammonia[J]. Catalysis Science & Technology, 2019, 9(20): 5774-5785.
[16] 马赫遥, 周曙光, 王晓祥, 等. 不同的WO₃掺杂量对CeO₂的NH₃-SCR催化性能影响研究[J]. 高校化学工程学报, 2022, 36(2): 242-248.
MA H Y, ZHOU S G, WANG X X, et al. Effects of WO₃ doping amounts of CeO₂ on NH₃-SCR catalytic performance[J]. Journal of Chemical Engineering of Chinese Universities, 2022, 36(2): 242-248 (in Chinese).
[17] TOPSOE N Y, DUMESIC J A, TOPSOE H. Vanadia-titania catalysts for selective catalytic reduction of nitric-oxide by ammonia[J]. Journal of Catalysis, 1995, 151(1): 241-252.
[18] DONG G J, BAI Y, ZHANG Y F, et al. Effect of the V⁴⁺⁽³⁺⁾/V⁵⁺ ratio on the denitration activity for V₂O₅-WO₃/TiO₂ catalysts[J]. New Journal of Chemistry, 2015, 39(5): 3588-3596.
[19] 苏茂, 刘少光, 戴炎彬, 等. 稀土氧化物对钒钛类催化剂性能的影响[C]//2011中国功能材料科技与产业高层论坛论文集(第一卷). 重庆, 2011: 372-376.
SU M, LIU S G, DAI Y B, et al. Effect of rare earth oxides on the properties of vanadium and titanium catalysts[C]//2011 China Functional Materials Technology and Industry High-level Forum proceedings (Volume 1). Chongqing, 2011: 372-376 (in Chinese).
[20] 胡建飞. 钛基SCR催化剂及其脱硝性能研究[D]. 太原: 太原理工大学, 2011.
HU J F. Research on denitrification performance of titanium-based SCR catalysts[D]. Taiyuan: Taiyuan University of Technology, 2011 (in Chinese).
[21] MA Z R, WU X D, FENG Y, et al. Low-temperature SCR activity and SO₂ deactivation mechanism of Ce-modified V₂O₅-WO₃/TiO₂ catalyst[J]. Progress in Natural Science: Materials International, 2015, 25(4): 342-352.
[22] CHEN M Y, ZHAO M M, TANG F S, et al. Effect of Ce doping into V₂O₅-WO₃/TiO₂ catalysts on the selective catalytic reduction of NO_x by NH₃[J]. Journal of Rare Earths, 2017, 35(12): 1206-1215.
[23] 裴鑫琦. 低温钒钛系SCR脱硝催化剂改性研究[D]. 北京: 华北电力大学(北京), 2021.
PEI X Q. Research on modification of low temperature V₂O₅/TiO₂ SCR catalysts[D]. Beijing: North China Electric Power University, 2021 (in Chinese).
[24] HE Y Y, FORD M E, ZHU M H, et al. Influence of catalyst synthesis method on selective catalytic reduction (SCR) of NO by NH₃ with V₂O₅-WO₃/TiO₂ catalysts[J]. Applied Catalysis B: Environmental, 2016, 193: 141-150.
[25] 乔明, 张继义, 宗路遥, 等. 催化脱硝技术研究进展——催化剂的种类、制备方法及催化活性[J]. 分子催化, 2020, 34(2): 165-181.
QIAO M, ZHANG J Y, ZONG L Y, et al. Research progress in catalytic denitrification performance: the catalyst type, preparation methods and activity[J]. Journal of Molecular Catalysis (China), 2020, 34(2): 165-181 (in Chinese).
[26] LI W Z, GAO F, LI Y, et al. Nanocrystalline anatase titania-supported vanadia catalysts: facet-dependent structure of vanadia[J]. The Journal of Physical Chemistry C, 2015, 119(27): 15094-15102.
[27] 郭梓阳, 霍旺晨, 张育新, 等. 锰基低温NH₃-SCR脱硝催化剂的研究概述[J]. 材料导报, 2021, 35(13): 13085-13099.
GUO Z Y, HUO W C, ZHANG Y X, et al. A review of Mn-based low temperature NH₃-SCR denitration catalyst[J]. Materials Reports, 2021, 35(13): 13085-13099 (in Chinese).
[28] 李娜, 陈泽东, 王晶晶, 等. 基于氧化铈的低温NH₃-SCR催化剂的研究进展[J]. 材料导报, 2022, 36(8): 54-63.
LI N, CHEN Z D, WANG J J, et al. Research progress of cerium oxide-based catalysts for NH₃-SCR at low temperature[J]. Materials Reports, 2022, 36(8): 54-63 (in Chinese).
[29] ZHANG S B, ZHAO Y C, YANG J P, et al. Simultaneous NO and mercury removal over MnO_x/TiO₂ catalyst in different atmospheres[J]. Fuel Processing Technology, 2017, 166: 282-290.
[30] YAO X J, KONG T T, YU S H, et al. Influence of different supports on the physicochemical properties and denitration performance of the supported Mn-based catalysts for NH₃-SCR at low temperature[J]. Applied Surface Science, 2017, 402: 208-217.
[31] 张哲. Mn-Ce系列催化剂的性能、表征及应用研究[D]. 武汉: 武汉理工大学, 2016.
ZHANG Z. Study on the properties, characterization and application of Mn-Ce series catalysts[D]. Wuhan: Wuhan University of Technology, 2016 (in Chinese).
[32] LI S H, HUANG B C, YU C L. A CeO₂-MnO_x core-shell catalyst for low-temperature NH₃-SCR of NO[J]. Catalysis Communications, 2017, 98: 47-51.
[33] QI G, YANG R T. Characterization and FTIR studies of MnO_x-CeO₂ catalyst for low-temperature selective catalytic reduction of NO with NH₃[J]. The Journal of Physical Chemistry B, 2004, 108(40): 15738-15747.
[34] PEÑA D A, UPHADE B S, REDDY E P, et al. Identification of surface species on titania-supported manganese, chromium, and copper oxide low-temperature SCR catalysts[J]. The Journal of Physical Chemistry B, 2004, 108(28): 9927-9936.
[35] CAO F, SU S, XIANG J, et al. The activity and mechanism study of Fe-Mn-Ce/γ-Al₂O₃ catalyst for low temperature selective catalytic reduction of NO with NH₃[J]. Fuel, 2015, 139: 232-239.
[36] 陈利强. 基于低温氨选择性催化还原NO的锰基催化剂制备及性能[D]. 哈尔滨: 黑龙江大学, 2017.
CHEN L Q. Preparation of Manganese based catalyst for low-temperature SCR of NO and its performance[D]. Harbin: Helongjiang University, 2017 (in Chinese).
[37] HU H, ZHA K W, LI H R, et al. In situ DRIFTs investigation of the reaction mechanism over MnO_x-MO_y/Ce_{0. 75}Zr_{0. 25}O₂ (M=Fe, Co, Ni, Cu) for the selective catalytic reduction of NO_x with NH₃[J]. Applied Surface Science, 2016, 387: 921-928.
[38] GAN L N, LI K Z, YANG W N, et al. Core-shell-like structured α-MnO₂@CeO₂ catalyst for selective catalytic reduction of NO: promoted activity and SO₂ tolerance[J]. Chemical Engineering Journal, 2020, 391: 123473.
[39] HUANG X S, DONG F, ZHANG G D, et al. A strategy for constructing highly efficient yolk-shell[email protected]@TiO_x catalyst with dual active sites for low-temperature selective catalytic reduction of NO with NH₃[J]. Chemical Engineering Journal, 2021, 419: 129572.
[40] SHI Y R, YI H H, GAO F Y, et al. Facile synthesis of hollow nanotube MnCoO_x catalyst with superior resistance to SO₂ and alkali metal poisons for NH₃-SCR removal of NO_x[J]. Separation and Purification Technology, 2021, 265: 118517.
[41] YU S H, JIANG N X, ZOU W X, et al. A general and inherent strategy to improve the water tolerance of low temperature NH₃-SCR catalysts via trace SiO₂ deposition[J]. Catalysis Communications, 2016, 84: 75-79.
[42] ZHANG Q L, LIU X, NING P, et al. Enhanced performance in NO_x reduction by NH₃ over a mesoporous Ce-Ti-MoO_x catalyst stabilized by a carbon template[J]. Catalysis Science & Technology, 2015, 5(4): 2260-2269.
[43] QI G, YANG R T, CHANG R. MnO_x-CeO₂ mixed oxides prepared by co-precipitation for selective catalytic reduction of NO with NH₃ at low temperatures[J]. Applied Catalysis B: Environmental, 2004, 51(2): 93-106.
[44] CHITPAKDEE C, JUNKAEW A, MAITARAD P, et al. Understanding the role of Ru dopant on selective catalytic reduction of NO with NH₃ over Ru-doped CeO₂ catalyst[J]. Chemical Engineering Journal, 2019, 369: 124-133.
[45] GAO F Y, TANG X L, YI H H, et al. Promotional mechanisms of activity and SO₂ tolerance of Co- or Ni-doped MnO_x-CeO₂ catalysts for SCR of NO_x with NH₃ at low temperature[J]. Chemical Engineering Journal, 2017, 317: 20-31.
[46] LIU Z M, ZHU J Z, LI J H, et al. Novel Mn-Ce-Ti mixed-oxide catalyst for the selective catalytic reduction of NO_x with NH₃[J]. ACS Applied Materials & Interfaces, 2014, 6(16): 14500-14508.
[47] 王美鑫. MnCeTiO_x低温NH₃-SCR脱硝催化剂改性及性能研究[D]. 太原: 太原理工大学, 2020.
WANG M X. Research on modification and performance of MnCeTiO_x for selective catalytic reduction of NO_x with NH₃ at low temperature[D]. Taiyuan: Taiyuan University of Technology, 2020 (in Chinese).
[48] SHEN B X, LIU T, ZHAO N, et al. Iron-doped Mn-Ce/TiO₂ catalyst for low temperature selective catalytic reduction of NO with NH₃[J]. Journal of Environmental Sciences, 2010, 22(9): 1447-1454.
[49] 朱少文, 沈伯雄, 池桂龙, 等. 铁钴共掺杂的Mn-Ce/TiO₂催化剂低温SCR脱硝[J]. 环境工程学报, 2017, 11(6): 3633-3639.
ZHU S W, SHEN B X, CHI G L, et al. Low-temperature SCR of NO over Fe and Co co-doped Mn-Ce/TiO₂ catalyst[J]. Chinese Journal of Environmental Engineering, 2017, 11(6): 3633-3639 (in Chinese).
[50] 吴彦霞, 梁海龙, 陈鑫, 等. Ni, Co掺杂对Mn-Ce/TiO₂催化剂脱硝活性的影响[J]. 化工环保, 2016, 36(3): 321-325.
WU Y X, LIANG H L, CHEN X, et al. Effects of doped Ni, Co on denitrification activity of Mn-Ce/TiO₂ catalyst[J]. Environmental Protection of Chemical Industry, 2016, 36(3): 321-325 (in Chinese).
[51] LIU H, FAN Z X, SUN C Z, et al. Improved activity and significant SO₂ tolerance of samarium modified CeO₂-TiO₂ catalyst for NO selective catalytic reduction with NH₃[J]. Applied Catalysis B: Environmental, 2019, 244: 671-683.
[52] MA Z R, WENG D, WU X D, et al. Effects of WO_x modification on the activity, adsorption and redox properties of CeO₂ catalyst for NO_x reduction with ammonia[J]. Journal of Environmental Sciences, 2012, 24(7): 1305-1316.
[53] 马赫遥, 周曙光, 王晓祥, 等. 不同的WO₃掺杂量对CeO₂的NH₃-SCR催化性能影响研究[J]. 高校化学工程学报, 2022, 36(2): 242-248.
MA H Y, ZHOU S G, WANG X X, et al. Effects of WO₃ doping amounts of CeO₂ on NH₃-SCR catalytic performance[J]. Journal of Chemical Engineering of Chinese Universities, 2022, 36(2): 242-248 (in Chinese).
[54] ZHANG L, ZHANG D S, ZHANG J P, et al. Design of meso-TiO₂@MnO_x-CeO_x/CNTs with a core-shell structure as DeNO_x catalysts: promotion of activity, stability and SO₂-tolerance[J]. Nanoscale, 2013, 5(20): 9821-9829.
[55] HUANG B J, YU D Q, SHENG Z Y, et al. Novel CeO₂@TiO₂ core-shell nanostructure catalyst for selective catalytic reduction of NO_x with NH₃[J]. Journal of Environmental Sciences, 2017, 55: 129-136.
[56] 苏士焜, 宗保宁, 荣峻峰. 金属氧化物催化剂用于NO催化氧化的研究进展[J]. 化工环保, 2022, 42(3): 249-254.
SU S K, ZONG B N, RONG J F. Research progress of metal oxide catalysts for catalytic oxidation of NO[J]. Environmental Protection of Chemical Industry, 2022, 42(3): 249-254 (in Chinese).
[57] 任冬冬. 中低温铁基SCR脱硝催化剂反应机理研究[D]. 南京: 东南大学, 2020.
REN D D. Study on reaction mechanism of iron based SCR de-NO_x catalyst at medium and low temperature[D]. Nanjing: Southeast University, 2020 (in Chinese).
[58] 查贤斌. 铁矿石催化剂SCR烟气低温脱硝及组分影响分析[D]. 南京: 东南大学, 2014.
ZHA X B. Low-temperature denitration of iron ore SCR flue gas and its component influence analysis[D]. Nanjing: Southeast University, 2014 (in Chinese).
[59] 王继封. Fe₂O₃-WO₃催化剂NH₃-SCR反应机理及低温活性调控[D]. 昆明: 昆明理工大学, 2020.
WANG J F. The research of Fe₂O₃-WO₃ catalyst on the NH₃-SCR reaction mechanism and low-temperature activity regulation[D]. Kunming: Kunming University of Science and Technology, 2020 (in Chinese).
[60] SUN J F, LU Y Y, ZHANG L, et al. Comparative study of different doped metal cations on the reduction, acidity, and activity of Fe₉M₁O_x (M=Ti⁴⁺, Ce^4+/3+, Al³⁺) catalysts for NH₃-SCR reaction[J]. Industrial & Engineering Chemistry Research, 2017, 56(42): 12101-12110.
[61] LIU F D, HE H, DING Y, et al. Effect of manganese substitution on the structure and activity of iron titanate catalyst for the selective catalytic reduction of NO with NH₃[J]. Applied Catalysis B: Environmental, 2009, 93(1/2): 194-204.
[62] FANG N J, GUO J X, SHU S, et al. Enhancement of low-temperature activity and sulfur resistance of Fe_0.3Mn_0.5Zr_0.2 catalyst for NO removal by NH₃-SCR[J]. Chemical Engineering Journal, 2017, 325: 114-123.
[63] LI Y L, LIU 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]. Applied Catalysis B: Environmental, 2020, 268: 118455.
[64] ZONG L Y, ZHANG G D, ZHAO J H, et al. Morphology-controlled synthesis of 3D flower-like TiO₂ and the superior performance for selective catalytic reduction of NO_x with NH₃[J]. Chemical Engineering Journal, 2018, 343: 500-511.
[65] CHEN S N, YAN Q H, ZHANG C, et al. A novel highly active and sulfur resistant catalyst from Mn-Fe-Al layered double hydroxide for low temperature NH₃-SCR[J]. Catalysis Today, 2019, 327: 81-89.