SCR脱硝催化剂抗砷中毒改性优化与再生研究进展

doi:10.16085/j.issn.1000-6613.2020-1072

摘要/Abstract

摘要：

选择性催化还原（SCR）是目前应用最为广泛的烟气脱硝技术，催化剂是整个SCR脱硝系统的核心。在实际应用过程中，催化剂存在各种失活问题，其中砷中毒是催化剂失活的重要原因之一。本文详细阐述了SCR脱硝催化剂砷中毒的物理和化学失活机理，其中物理失活是由于As₂O₃在催化剂表面沉积、氧化造成催化剂孔道堵塞所致，而化学失活是由于砷氧化物破坏催化剂酸位点、改变活性基团形态、降低催化剂氨吸附及氧化还原能力所致。然后，系统介绍了抗砷中毒SCR脱硝催化剂的研发路线以及现有抗砷中毒催化剂优化改进的主要技术手段，主要包括调整催化剂孔隙结构、优化催化剂化学配方和烟气侧砷氧化物吸附固化等，其中MoO₃是优选的催化剂活性助剂，金属元素（如Bi、In、Sn、Mg）是主要的抗砷助剂，钙基物质是典型的烟气侧砷氧化物吸附添加剂。最后，对砷中毒废弃催化剂的再生技术进行了简要介绍，包括湿法清洗、热还原法、复合再生等，在实际工业应用中，主要以物理清扫、湿法清洗配合活性组分添加的复合再生方式实现中毒催化剂再生。本文可对未来抗砷中毒SCR脱硝催化剂的研发与优化提供重要支撑。

关键词: 选择性催化还原, 催化剂, 砷中毒, 抗砷中毒, 再生

Abstract:

Selective catalytic reduction (SCR) is the most mature technology for flue gas denitrification in power plants, and the catalyst is the core. Arsenic poisoning is one of the most important sources for the deactivation of the catalyst. This review summarizes the physical and chemical deactivation mechanisms of the arsenic poisoned SCR catalysts. The physical deactivation is attributed to the deposition and oxidation of gaseous arsenic oxides over the surface of the catalysts, and the chemical deactivation is ascribed to the destruction of active acid sites caused by the arsenic species. Then, the development of SCR catalysts with the capability of anti-arsenic poisoning is presented, including the adjustment of the pore structures in the catalyst, optimization of the chemical formulation of the catalyst, and solidification of gaseous arsenic oxide. MoO₃ is the optimal active agent, metal ions such as Bi, In, Sn and Mg are the main additives for anti-arsenic poisoning, and Ca species is the effective sorbent for the gaseous arsenic species. Finally, the regeneration technologies for poisoned catalysts are briefly discussed, including the wet-solution washing, thermal reduction and the combination of multiple regeneration methods, among which the combination of mechanical blowing, wet-solution washing and active components implantation is widely utilized in the industrial processes at present. This review can provide fundamental instructions for the development of SCR catalysts for anti-arsenic poising.

Key words: selective catalytic reduction (SCR), catalyst, arsenic poisoning, anti-arsenic poisoning, regeneration

中图分类号:

陆强, 裴鑫琦, 徐明新, 王涵啸, 吴亚昌, 欧阳昊东. SCR脱硝催化剂抗砷中毒改性优化与再生研究进展[J]. 化工进展, 2021, 40(5): 2365-2374.

LU Qiang, PEI Xinqi, XU Mingxin, WANG Hanxiao, WU Yachang, OUYANG Haodong. Progress in the development and regeneration of SCR catalysts for anti-arsenic poisoning[J]. Chemical Industry and Engineering Progress, 2021, 40(5): 2365-2374.

图/表 4

参考文献 46

1	张道军, 马子然, 孙琦, 等. 选择催化还原(SCR)反应机理研究进展[J]. 化工进展, 2019, 38(4): 1611-1623.
	ZHANG Daojun, MA Ziran, SUN Qi, et al. Progress in the mechanism of selective catalytic reduction(SCR) reaction[J]. Chemical Industry and Engineering Progress, 2019, 38(4): 1611-1623.
2	张巍, 方毅伟, 卢程, 等. 改性催化剂织构强化低温NH₃-SCR脱硝性能的研究进展[J]. 化工进展, 2019, 38(6): 2539-2549.
	ZHANG Wei, FANG Yiwei, LU Cheng, et al. Research progress in texture modification of modified catalyst for low temperature NH₃-SCR denitrification[J]. Chemical Industry and Engineering Progress, 2019, 38(6): 2539-2549.
3	周锦晖, 李国波, 吴鹏, 等. 商业V₂O₅-WO₃/TiO₂脱硝催化剂砷中毒机理[J]. 分子催化, 2018, 32(5): 444-453.
	ZHOU Jinhui, LI Guobo, WU Peng, et al. The As poisoning mechanism over commercial V₂O₅-WO₃/TiO₂ catalyst[J]. Journal of Molecular Catalysis(China), 2018, 32(5): 444-453.
4	王宝冬, 汪国高, 刘斌, 等. 选择性催化还原脱硝催化剂的失活、失效预防、再生和回收利用研究进展[J]. 化工进展, 2013, 32(S1):133-139.
	WANG Baodong, WANG Guogao, LIU Bin, et al. Development of SCR catalyst deactivation, regeneration and recycling[J]. Chemical Industry and Engineering Progress, 2013, 32(S1): 133-139.
5	陈鸿伟, 赵宝宁, 张千, 等. 烟气飞灰对SCR脱硝催化剂的磨损性能试验研究[J]. 动力工程学报, 2018, 38(4): 286-290.
	CHEN Hongwei, ZHAO Baoning, ZHANG Qian, et al. Experimental study on wear resistance of SCR denitration catalyst to flue gas fly ash[J]. Journal of Chinese Society of Power Engineering, 2018, 38(4): 286-290.
6	赵莉, 韩健, 吴洋文, 等. 钒钛基SCR脱硝催化剂碱土金属中毒[J]. 化工进展, 2019, 38(3): 1419-1426.
	ZHAO Li, HAN Jian, WU Yangwen, et al. Study on alkaline earth metal poisoning of vanadium-titanium based SCR denitration catalyst[J]. Chemical Industry and Engineering Progress, 2019, 38(3): 1419-1426.
7	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]. Applied Chemical Industry, 2018, 47(12): 2616-2619.
8	CHANG Huazhen, SHI Chuanning, LI Mingguan, et al. The effect of cations (NH⁴⁺, Na⁺, K⁺, and Ca²⁺) on chemical deactivation of commercial SCR catalyst by bromides[J]. Chinese Journal of Catalysis, 2018, 39(4): 710-717.
9	LI Qichao, CHEN Sifan, LIU Zhenyu, et al. Combined effect of KCl and SO₂ on the selective catalytic reduction of NO by NH₃ over V₂O₅/TiO₂ catalyst[J]. Applied Catalysis B: Environmental, 2015, 164: 475-482.
10	赵继尧, 唐修义, 黄文辉. 中国煤中微量元素的丰度[J]. 中国煤田地质, 2002, 14(S1): 5-13, 17.
	ZHAO Jiyao, TANG Xiuyi, HUANG Wenhui. Abundance of trace elements in coal of China[J]. Coal Geology of China, 2002, 14(Sl): 5-13, 17.
11	竹涛, 张星, 高放, 等. 废弃SCR催化剂再生研究进展[J]. 环境工程, 2018, 36(10): 92-96, 183.
	ZHU Tao, ZHANG Xing, GAO Fang, et al. Research progress on regeneration of waste SCR catalyst[J]. Environmental Engineering, 2018, 36(10): 92-96, 183.
12	尹海芮, 王远洋. 燃煤电厂烟气脱硝废弃SCR催化剂的再生和回收研究进展[J]. 现代化工, 2019, 39(9): 16-20.
	YIN Hairui, WANG Yuanyang. Research progress on regeneration and recovery of waste SCR catalyst for flue gas denitrification in coal-fired power plants[J]. Modern Chemical Industry, 2019, 39(9): 16-20.
13	郑刘根, 刘桂建, 高连芬, 等. 中国煤中砷的含量分布、赋存状态、富集及环境意义[J]. 地球学报, 2006, 27(4): 355-366.
	ZHENG Liugen, LIU Guijian, GAO Lianfen, et al. Arsenic in Chinese coals: its abundance, distribution, modes of occurrence, enrichment processes, and environmental significance[J]. Acta Geoscientica Sinica, 2006, 27(4): 355-366.
14	PRITCHARD S, KANEKO S, SUYAMA K. Optimizing SCR catalyst design and performance for coal-fired boilers[C]//EPA/EPRI 1995 Joint Symposium Stationary Combustion NOx Control, USA: 1995.
15	朱春华, 陆强, 庄柯, 等. 燃煤电厂砷中毒SCR脱硝催化剂的失活特性研究[J]. 应用化工, 2018, 47(6): 1145-1149.
	ZHU Chunhua, LU Qiang, ZHUANG Ke, et al. Research on the deactivation of arsenic poisoned SCR de-NO_x catalyst in coal-fired power plants[J]. Applied Chemical Industry, 2018, 47(6): 1145-1149.
16	LU Qiang, PEI Xinqi, WU Yangwen, et al. Deactivation mechanism of the commercial V₂O₅-MoO₃/TiO₂ selective catalytic reduction catalyst by arsenic poisoning in coal-fired power plants[J]. Energy & Fuels, 2020, 34(4): 4865-4873.
17	孙克勤, 钟秦, 于爱华. SCR催化剂的砷中毒研究[J]. 中国环保产业, 2008(1): 40-42.
	SUN Keqin, ZHONG Qin, YU Aihua. Study on arsenic poisoning of SCR catalyst[J]. China Environmental Protection Industry, 2008(1): 40-42.
18	KONG Ming, LIU Qingcai, WANG Xiaoqing, et al. Performance impact and poisoning mechanism of arsenic over commercial V₂O₅-WO₃/TiO₂ SCR catalyst[J]. Catalysis Communications, 2015, 72: 121-126.
19	MORITA I, HIRAMO M, BIELAWSKI G. Development and commercial operating experience of SCR deNO_x catalysts for wet bottom coal fired boilers[C]//Power-Gen International, Orlando, Florida, 1998.
20	PENG Yue, LI Junhua, SI Wenzhe, et al. Insight into deactivation of commercial SCR catalyst by arsenic: an experiment and DFT study[J]. Environmental Science & Technology, 2014, 48(23): 13895-13900.
21	HU Wenshuo, GAO Xiang, DENG Yawen, et al. Deactivation mechanism of arsenic and resistance effect of SO₄^2- on commercial catalysts for selective catalytic reduction of NO with NH₃[J]. Chemical Engineering Journal, 2016, 293(23): 118-128.
22	阮东亮，盘思伟，韦正乐，等. 砷对商业V₂O₅-WO₃/TiO₂催化剂脱硝性能的影响[J]. 化工进展, 2014, 33(4): 925-929, 946.
	RUAN Dongliang, PAN Siwei, WEI Zhengle, et al. Effect of arsenic on de-NO efficiency over commercial V₂O₅-WO₃/TiO₂ catalyst[J]. Chemical Industry and Engineering Progress, 2014, 33(4): 925-929, 946.
23	LI Xiang, LI Junhua, PENG Yue, et al. Regeneration of commercial SCR catalysts: probing the existing forms of arsenic oxide[J]. Environmental Science & Technology, 2015, 49(16): 9971-9978.
24	JENSEN HOLM Hans, TOPSOE Nanyu, 崔建华. 选择催化还原（SCR）脱硝技术在中国燃煤锅炉上的应用（上）[J]. 热力发电, 2007, 36(8): 13-18.
	JENSEN HOLM Hans, TOPSOE Nanyu, CUI Jianhua. Application of SCR denitrification technology onto coal-fired boilers in China[J]. Thermal Power Generation, 2007, 36(8): 13-18.
25	JENSEN HOLM Hans, TOPSOE Nanyu, 崔建华. 选择催化还原（SCR）脱硝技术在中国燃煤锅炉上的应用（下）[J]. 热力发电, 2007, 36(9): 10-15.
	JENSEN HOLM Hans, TOPSOE Nanyu, CUI Jianhua. Application of SCR denitrification technology onto coal-fired boilers in China[J]. Thermal Power Generation, 2007, 36(9): 10-15.
26	PENG Yue, SI Wenzhe, LI Xiang, et al. Comparison of MoO₃ and WO₃ on arsenic poisoning V₂O₅/TiO₂ catalyst: DRIFTS and DFT study[J]. Applied Catalysis B: Environmental, 2016, 181: 692-698.
27	LI Xiang, LI Junhua, PENG Yue, et al. Mechanism of arsenic poisoning on SCR catalyst of CeW/Ti and its novel efficient regeneration method with hydrogen[J]. Applied Catalysis B: Environmental, 2016, 184: 246-257.
28	赵会民, 尹顺利, 刘长东, 等. 兼具抗砷中毒和宽活性温度窗口的低SO2氧化率SCR脱硝催化剂及其制备方法:CN201711121499.1[P]. 2018-05-15.
	ZHAO Huimin, YIN Shunli, LIU Changdong, et al. An anti-arsenic poisoning SCR catalyst with low SO2 oxidation rate and its preparation method: CN201711121499.1[P]. 2018-05-15.
29	张涛. 一种抗砷中毒的SCR脱硝催化剂及其制备方法: CN201710367686.1[P]. 2017-09-05.
	ZHANG Tao. An anti-arsenic poisoning SCR catalyst and its preparation method: CN201710367686.1[P]. 2017-09-05.
30	陆强, 杨勇平. 一种平板式抗砷中毒脱硝催化剂及其制备工艺: CN201810048084.4[P]. 2018-07-13.
	LU Qiang, YANG Yongping. A plate-type SCR catalyst with resistance to arsenic and its preparation method:CN201710367686.1[P]. 2018-07-13.
31	李想. 一种提升抗砷中毒性能的脱硝催化剂及其制备方法和应用:CN201810371240.0[P]. 2018-08-24.
	LI Xiang. A SCR catalyst for improving an anti-poisoning property to arsenic and its preparation method:CN201810371240.0[P]. 2018-08-24.
32	SENIOR Constancel, LIGNELL Davido, SAROFIM Adelf, et al. Modeling arsenic partitioning in coal-fired power plants[J]. Combustion and Flame, 2006, 147(3): 209-221.
33	何梓谦, 余圣辉, 张成, 等. 气氛对氧化物吸附气相砷的影响及机理分析[J]. 洁净煤技术, 2020, 26(4): 190-195.
	HE Ziqian, YU Shenghui, ZHANG Cheng, et al. Effects of atmosphere on gas-phase arsenic adsorption by oxides[J]. Clean Coal Technology, 2020, 26(4):190-195.
34	王泉海, 刘迎晖, 张军营, 等. CaO对烟气中砷的形态和分布的影响[J]. 环境科学学报, 2003, 23(4): 549-551.
	WANG Quanhai, LIU Yinghui, ZHANG Junying, et al. Effect of CaO on the speciation of arsenic in flue gases[J]. Acta Scientiae Circumstantiae, 2003, 23(4): 549-551.
35	LI Xiang, LI Xiansheng, ZHU Tianle, et al. Extraordinary deactivation offset effect of arsenic and calcium on CeO₂-WO₃ SCR catalysts[J]. Environmental Science & Technology, 2018, 52(15): 8578-8587.
36	王平, 钱利科, 姚友工. 燃煤电厂砷中毒SCR脱硝催化剂再生技术研究[J]. 四川理工学院学报（自然科学版）, 2016, 29(5): 9-13.
	WANG Ping, QIAN Like, YAO Yougong. Research on arsenic poison of the SCR catalyst regeneration technology in coal-fired power plant[J]. Journal of Sichuan University of Science & Engineering (Natural Sicence Edition), 2016, 29(5): 9-13.
37	PENG Yue, LI Junhua, SI Wenzhe, et al. Deactivation and regeneration of a commercial SCR catalyst: comparison with alkali metals and arsenic[J]. Applied Catalysis B: Environmental, 2015, 168/169: 195-202.
38	XUE Yudong, WANG Yunting. Effective industrial regeneration of arsenic poisoning waste selective catalytic reduction catalyst: contaminants removal and activity recovery[J]. Environmental Science and Pollution Research, 2018, 25(34): 34114-34122.
39	王俊杰, 张亚平, 李娟, 等. 砷中毒商业V₂O₅-WO₃/TiO₂催化剂的再生方法[J]. 工程热物理学报, 2018, 39(2): 450-456.
	WANG Junjie, ZHANG Yaping, LI Juan, et al. Regeneration method of arsenic poisoned commercial SCR catalyst[J]. Journal of Engineering Thermophysics, 2018, 39(2): 450-456.
40	范美玲, 杨晓博, 赵长多, 等. 碳酸钠和过硫酸铵对砷中毒脱硝催化剂清洗再生效果对比[J]. 热力发电, 2017, 46(9): 112-116.
	FAN Meiling, YANG Xiaobo, ZHAO Zhangduo, et al. Comparison of effects of ammonium peroxydisulfate and sodium carbonate on regeneration of arsenic poisoned catalysts[J]. Thermal Power Generation, 2017, 46(9): 112-116.
41	黄力, 纵宇浩, 王虎, 等. 砷中毒平板式脱硝催化剂的氢还原再生[J]. 绿色科技, 2016(16): 58-59, 61.
	HUANG Li, ZONG Yuhao, WANG Hu, et al. Regeneration of As-poisoned plate-type de-NO_x catalyst by hydrogen reduction method[J]. Journal of Green Science and Technology, 2016(16): 58-59, 61.
42	MASASHI Kiyosawa, NORIHISA Kobayashi. Method for removing arsenic compound, method for regenerating NO_x removal catalyst, and NO_x removal catalyst:US201214007940[P]. 2015-08-25.
43	赵博, 李浙飞, 周卫可, 等. 含砷SCR脱硝催化剂再生处理实验研究[J]. 能源环境保护, 2019, 33(2): 25-28.
	ZHAO Bo, LI Zhefei, ZHOU Weike, et al. Experimental study on regeneration of arsenic-containing SCR denitration catalyst[J]. Energy Environmental Protection, 2019, 33(2): 25-28.
44	陆强, 唐昊, 李慧，等. 一种砷中毒SCR脱硝催化剂的再生方法: CN201710741285.8[P]. 2017-12-08.
	LU Qiang, TANG Hao, LI Hui, et al. Method for regenerating arsenic poisoning SCR catalyst: CN201710741285.8[P]. 2017-12-08.
45	宋文雷，李扬，王伟. 燃煤电站锅炉脱硝催化剂再生技术的研究应用[J]. 电站系统工程, 2018, 34(1): 5-8.
	SONG W L, LI Y, WANG W. Research and application of regeneration technology of boiler denitration catalyst[J]. Power System Engineering, 2018, 34(1): 5-8.
46	李想，李俊华，何煦，等. 烟气脱硝催化剂中毒机制与再生技术[J]. 化工进展, 2015, 34(12): 4129-4138.
	LI Xiang, LI Junhua, HE Xu, et al. Poisoning mechanism and regeneration process of the denitration catalyst[J]. Chemical Industry and Engineering Progress, 2015, 34(12): 4129-4138.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[6]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[7]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[8]	王晋刚, 张剑波, 唐雪娇, 刘金鹏, 鞠美庭. 机动车尾气脱硝催化剂Cu-SSZ-13的改性研究进展[J]. 化工进展, 2023, 42(9): 4636-4648.
[9]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.
[10]	张启, 赵红, 荣峻峰. 质子交换膜燃料电池中氧还原反应抗毒性电催化剂研究进展[J]. 化工进展, 2023, 42(9): 4677-4691.
[11]	王伟涛, 鲍婷玉, 姜旭禄, 何珍红, 王宽, 杨阳, 刘昭铁. 醛酮树脂基非金属催化剂催化氧气氧化苯制备苯酚[J]. 化工进展, 2023, 42(9): 4706-4715.
[12]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[13]	吴海波, 王希仑, 方岩雄, 纪红兵. 3D打印催化材料开发与应用进展[J]. 化工进展, 2023, 42(8): 3956-3964.
[14]	向阳, 黄寻, 魏子栋. 电催化有机合成反应的活性和选择性调控研究进展[J]. 化工进展, 2023, 42(8): 4005-4014.
[15]	王耀刚, 韩子姗, 高嘉辰, 王新宇, 李思琪, 杨全红, 翁哲. 铜基催化剂电还原二氧化碳选择性的调控策略[J]. 化工进展, 2023, 42(8): 4043-4057.