NH3-SCR脱硝催化剂现状及中毒失活现象研究进展

doi:10.19964/j.issn.1006-4990.2021-0735

摘要/Abstract

摘要：

随着国家能源深度调峰的推进并降低锅炉负荷运行，发现锅炉出口烟温难以驱动选择性催化还原脱硝反应的问题，通过综述氨选择性催化还原反应（NH₃-SCR）催化剂在国内外的研究进展，发现单一贵金属催化剂温度窗口窄、易中毒和比表面积较小等问题影响了其催化活性，而复合的金属氧化物催化剂、新兴的生物炭催化剂和沸石催化剂具有多孔性和良好的稳定性等优点。催化剂脱硝机理可以简单表示为其表面的酸性位点吸附氨气和氧气并与之反应，催化剂的中毒原因可总结为其内部空隙被碱金属堵塞、金属氧化物被二氧化硫抢先反应和酸性位点被羟基覆盖，具体表现为催化剂的活性降低、吸附NH₃的效率下降。对比了商用催化剂和新兴催化剂的脱硝性能得出结论，未来的研究方向是研发耐硫、耐水、耐碱的低温高效脱硝催化剂。

关键词: SCR催化剂, 脱硝, 低温, 中毒

Abstract:

With the promotion of national energy deep peak shaving and the reduction of boiler load operation，it is found that the flue gas temperature at the outlet of the boiler is difficult to drive the selective catalytic reduction denitration reaction.By summarizing the research progress of NH₃-SCR denitration catalyst at home and abroad，it was concluded that the single noble metal catalyst had the factors affecting its catalytic activity，such as narrow temperature window，easy poisoning characteristics and small specific surface area，while the composite metal oxide catalyst，the new biochar catalysts and zeolite catalysts had the advantages of porosity and good stability.The denitration mechanism of the catalyst could be simply expressed as that the acidic sites on its surface adsorbed gaseous NH₃ and O₂ and react with them.The poisoning causes of the catalyst could be summarized as that its internal voids were blocked by alkali metals，metal oxides were preempted by SO₂ and the acidic sites were covered by hydroxyl groups.Specifically，the activity of the catalyst was decreased and the efficiency of NH₃ adsorption was decreased.By comparing the denitration performance of commercial catalysts and emerging catalysts，it was concluded that the future research direction was to develop low-temperature and high-efficiency denitration catalysts with sulfur resistance，water resistance and alkali resistance.

Key words: SCR catalyst, denitration, low temperature, poisoning

中图分类号:

O643.6

李可君,李芳芹,任建兴,刘鑫,陈林峰,蔡健明. NH₃-SCR脱硝催化剂现状及中毒失活现象研究进展[J]. 无机盐工业, 2022, 54(11): 18-24.

LI Kejun,LI Fangqin,REN Jianxing,LIU Xin,CHEN Linfeng,CAI Jianming. Current situation of NH₃-SCR denitration catalyst and research progress on poisoning and deactivation[J]. Inorganic Chemicals Industry, 2022, 54(11): 18-24.

图/表 5

图1

图2

图3

图4

表1

参考文献 54

1	葛挺.“十四五”期间火电技术发展方向分析[J].河南电力,2020(S2):1-3.
	GE Ting.Analysis of the development direction of thermal power technology during the“14th Five-Year Plan” period[J].Henan Electric Power,2020(S2):1-3.
2	姚小江,张雷,孔婷婷,等.低温氨-选择性催化还原氮氧化物催化剂的研究进展[J].工业催化,2016,24(6):1-9.
	YAO Xiaojiang, ZHANG Lei, KONG Tingting, et al.Research progress in selective catalytic reduction of nitrogen oxides by ammonia at low temperature[J].Industrial Catalysis,2016,24(6):1-9.
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 Jinyu.Experimental study and simulation analysis on water and sulfur resistance of Mn based denitration catalyst doped with Ce[D].Qingdao：Qingdao University，2020.
4	HAN Lupeng, CAI Sixiang, GAO Min, 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(19):10916-10976.
5	ODRIOZOLA J A, HEINEMANN H, SOMORJAI G A, et al.AES and TDS study of the adsorption of NH₃ and NO on V₂O₅ and TiO₂ surfaces：Mechanistic implications[J].Journal of Catalysis,1989,119(1):71-82.
6	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.
7	LARRUBIA M A, RAMIS G, BUSCA G.An FT-IR study of the adsorption of urea and ammonia over V₂O₅-MoO₃-TiO₂ SCR catalysts[J].Applied Catalysis B：Environmental,2000,27(3):L145-L151.
8	梁冉冉.SCR催化剂脱硝及中毒机理的量子化学研究[D].北京：华北电力大学，2017.
	LIANG Ranran.Quantum chemistry research on DeNO _x and poisoning mechanism of SCR catalyst[D].Beijing：North China Electric Power University，2017.
9	OZKAN U S, CAI Yeping, KUMTHEKAR M W.Effect of crystal morphology in selective catalytic reduction of nitric oxide over V₂O₅ catalysts[J].Applied Catalysis A：General,1993,96(2):365-381.
10	刘福东,单文坡,石晓燕,等.用于NH₃选择性催化还原NO的非钒基催化剂研究进展[J].催化学报,2011,32(7):1113-1128.
	LIU Fudong, SHAN Wenpo, SHI Xiaoyan, et al.Research progress in vanadium-free catalysts for the selective catalytic reduction of NO with NH₃ [J].Chinese Journal of Catalysis,2011,32(7):1113-1128.
11	LIU Zhong, HAN Jian, ZHAO Li, et al.Effects of Se and SeO₂ on the denitrification performance of V₂O₅-WO₃/TiO₂ SCR cataly-st[J].Applied Catalysis A：General,2019,587.Doi:10.1016/j.apcata.2019.117263. doi: 10.1016/j.apcata.2019.117263
12	XU Junqiang, CHEN Guorong, GUO Fang, et al.Development of wide-temperature vanadium-based catalysts for selective catalytic reducing of NO _x with ammonia：Review[J].Chemical Engineering Journal,2018,353: 507-518.
13	LIU Guangli, HAN Dongtai, CHENG Jie, et al.Performance of C₂H₄ reductant in activated-carbon-supported MnO _x -based SCR catalyst at low temperatures[J].Energies,2018,12(1).Doi:10.3390/en12010123. doi: 10.3390/en12010123
14	许硕.锰系催化剂的制备及其低温SCR脱硝性能的研究[D].哈尔滨：哈尔滨工程大学，2016.
	XU Shuo.Research on Mn-based series catalysts and mechanism for selective catalytic reduction of NO _x at low-temperature[D].Harbin：Harbin Engineering University，2016.
15	KAPTEIJN F, SINGOREDJO L, ANDREINI A, et al.Activity and selectivity of pure manganese oxides in the selective catalytic reduction of nitric oxide with ammonia[J].Applied Catalysis B：Environmental,1994,3(2/3):173-189.
16	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[J].Journal of Catalysis,2012,288: 74-83.
17	LI Lulu, SUN Bowen, SUN Jingfang, et al.Novel MnO _x -CeO₂ nanosphere catalyst for low-temperature NH₃-SCR[J].Catalysis Communications,2017,100: 98-102.
18	JIANG Haoxi, WANG Yaodong, ZHOU Jiali, et al.Morphology control of manganese-based catalysts for low-temperature selective catalytic reduction of NO _x [J].Materials Letters,2018,233: 250-253.
19	牟金成.新型铁基催化剂的制备及其低温NH₃选择性催化还原NO _x 研究[D].大连：大连理工大学，2020.
	MOU Jincheng.Investigation on the preparation and application in low-temperature selective catalytic reduction of NO _x with NH₃ over novel Fe-based catalysts[D].Dalian：Dalian University of Technology，2020.
20	SHAVEL A, LIZ-MARZÁN L M.Shape control of iron oxide nanoparticles[J].Physical Chemistry Chemical Physics：PCCP,2009,11(19):3762-3766.
21	YANG Xingye, LI Bin, SUN Liang, et al.Effect of surface structure of α-Fe₂O₃ on the selective catalytic reduction of NO by NH₃ [J].物理化学学报,2012,28(1):184-188.
	YANG Xingye, LI Bin, SUN Liang, et al.Effect of surface structure of α-Fe₂O₃ on the selective catalytic reduction of NO by NH₃ [J].Acta Physico-Chimica Sinica,2012,28(1):184-188.
22	LIU Caixia, YANG Shijian, MA Lei, et al.Comparison on the performance of α-Fe₂O₃ and γ-Fe₂O₃ for selective catalytic reduction of nitrogen oxides with ammonia[J].Catalysis Letters,2013,143(7):697-704.
23	余雅昕.铁基NH₃-SCR催化剂的低温脱硝性能及抗SO₂中毒机制研究[D].南京：南京大学，2020.
	YU Yaxin.Study on the mechanism of SO₂ resistance and the catalytic performance in low-temperature selective catalytic reduction of NO by NH₃ over Fe-based catalysts[D].Nanjing：Nanjing University，2020.
24	YANG Weijie, REN Jianuo, ZHANG Hanwen, et al.Single-atom iron as a promising low-temperature catalyst for selective catalytic reduction of NO _x with NH₃：A theoretical prediction[J].Fuel,2021,302.Doi:10.1016/j.fuel.2021.121041. doi: 10.1016/j.fuel.2021.121041
25	HE Chuan, SHEN Boxiong, CHEN Jianhong, et al.Adsorption and oxidation of elemental mercury over Ce-MnO _x /Ti-PILCs[J].Environmental Science & Technology,2014,48(14):7891-7898.
26	ZHOU Jue, GUO Ruitang, ZHANG Xinfu, et al.Cerium oxide-based catalysts for low-temperature selective catalytic reduction of NO _x with NH₃：A review[J].Energy & Fuels,2021,35(4):2981-2998.
27	SHAN Ye, LIU Yangxian, LI Ying, et al.A review on application of cerium-based oxides in gaseous pollutant purification[J].Separation and Purification Technology,2020,250.Doi:10.1016/j.seppur.2020.117181. doi: 10.1016/j.seppur.2020.117181
28	PEYROVI P, GILLOT S, DACQUIN J P, et al.The activity of CeVO₄-based catalysts for ammonia-SCR：Impact of surface cerium enrichment[J].Catalysis Letters,2021,151(4):1003-1012.
29	CHEN Chuanmin, CAO Yue, LIU Songtao, et al.Review on the latest developments in modified vanadium-titanium-based SCR catalysts[J].Chinese Journal of Catalysis,2018,39(8):1347-1365.
30	LIU Caixia, CHEN Liang, LI Junhua, et al.Enhancement of activity and sulfur resistance of CeO₂ supported on TiO₂-SiO₂ for the selective catalytic reduction of NO by NH₃ [J].Environmental Science & Technology,2012,46(11):6182-6189.
31	Jinsun CHA, CHOI J C, KO J H, et al.The low-temperature SCR of NO over rice straw and sewage sludge derived char[J].Chemical Engineering Journal,2010,156(2):321-327.
32	汪怀建,涂翔,黄碧纯,等.生物炭应用于低温NH₃-SCR脱硝催化剂的研究进展[J].江西农业大学学报,2021,43(2):445-458.
	WANG Huaijian, TU Xiang, HUANG Bichun, et al.Review on application of biochar to denitrification catalysts for low-temperature NH₃-SCR[J].Acta Agriculturae Universitatis Jiangxiensis,2021,43(2):445-458.
33	IWAMOTO M, FURUKAWA H, MINE Y, et al.Copper（Ⅱ） ion-exchanged ZSM-5 zeolites as highly active catalysts for direct and continuous decomposition of nitrogen monoxide[J].Journal of the Chemical Society，Chemical Communications,1986(16).Doi:10.1039/C39860001272. doi: 10.1039/C39860001272
34	PEREIRA M V L, NICOLLE A, BERTHOUT D.Hydrothermal aging effects on Cu-zeolite NH₃-SCR catalyst[J].Catalysis Today,2015,258: 424-431.
35	SHWAN S, JANSSON J, OLSSON L, et al.Deactivation mechanisms of iron-exchanged zeolites for NH₃-SCR applications[J].Catalysis Today,2015,258: 432-440.
36	章凌,段宏昌,谭争国,等.用于柴油车尾气消除反应（NH₃-SCR）的八元环沸石分子筛研究进展[J].高等学校化学学报,2020,41(1):19-27.
	ZHANG Ling, DUAN Hongchang, TAN Zhengguo, et al.Recent advances in the preparation of 8MR zeolites for the selective catalytic reduction of NO _x （NH₃-SCR） in diesel engines[J].Chemical Journal of Chinese Universities,2020,41(1):19-27.
37	王彬宇,李莉,李菁,等.用工业固体废料合成沸石分子筛的研究进展[J].高等学校化学学报,2021,42(1):40-59.
	WANG Binyu, LI Li, LI Jing, et al.Recent progresses on the synthesis of zeolites from the industrial solid wastes[J].Chemical Journal of Chinese Universities,2021,42(1):40-59.
38	GELVES J F, DORKIS L, MÁRQUEZ M A, et al.Activity of an iron colombian natural zeolite as potential geo-catalyst for NH₃-SCR of NO _x [J].Catalysis Today,2019,320: 112-122.
39	FENG Xi, LIN Qingjin, CAO Yi, et al.Neodymium promotion on the low-temperature hydrothermal stability of a Cu/SAPO-34 NH₃-SCR monolith catalyst[J].Journal of the Taiwan Institute of Chemical Engineers,2017,80: 805-812.
40	LISI L, CIMINO S.Poisoning of SCR catalysts by alkali and alkaline earth metals[J].Catalysts,2020,10(12).Doi:10.3390/catal10121475. doi: 10.3390/catal10121475
41	LIU Chang, SHI Jianwen, GAO Chen, et al.Manganese oxide-based catalysts for low-temperature selective catalytic reduction of NO _x with NH₃：A review[J].Applied Catalysis A：General,2016,522: 54-69.
42	SHEN Boxiong, LIU Ting.Deactivation of MnO _x -CeO _x /ACF catalysts for low-temperature NH₃-SCR in the presence of SO₂ [J].Acta Physico-Chimica Sinica,2010,26(11):3009-3016.
43	WANG Chizhong, YANG Shijian, CHANG Huazhen, et al.Dispersion of tungsten oxide on SCR performance of V₂O₅WO₃/TiO₂：Acidity，surface species and catalytic activity[J].Chemical Engineering Journal,2013,225: 520-527.
44	KIJLSTRA W S, BRANDS D S, POELS E K, et al.Kinetics of the selective catalytic reduction of NO with NH₃ over MnO _x /Al₂O₃ catalysts at low temperature[J].Catalysis Today,1999,50(1):133-140.
45	ZHAO Ziwei, LI Erwei, QIN Yu, et al.Density functional theory （DFT） studies of vanadium-titanium based selective catalytic reduction（SCR） catalysts[J].Journal of Environmental Sciences （China）,2020,90: 119-137.
46	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 Ziyang, HUO Wangchen, ZHANG Yuxin, et al.A review of Mn-based low temperature NH₃-SCR denitration catalyst[J].Materials Reports,2021,35(13):13085-13099.
47	JIANG Ye, LAI Chengzhen, LI Qingyi, et al.The poisoning effect of KCl and K₂O on CeO₂-TiO₂ catalyst for selective catalytic reduction of NO with NH₃ [J].Fuel,2020,280.Doi:10.1016/j.fuel.2020.118638. doi: 10.1016/j.fuel.2020.118638
48	JIANG Ye, LIU Tianyu, LAI Chengzhen, et al.Deactivation of CeO₂-TiO₂ catalyst by K₂SO₄ for NH₃-SCR：An experimental and DFT study[J].Applied Surface Science,2021,547.Doi:10.1016/j.apsusc.2021.149196. doi: 10.1016/j.apsusc.2021.149196
49	TANG Xiaolong, SHI Yiran, GAO Fengyu, et al.Promotional role of Mo on Ce_0.3FeO _x catalyst towards enhanced NH₃-SCR catalytic performance and SO₂ resistance[J].Chemical Engineering Journal,2020,398.Doi:10.1016/j.cej.2020.125619. doi: 10.1016/j.cej.2020.125619
50	PHULE A D, CHOI J H, KIM J H.High performance of catalytic sheet filters of V₂O₅-WO₃/TiO₂ for NO _x reduction[J].Environmental Science and Pollution Research International,2021,28(26):34009-34016.
51	ZHANG Xianlong, LV Shuangshuang, ZHANG Xincheng, et al.Improvement of the activity and SO₂ tolerance of Sb-modified Mn/PG catalysts for NH₃-SCR at a low temperature[J].Journal of Environmental Sciences,2021,101: 1-15.
52	XIONG Shangchao, PENG Yue, WANG Dong, et al.The role of the Cu dopant on a Mn₃O₄ spinel SCR catalyst：Improvement of low-temperature activity and sulfur resistance[J].Chemical Engineering Journal,2020,387 .Doi:10.1016/j.cej.2020.124090. doi: 10.1016/j.cej.2020.124090
53	李锋,金保升,刘涛,范红梅.以工业级TiO₂为载体负载不同助催化剂V₂O₅基脱氮催化剂的性能[J].环境化学,2005,24(4):374-378.
	LI Feng, JIN Baosheng, LIU Tao, et al.Study of deNO _x behavior of V₂O₅-based catalyst with different catalyst promoters supported on commercial anatase TiO₂ [J].Environmental Chemistry,2005,24(4):374-378.
54	朱崇兵,金保升,李锋,等.V₂O₅-WO₃/TiO₂基催化剂SCR法脱硝试验研究[J].华东电力,2007,35(6):18-22.
	ZHU Chongbing, JIN Baosheng, LI Feng, et al.Experiment study on SCR DeNO _x behavior of V₂O₅-WO₃/TiO₂ catalysts[J].East China Electric Power,2007,35(6):18-22.

催化剂	反应条件	NO _x 最佳转化率
V-W-Ti商品催化剂^[53]	n（NH₃）∶n（NO）=1，5% O₂，24 000 h^-1	93.4%（380 ℃）
1% V₂O₅-10% WO₃/ TiO₂^[54]	1×10^-3 NH₃，1×10^-3 NO，5% O₂，24 000 h^-1	86.98%（370 ℃）
MnO₂-CeO₂纳米球^[17]	5×10^-4 NH₃，5×10^-4 NO，5% O₂，1×10^-4 SO₂，60 000 mL/（g·h）	＞97%（120~250 ℃）
MnO₂-PVP（200）^[18]	5×10^-4 NH₃，5×10^-4 NO，5% O₂，50 000 h^-1	98%（160 ℃）
Ce/Ti-Si（3∶1）^[30]	5×10^-4 NH₃，5×10^-4 NO，3% O₂，28 000 h^-1	90%（250~450 ℃）
MnO _x /TiO₂^[32]	5×10^-4 NH₃，5×10^-4 NO，5% O₂，24 000 h^-1	98%（200 ℃）
CuNd/SAPO-34^[39]	2×10^-4 NH₃，2×10^-4 NO，10% O₂，5% H₂O，40 000 h^-1	86%（200 ℃）
6%V₂O₅-9%WO₃/TiO₂^[49]	7×10^-4 NH₃，7×10^-4 NO，5% O₂，1×10^-3 SO₂，129 670 h^-1	95%~97%（220~300 ℃）
（Cu _x Mn_3-_x ）_1-_δ O₄^[52]	5×10^-4 NH₃，5×10^-4 NO，3% O₂，5% H₂O，5×10^-4 SO₂，100 000 h^-1	80%~90%（150~200 ℃）

[1]	吴兵党, 潘莹露, 赵勤政, 吴玮, 许晓毅, 黄天寅. 新型聚镧混凝剂的制备及其在低温低浊水中的深度除磷性能[J]. 无机盐工业, 2024, 56(2): 127-135.
[2]	赖晓玲, 周微, 臧甲忠, 董子超, 胡明亮, 孙绍宸. 氧化钙基吸收剂低温循环吸收二氧化碳的研究进展[J]. 无机盐工业, 2023, 55(5): 16-23.
[3]	闫芳宁,郭锦春,黄雪莉,周婷婷,王雪莹,罗清龙,邹雪净. 258.15 K下五元体系Li⁺，Na⁺，Mg²⁺//SO₄^2-，Cl^--H₂O相平衡研究[J]. 无机盐工业, 2023, 55(2): 61-66.
[4]	徐敬尧,周小丽,孙敬会,曹阿林,卿培林. 基于复合熔盐低温制备片状α-氧化铝的研究[J]. 无机盐工业, 2023, 55(2): 73-78.
[5]	郭爽, 邢冬娴, 郭校, 季晓杰, 汤建伟, 化全县, 王保明, 刘咏. 磷石膏基建筑石膏的制备及改性研究[J]. 无机盐工业, 2023, 55(12): 102-110.
[6]	杨庭龙,王富中,刘飞. 锆基双金属氧化物催化剂硫中毒的研究[J]. 无机盐工业, 2023, 55(1): 151-158.
[7]	祝悦,裘晟波,刘程琳,于建国. 机械活化法强化锂辉石矿相重构过程研究[J]. 无机盐工业, 2023, 55(1): 81-86.
[8]	周微,张耿睿,于海斌,马新宾,刘飞,刘家旭. MnO _x -ZSM-5脱硝催化剂制备的溶剂效应研究[J]. 无机盐工业, 2022, 54(8): 138-144.
[9]	张吉,宁延生,郭西凤,朱建平,王阔. 利用含锰硅胶低温制备钾水玻璃[J]. 无机盐工业, 2022, 54(5): 126-130.
[10]	杜沛佞,罗仕忠,谭仁俊,敬方梨. 钇掺杂三氧化二铁催化剂的脱硝性能研究[J]. 无机盐工业, 2022, 54(11): 137-142.
[11]	余沃晖,张盼,赵一明,查中发,吴瑞龙,齐立强. 低温脱硝催化剂研究进展[J]. 无机盐工业, 2022, 54(10): 57-68.
[12]	杨文振,熊萍,孙秀云,韩卫清. 医药废硫酸钠盐燃烧特性及低温炭化除杂研究[J]. 无机盐工业, 2021, 53(9): 76-82.
[13]	黄力,王虎,纵宇浩,常峥峰,刘洋,李金珂,韩沛. Cr对工业V-Mo/Ti脱硝催化剂的毒化作用研究[J]. 无机盐工业, 2021, 53(8): 112-116.
[14]	刘兴誉,贾媛媛,巫树锋,唐中华,张鹏,刘军强,蒲欣. 铈基SCR脱硝催化剂研究进展[J]. 无机盐工业, 2021, 53(8): 15-20.
[15]	苏少龙,曲晓龙,钟读乐,孙彦民,南军,李世鹏. 铜-铈/ZSM-5分子筛催化剂制备及脱硝性能研究[J]. 无机盐工业, 2021, 53(6): 190-193.

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会

NH₃-SCR脱硝催化剂现状及中毒失活现象研究进展

Current situation of NH₃-SCR denitration catalyst and research progress on poisoning and deactivation

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 5

参考文献 54

相关文章 15

Metrics

本文评价

推荐阅读 0

首 页