低温SCR脱硝催化剂研究进展

doi:10.12034/j.issn.1009-606X.218233

摘要/Abstract

摘要： 氮氧化物NOx(NO, NO2和N2O)是全球大气污染的主要污染物之一，引起光化学烟雾、酸雨、臭氧层破坏等环境问题，严重影响人们的生存环境和生活质量，引起了世界各国的广泛关注。针对固定源和移动源燃烧排放，各国制定了日益严格的排放标准。目前主要的脱硝技术分为选择性催化还原(SCR)、选择性非催化还原(SNCR)、氧化脱硝和活性炭吸附脱硝等。SNCR的应用有较高的条件，影响其成功运行的主要因素有温度、氨氮比、氨气在烟气中的分布和停留时间等，故SNCR的工业应用存在一定的局限性。SCR脱硝技术比其它脱硝技术应用更广泛，其中脱硝多安排于除尘脱硫后，此时温度多处于100?250℃之间。为提高SCR脱硝性能，低温SCR脱除NOx是目前研究最热门的烟气脱硝技术。本工作综述了近年来低温SCR脱硝催化剂的研究进展，介绍了锰基催化剂、钒基催化剂及碳基催化剂的发展现状，对单组分Mn基催化剂、负载型Mn基催化剂和复合型Mn基催化剂进行了综述，从V基催化剂的制备对脱销的影响和脱硝机理进行了表述，综述了过渡金属掺杂对C基催化剂的影响，阐述了烟气中H2O和SO2对催化反应的影响及低温SCR反应的脱硝机理，对低温SCR催化剂进行了总结并对其未来发展进行了展望。

关键词: 低温, 选择性催化还原, 脱硝, 催化剂, 机理

Abstract: Nitrogen oxide NOx (NO, NO2, and N2O) is one of the major pollutants in the air pollution, it can cause environmental problems such as photochemical smog, acid rain, and ozone layer destruction, which has posed threat to people's living environment and quality of life, and attracted great attention from the world. Countries made stricter emission standards for burning emissions from both fixed and mobile sources. The major denitrification technologies include selective catalytic reduction (SCR), selective non-catalytic reduction (SNCR), oxidative denitrification, and activated carbon adsorption and denitrification at present. The SNCR has higher conditions in industrial applications, the main factors affecting successful operation are temperature, ammonia?nitrogen ratio, distribution of ammonia gas in the flue gas and residence time, so there were certain limitations in industrial application of SNCR. Compared with other denitrification technologies, SCR denitration technology is more widely used in industrial application, in which denitration is mostly arranged after dust removal and desulfurization, at this time, the temperature is mostly between 100?250℃. The performance of SCR denitrification in low-temperature must be improved, which is one of the most promising flue gas DeNOx technology. In this paper, the recent works on low-temperature SCR catalysts were reviewed on manganese-based catalysts, vanadium-based catalysts and carbon-based catalysts. Single-component Mn-based catalysts, supported Mn-based catalysts and composite Mn-based catalysts were reviewed, the effects of preparation of V-based catalysts on the de-dumping and denitrification mechanisms were described. The effect of transition metal doping on C-based catalysts was reviewed. The influence of H2O and SO2 resistance on low-temperature NH3-SCR catalytic activity and reaction mechanism were also discussed. Finally, the virtues advantages and defects of low temperature SCR catalysts were summarized, and the future development direction was also given out.

Key words: low-temperature, selective catalytic reduction, denitrification, catalyst, mechanism

宁汝亮刘霄龙朱廷钰. 低温SCR脱硝催化剂研究进展[J]. 过程工程学报, 2019, 19(2): 223-234.

Ruliang NING Xiaolong LIU Tingyu ZHU. Research progress of low-temperature SCR denitration catalysts[J]. Chin. J. Process Eng., 2019, 19(2): 223-234.

参考文献

1. Yu, S.; Jiang, N.; Zou, W.; Li, L.; Tang, C.; Dong, L. A general and inherent strategy to improve the water tolerance of low temperature NH3-SCR catalysts via trace SiO2 deposition. Catalysis Communications 2016, 84, 75-79.
2. Qiu, Y.; Liu, B.; Du, J.; Tang, Q.; Liu, Z.; Liu, R.; Tao, C. The monolithic cordierite supported V2O5 –MoO3/TiO2 catalyst for NH3-SCR. Chemical Engineering Journal 2016, 294, 264-272.
3. Li, J.; Chang, H.; Ma, L.; Hao, J.; Yang, R.T. Low-temperature selective catalytic reduction of NOx with NH3 over metal oxide and zeolite catalysts—a review. Catalysis Today 2011, 175, 147-156.
4. Fang, N.; Guo, J.; Shu, S.; Luo, H.; Chu, Y.; Li, J. Enhancement of low-temperature activity and sulfur resistance of Fe0.3Mn0.5Zr0.2 catalyst for no removal by NH3-SCR. Chemical Engineering Journal 2017, 325, 114-123.
5. Xia, Q,; Qin, Z. Investigation of selective catalytic reduction of NOx with V2O5/TiO2 as catalysts. Journal of Safety and Environmental 2004, 4, 16-18.
6. Tian, W.; Yang, H.; Fan, X.; Zhang, X. Catalytic reduction of NOx with NH3 over different-shaped MnO2 at low temperature. Journal of hazardous materials 2011, 188, 105-109.
7. Tang, X.; Hao, J.; Xu, W.; Li, J. Low temperature selective catalytic reduction of NOx with NH3 over amorphous mnox catalysts prepared by three methods. Catalysis Communications 2007, 8, 329-334.
8. Zhang, Y.; Zhao, X.; Xu, H.; Shen, K.; Zhou, C.; Jin, B.; Sun, K. Novel ultrasonic-modified MnOx/TiO2 for low-temperature selective catalytic reduction (SCR) of no with ammonia. Journal of colloid and interface science 2011, 361, 212-218.
9. Wu, Z.; Jin, R.; Liu, Y.; Wang, H. Ceria modified MnOx/TiO2 as a superior catalyst for NO reduction with NH3 at low-temperature. Catalysis Communications 2008, 9, 2217-2220.
10. Thirupathi, B.; Smirniotis, P.G. Effect of nickel as dopant in Mn/TiO2 catalysts for the low-temperature selective reduction of NO with NH3. Catalysis Letters 2011, 141, 1399-1404.
11. Thirupathi, B.; Smirniotis, P.G. Nickel-doped Mn/TiO2 as an efficient catalyst for the low-temperature SCR of NO with NH3: Catalytic evaluation and characterizations. Journal of Catalysis 2012, 288, 74-83.
12. Shen, B.; Liu, T.; Zhao, N.; Yang, X.; Deng, L. Iron-doped Mn-Ce/TiO2 catalyst for low temperature selective catalytic reduction of NO with NH3. Journal of Environmental Sciences 2010, 22, 1447-1454.
13. Luo, S.; Zhou, W.; Xie, A.; Wu, F.; Yao, C.; Li, X.; Zuo, S.; Liu, T. Effect of MnO2 polymorphs structure on the selective catalytic reduction of NOx with NH3 over TiO2–palygorskite. Chemical Engineering Journal 2016, 286, 291-299.
14. Huang, J.; Tong, Z.; Huang, Y.; Zhang, J. Selective catalytic reduction of NO with NH3 at low temperatures over iron and manganese oxides supported on mesoporous silica. Applied Catalysis B: Environmental 2008, 78, 309-314.
15. Jing, G.U.O.; Caiting, L.I.; Pei, L.U.; Huafei, C.U.I.; Dunliang, P.; Qingbo, W.E.N. Research on SCR denitrification of MnOx/Al2O3 modified by CeO2 and its mechanism at low temperature. Chinese Journal of Environmental Science 2011, 32, 2240-2246.
16. Li, Y.; Li, Y.; Wang, P.; Hu, W.; Zhang, S.; Shi, Q.; Zhan, S. Low-temperature selective catalytic reduction of NOx with NH3 over MnFeOx nanorods. Chemical Engineering Journal 2017, 330, 213-222.
17. Lian, Z.; Liu, F.; He, H.; Shi, X.; Mo, J.; Wu, Z. Manganese–niobium mixed oxide catalyst for the selective catalytic reduction of NOx with NH3 at low temperatures. Chemical Engineering Journal 2014, 250, 390-398.
18. Zuo, J.; Chen, Z.; Wang, F.; Yu, Y.; Wang, L.; Li, X. Low-temperature selective catalytic reduction of NOx with NH3 over novel Mn–Zr mixed oxide catalysts. Industrial & Engineering Chemistry Research 2014, 53, 2647-2655.
19. Liu, Z.; Liu, Y.; Li, Y.; Su, H.; Ma, L. WO3 promoted Mn–Zr mixed oxide catalyst for the selective catalytic reduction of NOx with NH3. Chemical Engineering Journal 2016, 283, 1044-1050.
20. Wan, Y.; Zhao, W.; Tang, Y.; Li, L.; Wang, H.; Cui, Y.; Gu, J.; Li, Y.; Shi, J. Ni-Mn bi-metal oxide catalysts for the low temperature SCR removal of NO with NH3. Applied Catalysis B: Environmental 2014, 148-149, 114-122.
21. Cha, W.; Chin, S.; Park, E.; Yun, S.-T.; Jurng, J. Effect of V2O5 loading of V2O5/TiO2 catalysts prepared via CVC and impregnation methods on NOx removal. Applied Catalysis B: Environmental 2013, 140-141, 708-715.
22. Boningari, T.; Koirala, R.; Smirniotis, P.G. Low-temperature catalytic reduction of NO by NH3 over vanadia-based nanoparticles prepared by flame-assisted spray pyrolysis: Influence of various supports. Applied Catalysis B: Environmental 2013, 140-141, 289-298.
23. Boningari, T.; Koirala, R.; Smirniotis, P.G. Low-temperature selective catalytic reduction of NO with NH3 over V/ZrO2 prepared by flame-assisted spray pyrolysis: Structural and catalytic properties. Applied Catalysis B: Environmental 2012, 127, 255-264.
24. Jiang, Y.; Gao, X.; Zhang, Y.; Wu, W.; Song, H.; Luo, Z.; Cen, K. Effects of PbCl2 on selective catalytic reduction of NO with NH3 over vanadia-based catalysts. Journal of hazardous materials 2014, 274, 270-278.
25. Li, Q.; Yang, H.; Ma, Z.; Zhang, X. Selective catalytic reduction of NO with NH3 over CuOx-carbonaceous materials. Catalysis Communications 2012, 17, 8-12.
26. Li, Q.; Yang, H.; Qiu, F.; Zhang, X. Promotional effects of carbon nanotubes on V2O5/TiO2 for NOx removal. Journal of hazardous materials 2011, 192, 915-921.
27. Fan, X.; Qiu, F.; Yang, H.; Tian, W.; Hou, T.; Zhang, X. Selective catalytic reduction of NOx with ammonia over Mn–Ce–Ox/TiO2-carbon nanotube composites. Catalysis Communications 2011, 12, 1298-1301.
28. Zhang L, Zhang D, Zhang J. Design of meso-TiO2@MnOx-CeOx/CNTs with a core–shell structure as DeNOx catalysts: promotion of activity, stability and SO2-tolerance. Nanoscale, 2013, 20, 9821-9829.
29. Zhang, Y.; Zheng, Y.; Wang, X.; Lu, X. Preparation of Mn–FeOx/CNTs catalysts by redox co-precipitation and application in low-temperature no reduction with NH3. Catalysis Communications 2015, 62, 57-61.
30. Huang, B.; Huang, R.; Jin, D.; Ye, D. Low temperature SCR of NO with NH3 over carbon nanotubes supported vanadium oxides. Catalysis Today 2007, 126, 279-283.
31. Huang, Z.; Liu, Z.; Zhang, X.; Liu, Q. Inhibition effect of H2O on V2O5/AC catalyst for catalytic reduction of NO with NH3 at low temperature. Applied Catalysis B: Environmental 2006, 63, 260-265.
32. Wu, Z.; Jin, R.; Wang, H.; Liu, Y. Effect of ceria doping on SO2 resistance of Mn/TiO2 for selective catalytic reduction of NO with NH3 at low temperature. Catalysis Communications 2009, 10, 935-939.
33. Sun, D.; Liu, Q.; Liu, Z.; Gui, G.; Huang, Z. An in situ drifts study on SCR of NO with NH3 over V2O5/AC surface. Catalysis Letters 2009, 132, 122-126.
34. Jiang, B.; Deng, B.; Zhang, Z.; Wu, Z.; Tang, X.; Yao, S.; Lu, H. Effect of Zr addition on the low-temperature SCR activity and SO2 tolerance of Fe–Mn/Ti catalysts. The Journal of Physical Chemistry C 2014, 118, 14866-14875.
35. Zhu, Z.P.; Liu, Z.Y.; Niu, H.X.; Liu, S.J. Promoting effect of SO2 on activated carbon-supported vanadia catalyst for NO reduction by NH3 at low temperatures. Journal of Catalysis 1999, 187, 245-248.
36. Gálvez, M.E.; Boyano, A.; Lázaro, M.J.; Moliner, R. A study of the mechanisms of no reduction over vanadium loaded activated carbon catalysts. Chemical Engineering Journal 2008, 144, 10-20.
37. Ettireddy, P.R.; Ettireddy, N.; Boningari, T.; Pardemann, R.; Smirniotis, P.G. Investigation of the selective catalytic reduction of nitric oxide with ammonia over Mn/TiO2 catalysts through transient isotopic labeling and in situ FT-IR studies. Journal of Catalysis 2012, 292, 53-63.
38. Yang, S.; Wang, C.; Li, J.; Yan, N.; Ma, L.; Chang, H. Low temperature selective catalytic reduction of NO with NH3 over Mn–Fe spinel: Performance, mechanism and kinetic study. Applied Catalysis B: Environmental 2011, 110, 71-80.
39. Grossale, A.; Nova, I.; Tronconi, E.; Chatterjee, D.; Weibel, M. The chemistry of the NO/NO2–NH3 “fast” SCR reaction over Fe-ZSM5 investigated by transient reaction analysis. Journal of Catalysis 2008, 256, 312-322.
40. Wang, Y.; Ge, C.; Zhan, L.; Li, C.; Qiao, W.; Ling, L. MnOx–CeO2/activated carbon honeycomb catalyst for selective catalytic reduction of NO with NH3 at low temperatures. Industrial & Engineering Chemistry Research 2012, 51, 11667-11673.
41. Tronconi, E.; Nova, I.; Ciardelli, C.; Chatterjee, D.; Weibel, M. Redox features in the catalytic mechanism of the “standard” and “fast” NH3-SCR of NOx over a V-based catalyst investigated by dynamic methods. Journal of Catalysis 2007, 245, 1-10.
42. Wang, J.; Yan, Z.; Liu, L.; Chen, Y.; Zhang, Z.; Wang, X. In situ drifts investigation on the SCR of NO with NH3 over V2O5 catalyst supported by activated semi-coke. Applied Surface Science 2014, 313, 660-669.

[1]	赵晓腾周新涛罗中秋韦宇兰雄陆艳. 二氧化钛基复合材料对常见染料的去除性能及其机理研究进展[J]. 过程工程学报, 2022, 22(9): 1169-1180.
[2]	王义源马淑花王晓辉欧彦君高利珍. 高铝粉煤灰负载锰基催化剂的催化氧化NO性能研究[J]. 过程工程学报, 2022, 22(9): 1262-1270.
[3]	兰雄刘钦周新涛罗中秋赵晓腾陆艳. 吸附法脱除废水中四环素的研究进展[J]. 过程工程学报, 2022, 22(8): 989-1000.
[4]	师吉兰徐勇强王海锋何亚群. 废旧塑料摩擦荷电机理及摩擦电选技术研究进展[J]. 过程工程学报, 2022, 22(8): 1001-1010.
[5]	徐家明皇甫林史玉婷郭洪范高士秋李长明余剑. 低温烟气脱硝催化剂制备工艺及性能探究[J]. 过程工程学报, 2022, 22(7): 863-872.
[6]	魏汝飞孟东祥李家新龙红明朱玉龙李振营. 机械活化条件下超细铁矿粉一氧化碳还原特性及机理[J]. 过程工程学报, 2022, 22(7): 891-899.
[7]	林振浩李军业金志江钱锦远. LNG接收站用低温球阀阀座唇形密封圈接触特性分析[J]. 过程工程学报, 2022, 22(6): 819-827.
[8]	冯凡曾坚贤黄小平张锐吴振威. 沸石咪唑骨架膜的制备及其应用进展[J]. 过程工程学报, 2022, 22(6): 709-719.
[9]	申展江志东张鹏飞张子瑜车海英马紫峰. 低温甲醇水重整制氢催化剂研究进展[J]. 过程工程学报, 2022, 22(5): 573-585.
[10]	王书欢周理龙李正杰韩继龙刘润静 Jimmy Yun. 催化臭氧氧化降解水中有机污染物的研究进展[J]. 过程工程学报, 2022, 22(5): 586-600.
[11]	丁桂珍郑刘根吴盾迟文飞. 基于非等温法的废弃环氧树脂电路板热解动力学分析[J]. 过程工程学报, 2022, 22(5): 680-688.
[12]	张晟林于佳元王蕾闫瑞一李春山. 磷钼钒酸催化甲基丙烯醛氧化反应机制及过程研究[J]. 过程工程学报, 2022, 22(3): 385-392.
[13]	赵高峰赵炜珍刘晓敏. 紫精类变色材料的合成与应用研究[J]. 过程工程学报, 2022, 22(3): 304-317.
[14]	范川林杜占潘锋邹正李军李洪钟朱庆山. 过程工程所流化床直接还原技术研究进展[J]. 过程工程学报, 2022, 22(10): 1325-1332.
[15]	杨建林赵璐马淑花王晓辉王月娇. 莫来石-刚玉催化剂载体制备及其性能研究[J]. 过程工程学报, 2022, 22(1): 79-88.