Progress in the Development of SCR Denitration Catalysts with Resistance of High-temperature Deactivation
LU Qiang1, WU Yachang1, XU Mingxin1,*, QU Yanchao2, WANG Hanxiao1, PEI Xinqi1, OUYANG Haodong1
1 National Engineering Laboratory for Biomass Power Generation Equipment, North China Electric Power University, Beijing 102206, China 2 Beijing National Power Group Co., Ltd., Beijing 102206, China
Abstract: The V2O5-WO3(MoO3)/TiO2 catalysts are widely utilized in the commercial fields of selective catalytic reduction (SCR) denitration. However, many factors can result in the deactivation of the catalysts in the process of SCR denitration operation, especially in the industrial processes of waste incinerators and oil/gas turbines, among which the thermal deactivation in high-temperature flue gas is important. This review summarizes the deactivation mechanisms of the SCR catalysts at high temperatures, including the crystalline transformation of TiO2 support, the catalytic oxidation of NH3 by V2O5, and the competitive adsorption between water vapor and NH3. Then, the developments of SCR denitration catalysts with the resistance of high-temperature deactivation are presented, i.e., improving the thermal stability of support and inhibiting the catalytic oxidation of gaseous NH3. Ti-based composite supports, including Ti-Zr/Ti-Si supports and zeolites, are considered to be optimal for improving the thermal stability of support, while metal oxides, such as Fe2O3 and WO3, are the main active components to prevent the NH3 catalytic oxidation. In addition,the technologies for the thermal resistance improvement of SCR denitration catalysts are briefly discussed, including the addition of anti-water components and the application of hydrophobic supports. With the presence of anti-water components such as noble metals (Pt, Pd) and metal oxides (WO3, CeO2), the adsorption of gaseous reactants over the catalyst can be promoted. Besides, using the hydrophobic carriers, such as zeolites and carriers coated with water-resistant layers, can also suppress the adsorption of water vapor. Finally, the developing prospects of SCR denitration catalysts with superior resistance to high temperature are discussed. This review can provide some fundamental instructions for the improvement of SCR denitration catalysts with the resistance of thermal deactivation in the high-temperature flue gas.
1 The National Bureau of Statistics of People's Republic of China. China statistical yearbook on environment 2018, China Academic Journal Electronic Publishing House, China, 2019 (in Chinese). 中华人民共和国国家统计局. 中国环境统计年鉴2018, 中国统计出版社, 2019. 2 Zhao W, Sun S H, Liu L Y, et al. Electric Power Technology and Environmental Protection, 2015, 31(1), 25(in Chinese). 赵伟, 孙少华, 刘路遥, 等. 电力科技与环保, 2015, 31(1), 25. 3 Dong Y W, Li J, Liang W J, et al. Industrial Catalysis, 2017, 25(9), 48(in Chinese). 董逸雯, 李坚, 梁文俊, 等. 工业催化, 2017, 25(9), 48. 4 Zhang S L, Zhong Q. Journal of Molecular Catalysis A: Chemical, 2013, 373, 108. 5 Zhang X, Wu J S, Wei D, et al. Science & Technology Review, 2012, 30(33), 35(in Chinese). 张新, 吴俊升, 魏丹, 等. 科技导报, 2012, 30(33), 35. 6 Iswarya V, Bhuvaneshwari M, Chandrasekaran N, et al. Aquatic Toxico-logy, 2018, 197, 89. 7 Zheng Y, Jensen A D,Johnsson J E. Applied Catalysis B: Environmental, 2005, 60(3-4), 253. 8 Nam I, Eldridge J W, Kittrell J R, et al. Industrial & Engineering Che-mistry Product Research and Development, 1986, 25(2), 192. 9 Yu Y K, He C, Chen J S, et al. Journal of Fuel Chemistry & Technology, 2012, 40(11), 1359. 10 Ramis G, Busca G, Bregani F, et al. Applied Catalysis, 1990, 64(1-2), 259. 11 Ramis G, Yi L, Busca G. Catalysis Today, 1996, 28(4), 373. 12 Topsoe N, Topsoe H, Dumesic J. Journal of Catalysis, 1995, 151(1), 226. 13 Topsoe N, Dumesic J, Topsoe H. Journal of Catalysis, 1995, 151(1), 241. 14 Lee S M, Hong S C. Applied Catalysis B: Environmental, 2015, 163, 30. 15 Li H B, Weng J, Li X H, et al. Science and Technology Innovation Herald, 2015, 12(26), 20(in Chinese). 李红波, 翁骥, 李小海, 等. 科技创新导报, 2015, 12(26), 20. 16 Sun J X. Mechanism study and numerical simulation of hydrothermal aging of urea-SCR catalyst for diesel engine. Master's Thesis, Dalian University of Technology, China, 2019 (in Chinese). 孙家兴. 柴油机SCR催化剂水热老化的机理研究及数值模拟. 硕士学位论文, 大连理工大学, 2019. 17 Chapman D M. Applied Catalysis A: General, 2011, 392(1), 143. 18 Wang L. The characteristic reaction of WO3/TiO2-ZrO2 series high-temperature SCR DeNOx catalysts and its application. Master's Thesis, North China Electric Power University (Beijing), China, 2016 (in Chinese). 王磊. WO3/TiO2-ZrO2系列高温SCR脱硝催化剂脱硝特性与应用研究. 硕士学位论文, 华北电力大学(北京), 2016. 19 Xu B Q, Xu H D, Lin T, et al. Chinese Journal of Catalysis, 2016, 37(8), 1354. 20 Xu B Q, Xu H D, Cao Y, et al. Chinese Journal of Inorganic Chemistry, 2016, 32(3), 517(in Chinese). 徐宝强, 徐海迪, 曹毅, 等. 无机化学学报, 2016, 32(3), 517. 21 Wang I, Chang W F, Shiau R, et al. Journal of Catalysis, 1983, 83(2), 428. 22 Lu Q, Wang L, Lin Z W, et al. Journal of Chinese Society of Power Engineering, 2016, 36(11), 901(in Chinese). 陆强, 王磊, 蔺卓玮, 等. 动力工程学报, 2016, 36(11), 901. 23 Wang L F. Preparation of WO3-doped TiO2-ZrO2-based NH3-SCR catalysts and investigation on the mechanism of NOx reduction from flue gas and poisoning. Master's Thesis, Southeast University, China, 2016 (in Chinese). 王龙飞. WO3掺杂TiO2-ZrO2催化剂的制备及脱硝与中毒机理研究. 硕士学位论文, 东南大学, 2016. 24 Wang L F, Zhang Y P, Guo W Q, et al. Journal of Chemical Industry and Engineering, 2015, 66(10), 101(in Chinese). 王龙飞, 张亚平, 郭婉秋, 等. 化工学报, 2015, 66(10), 101. 25 Chen L, Li J, Ge M. Chemical Engineering Journal, 2011, 170(2-3), 531. 26 Jia B H, Guo J X, Shu S, et al. Molecular Catalysis, 2017, 443, 25. 27 Casanova M,Schermanz K, Llorca J, et al. Catalysis Today, 2012, 184(1), 227. 28 Kobayashi M, Kuma R, Masaki S, et al. Applied Catalysis B: Environmental, 2005, 60(3-4), 173. 29 Song C F, Lu M K, Yang P, et al. Thin Solid Films, 2002, 413(1), 155. 30 Zhong L C. Study on the performance of TiO2-based SCR catalysts with SiO2 addition. Master's Thesis, Shanghai Jiao Tong University, China, 2013 (in Chinese). 钟柳成. 添加SiO2对以TiO2为载体的SCR催化剂性能的影响. 硕士学位论文, 上海交通大学, 2013. 31 Liu Q, Jin Q J, Gui G R, et al. Chinese Journal of Environmental Engineering, 2017, 11(10), 5495(in Chinese). 刘青, 金奇杰, 眭国荣, 等. 环境工程学报, 2017, 11(10), 5495. 32 Zhao M M, Chen M Y, Zhang P J, et al. Journal of Molecular Catalysis, 2017, 31(3), 223(in Chinese). 赵梦梦, 陈梦寅, 张鹏举, 等. 分子催化, 2017, 31(3), 223. 33 Liu J S. Study on the design, synthesis, characterization and catalytic performance of Fe-based catalysts supported on Beta coated by oxide thin films for NH3-SCR reaction. Ph.D. Thesis, China University of Petroleum (Beijing), China, 2018 (in Chinese). 刘计省. 氧化物薄膜包覆的Fe基Beta分子筛核壳结构催化剂的设计,制备,表征及对NH3-SCR反应的研究. 博士学位论文, 中国石油大学(北京), 2018. 34 Salker A V, Weisweiler W. Applied Catalysis A: General, 2000, 203(2), 221. 35 Li L D, Zhang F X, Guan N J, et al. Catalysis Communications, 2007, 8(3), 583. 36 Sultana A, Nanba T, Sasaki M, et al. Catalysis Today, 2011, 164(1), 495. 37 Long R Q, Yang R T. Catalysis Letters, 2001, 74(3), 201. 38 Chen Z, Liu Q, Guo L, et al. Applied Catalysis B: Environmental, 2021, 286, 119816. 39 Wang D E, Wang L, Gao G L, et al. The Chinese Journal of Process Engineering, 2020, 20(6), 718(in Chinese). 王殿二, 王玲, 高国龙, 等. 过程工程学报, 2020, 20(6), 718. 40 Wang P, Yu D, Zhang L D, et al. Applied Catalysis A: General, 2020, 607, 117806. 41 Shi J, Zhang Y, Zhang Z H, et al. Catalysis Communications, 2018, 115, 59. 42 Grzybek J, Gil B, Roth W J, et al. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2018, 196, 281. 43 Liu F D, He H, Zhang C B, et al. Catalysis Today, 2011, 175(1), 18. 44 Long R Q, Yang R T. Journal of Catalysis, 2002, 207(2), 224. 45 Wang F, Yao G H, Gui K T. Proceedings of the Chinese Society for Electrical Engineering, 2009, 29(29), 49(in Chinese). 王芳, 姚桂焕, 归柯庭. 中国电机工程学报, 2009, 29(29), 49. 46 Shen L T. Experimental study of catalytic reduction of nitrous oxide over Fe-Mo/ZSM-5 catalyst. Master's Thesis, Taiyuan University of Technology, China, 2007 (in Chinese). 申林涛. Fe-Mo/ZSM-5催化剂上氮氧化物催化还原性能的实验研究. 硕士学位论文, 太原理工大学, 2007. 47 Guo L Y, Zhu L, Zhuang K, et al. Environmental Engineering, 2019, 37(5), 163(in Chinese). 郭丽颖, 朱林, 庄柯, 等. 环境工程, 2019, 37(5), 163. 48 Wang H M, Ning P, Zhang Y Q, et al. Journal of Hazardous Materials, 2020, 388, 121812. 49 Kobayashi M, Miyoshi K. Applied Catalysis B: Environmental, 2007, 72(3-4), 253. 50 Bian X, Hu L, Peng P, et al. Journal of Northeastern University(Natural Science), 2019, 40(12), 1716(in Chinese). 边雪, 胡吕, 彭朋, 等. 东北大学学报(自然科学版), 2019, 40(12), 1716. 51 Cao L, Wu X D, Xu Y F, et al. Catalysis Communications, 2018, 120, 55. 52 Peng Y, Li K Z, Li J H. Applied Catalysis B: Environmental, 2013, 140-141, 483. 53 Arce-Sarria A, Caicedo-Rosero C L, Lara-Ramos J A, et al. Data in Brief, 2019, 25, 104151. 54 Ren X N, Li Z G, Liu S X, et al. Industrial Catalysis, 2013, 21(11), 36(in Chinese). 任晓宁, 李振国, 刘双喜, 等. 工业催化, 2013, 21(11), 36. 55 Chen L, Li J H, Ge M F, et al. Catalysis Today, 2010, 153(3), 77. 56 Liu Z M, L H Y, Feng X, et al. Molecular Catalysis, 2018, 445, 179. 57 Jin R B, Liu Y, Wu Z B, et al. Catalysis Today, 2010, 153(3), 84. 58 Shu Y,Aikebaier T, Quan X, et al. Applied Catalysis B: Environmental, 2014, 150-151, 630. 59 Wang J Y, Zhu H Z, An Z W, et al. Journal of Chemical Industry and Engineering, 2019, 70(12), 4635(in Chinese). 王金玉, 朱怀志, 安泽文, 等. 化工学报, 2019, 70(12), 4635. 60 Grossale A, Nova I, Tronconi E. Catalysis Today, 2008, 136(1), 18. 61 Wang Y C. The influence of acid/rare earth elements (Ce, La)-modification on the hydrothermal stability of Cu-SAPO-34 for NH3-SCR. Master's Thesis, Kunming University of Science and Technology, China, 2016 (in Chinese). 王燕彩. 酸或稀土元素(Ce、La)改性对Cu-SAPO-34上NH3选择性催化还原NOx抗水热性能的影响. 硕士学位论文, 昆明理工大学, 2016. 62 Camposilvan E, Flamant Q, Anglada M. Journal of the Mechanical Behavior of Biomedical Materials, 2015, 47, 95. 63 Ren Z Y, Fan H, Wang R. Catalysis Communications, 2017, 100, 71.
渝公网安备50019002502923号 版权所有：《材料导报》编辑部
2022, Vol. 36 
