过渡金属型锰基低温NH3-SCR脱硝催化剂研究综述

doi:10.11962/1006-4990.2020-0086

摘要/Abstract

摘要：

综述了一元至多元过渡金属与锰的复合氧化物和负载型过渡金属与锰基催化剂的低温脱硝性能,着重阐述了在不同活性组分下,制备出不同结构的过渡金属催化剂对脱硝活性的影响。分析总结了过渡金属催化剂在低温NH₃-SCR中的反应机理及其抗水抗硫性能,最后,针对过渡金属催化剂存在的问题,展望了该领域未来可能的发展方向和研究热点。

关键词: 过渡金属, 低温SCR, 抗硫抗水性, 脱硝机理

Abstract:

The low temperature NO_x elimination properties of both single or multi-transition metal manganese-based catalysts and supported single or multi-transition metal manganese-based catalysts were summarized.The influence of transition metal catalysts with different structures prepared under different active components on denitration activity was emphatically expounded.The reaction mechanism of transition metal catalyst in low temperature NH₃-SCR and its sulfur and water resistance were analyzed and summarized.Finally,aiming at present problems,the potential development direction and research hotspot of tran sition metal catalysts in the future were prospected.

Key words: transition metal, low-temperature SCR, sulfur and water resistance, denitration mechanism

中图分类号:

O643.36

冯晴,曾贤君,张利杰,李贺,孟广莹,孙彦民. 过渡金属型锰基低温NH₃-SCR脱硝催化剂研究综述[J]. 无机盐工业, 2021, 53(1): 7-13.

Feng Qing,Zeng Xianjun,Zhang Lijie,Li He,Meng Guangying,Sun Yanmin. Summary of transition metal manganese-based denitration catalyst for low temperature NH₃-SCR[J]. Inorganic Chemicals Industry, 2021, 53(1): 7-13.

图/表 3

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参考文献 55

[1]	Xin Ying, Li Qian, Zhang Zhaoliang. Zeolitic materials for De-NO_xselective catalytic reduction[J]. Chem.Cat.Chem., 2018,10:29-41. doi: 10.1002/cctc.v10.1
[2]	Damma D, Boningari T, Ettireddy P R, et al. Direct decomposition of NO_x over TiO₂ supported transition metal oxides at low temperatur-es[J]. Industrial & Engineering Chemistry Research, 2018,57(49):16615-16621.
[3]	Chen Minjun, Yang Jianping, Liu Yong, et al. TiO₂ interpenetratingnetworks decorated with SnO₂ nanocrystals:Enhanced activity of selective catalytic reduction of NO with NH₃[J]. Journal of Materlals Chemistry A, 2015,3(4):1405-1409.
[4]	Thirupathi B, 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[J]. App-lied Catalysis B:Environmental, 2012,127:255-264.
[5]	Yang Liu, You Xiaochen, Sheng Zhongyi, et al. Promoting effect of noble metals(Rh,Ru,Pt,Pd)doping on the performances of MnO_x-CeO₂/graphene catalysts for selective catalytic reduction of NO with NH₃ at low temperature[J]. New Journal of Chemistry, 2018: 10.1039.C8NJ01417E-.
[6]	Wang Xiuyun, Wen Wu, Su Yanqing, et al. Influence of transition metals(M=Co,Fe and Mn)on ordered mesoporous CuM/CeO₂ cata-lysts and applications in selective catalytic reduction of NO_x with H₂[J]. RSC Advances, 2015,5(77):63135-63141. doi: 10.1039/C5RA12027F
[7]	Liu Jie, Li Xinyong, Zhao Qidong, et al. Mechanistic investigation of the enhanced NH₃-SCR on cobalt-decorated Ce-Ti mixed oxide:In situ FTIR analysis for structure-activity correlation[J]. Applied Ca-talysis B:Environmental, 2017,200:297-308.
[8]	Smirniotis P G, Pena D A, Uphade B S. Low-temperature selective catalytic reduction (SCR) of NO with NH₃ by using Mn,Cr,and Cu oxides supported on hombikat TiO₂[J]. Chembiochem, 2001,32(40):2479-2482.
[9]	Wang Peng, Sun Hong, Quan Xie, et al. Enhanced catalytic activity over MIL-100(Fe) loaded ceria catalysts for the selective catalytic reduction of NO_x with NH₃ at low temperature[J]. Journal of Hazar-dous Materials, 2015,301(1):512-521.
[10]	Li Xiaojian, Du Yali, Guo Xingmei, et al. Synjournal of a novel NiMnTi mixed metal oxides from LDH precursor and its catalytic application for selective catalytic reduction of NO_x with NH₃[J]. Catalysis Letters, 2019,149:456-464. doi: 10.1007/s10562-018-2626-7
[11]	Li Lulu, Wu Yaohui, Hou Xueyan, et al. An investigation of two-phase intergrowth and coexistence in Mn-Ce-Ti-O catalysts for the selective catalytic reduction of NO with NH₃:Structure activity relationship and reaction mechanism[J]. Industrial & Engineering Chemistry Research, 2019,58:849-862.
[12]	Yang Gang, Zhao Haitao, Luo Xiang, et al. Promotion effect and mechanism of the addition of Mo on the enhanced low temperature SCR of NO_x by NH₃ over MnO_x/γ-Al₂O₃ catalysts[J]. Applied Ca-talysis B:Environmental, 2019,245:743-752.
[13]	Wang Zhongyi, Guo Ruitang, Shi Xu, et al. The enhanced perfor-mance of Sb-modified Cu/TiO₂ catalyst for selective catalytic reduc-tion of NO_x with NH₃[J]. Applied Surface Science, 2019,475:334-341. doi: 10.1016/j.apsusc.2018.12.281
[14]	Damma D, Ettireddy P R, Reddy B M, et al. A review of low tem-perature NH₃-SCR for removal of NO_x[J]. Catalysts, 2019,9(4):349. doi: 10.3390/catal9040349
[15]	Shen Boxiong, Wang Fumei, Liu Ting. Homogeneous MnO_x-CeO₂ pellets prepared by a one-step hydrolysis process for low-tem-perature NH₃-SCR[J]. Powder Technology, 2014,253:152-157. doi: 10.1016/j.powtec.2013.11.015
[16]	Andreoli S, Deorsola F A, Pirone R. MnO_x-CeO₂ catalysts synthe-sized by solution combustion synjournal for the low-temperature NH₃-SCR[J]. Catalysis Today, 2015,253:199-206. doi: 10.1016/j.cattod.2015.03.036
[17]	Tang Xingfu, Li Junhua, Wei Lisi, et al. MnO_x-SnO₂ catalysts synt-hesized by a redox coprecipitation method for selective catalytic reduction of NO by NH₃[J]. Chinese Journal of Catalysis, 2008,29(6):531-536. doi: 10.1016/S1872-2067(08)60049-2
[18]	Chen Zhihang, Yang Qing, Li Hua, et al. Cr-MnO_x mixed-oxide ca-talysts for selective catalytic reduction of NO_x with NH₃ at low tem-perature[J]. Journal of Catalysis, 2010,276(1):56-65. doi: 10.1016/j.jcat.2010.08.016
[19]	Zhang Lei, Shi Liyi, Huang Lei, et al. Rational design of high-per-formance DeNO_x catalysts based on Mn_xCo₃O₄ nanocages derived from metal-organic frameworks[J]. ACS Catalysis, 2014,4(6):1753-1763. doi: 10.1021/cs401185c
[20]	Li Yi, Wan Yuan, Li Yanping, et al. Low-temperature selective ca-talytic reduction of NO with NH₃ over Mn₂O₃-doped Fe₂O₃ hexago-nal microsheets[J]. ACS Applied Materials & Interfaces, 2016,8(8): 10.1021/acsami.5b10264. doi: 10.1021/acsami.5b11397 pmid: 26863181
[21]	Fang De, Xie Junlin, Mei Di, et al. Effect of CuMn₂O₄ spinel in Cu-Mn oxide catalysts on selective catalytic reduction of NO_x with NH₃ at low temperature[J]. Rsc Advances, 2014,4(49):25540. doi: 10.1039/c4ra02824d
[22]	Han Yanlin, Mu Jinchen, Li Xinyong, et al. Triple-shelled NiMn₂O₄ hollow spheres as an efficient catalyst for low-temperature selective catalytic reduction of NO_x with NH₃[J]. Chemical Communications, 2018,10:1-3.
[23]	Gao Fengyu, Tang Xiaolong, Yi Honghong, et al. Improvement of activity,selectivity and H₂O&SO₂-tolerance of micro-mesoporous CrMn₂O₄ spinel catalyst for low-temperature NH₃-SCR of NO_x[J]. Applied Surface Science, 2019,466:411-424. doi: 10.1016/j.apsusc.2018.09.227
[24]	Yan Qinghua, Chen Sining, Zhang Cheng, et al. Synjournal and ca-talytic performance of Cu₁Mn_0.5Ti_0.5O_x mixed oxide as low-tempe-rature NH₃-SCR catalyst with enhanced SO₂ resistance[J]. App-lied Catalysis B:Environment, 2018,238:236-247.
[25]	Liu Jie, Li Xinyong, Li Ruoyun, et al. Facile synjournal of tube-shap-ed Mn-Ni-Ti solid solution and preferable Langmuir-Hinshelwood mechanism for selective catalytic reduction of NO_x by NH₃[J]. Applied Catalysis A: General, 2018,549:289-301. doi: 10.1016/j.apcata.2017.10.010
[26]	黄金, 仲兆平, 朱林, 等. 锰铈改性钒钨钛中低温 SCR 催化剂脱硝及抗水抗硫性能[J]. 化工进展, 2018,37(6):2242-2248.
[27]	Yan Qinghua, Chen Sining, Qiu Lei, et al. The synjournal of Cu_yMn_zAl_11-zO_x mixed oxide as a low-temperature NH₃-SCR cataly-st with enhanced catalytic performance[J]. Dalton Transaction, 2018,47:2992-3004. doi: 10.1039/C7DT02000G
[28]	Geng Yang, Shan Wenpo, Yang Shijian, et al. W-modified Mn-Ti mixed oxide catalyst for the selective catalytic reduction of NO with NH₃[J]. Industrial & Engineering Chemistry Research, 2018,57:9112-9119.
[29]	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.
[30]	Wang Xiaomei, Li Xinyong, Zhao Qidong, et al. Improved activity of W-modified MnO_x-TiO₂ catalysts for the selective catalytic re-duction of NO with NH₃[J]. Chemical Engineering Journal, 2016,288:216-222. doi: 10.1016/j.cej.2015.12.002
[31]	Zhang Tao, Qiu Feng, Chang Huazhen, et al. Novel W-modified SnMnCeO_x catalyst for the selective catalytic reduction of NO_x with NH₃[J]. Catalysis Communications, 2017,100:117-120. doi: 10.1016/j.catcom.2017.06.035
[32]	France L J, Yang Qing, Li Wan, et al. Ceria modified FeMnO_x-enh-anced performance and sulphur resistance for low-temperature SCR of NO_x[J]. Applied Catalysis B:Environmental, 2017,206:203-215. doi: 10.1016/j.apcatb.2017.01.019
[33]	Liu Zhiming, Zhu Junzhi, Li Junhua, et al. Novel Mn-Ce-Ti mixed-oxide catalyst for the selective catalytic reduction of NO_x with NH₃[J]. ACS Applied Materials & Interfaces, 2014,6:14500-14508. doi: 10.1021/am5038164 pmid: 25046245
[34]	Gao Fengyu, Tang Xiaolong, Yi Honghong, et al. Promotional mech-anisms 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. doi: 10.1016/j.cej.2017.02.042
[35]	Fang Ningjie, Guo Jiaxiu, Shu Song, et al. Enhancement of low-tem-perature 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. doi: 10.1016/j.cej.2017.05.053
[36]	Shen Boxiong, Wang Yinxin, Wang Fumei, et al. The effect of Ce-Zr on NH₃-SCR activity over MnO_x(0.6)/Ce_0.5Zr_0.5O₂ at low tempera-ture[J]. Chemical Engineering Journal, 2014,236:171-180. doi: 10.1016/j.cej.2013.09.085
[37]	Yao Xiaojiang, Li Lulu, Zou Weixin, et al. Preparation,characte-rization,and catalytic performance of high efficient CeO₂-MnO_x-Al₂O₃ catalysts for NO elimination[J]. Chinese Journal of Catalysis, 2016,37(8):1369-1380. doi: 10.1016/S1872-2067(15)61098-1
[38]	Lee S M, Park K H, Hong S C . MnO_x/CeO₂-TiO₂ mixed oxide cataly-sts for the selective catalytic reduction of NO with NH₃ at low temperature[J]. Chemical Engineering Journal, 2012, 195-196.
[39]	Wang Chao, Yu Feng, Zhu Mingyuan, et al. Microspherical MnO₂-CeO₂-Al₂O₃ mixed oxide for monolithic honeycomb catalyst and application in selective catalytic reduction of NO_x with NH₃ at 50-150 ℃[J]. Chemical Engineering Journal, 2018,346:182-192. doi: 10.1016/j.cej.2018.04.033
[40]	Smirniotis P G, Sreekanth P M, Pena D A, et al. Manganese oxide catalysts supported on TiO₂,Al₂O₃,and SiO₂:A comparison for low-temperature SCR of NO with NH₃[J]. Industrial & Engineering Chemistry Research, 2006,45:6436-6443.
[41]	Schill L, Putluru S S R,Jensen A D.et al.Mn-Fe/Al₂O₃ catalyst synthesized by deposition precipitation for low-temperature selec-tive catalytic reduction of NO with NH₃[J]. Catalysis Letters, 2015,145(9):1724-1732.
[42]	陈焕章, 李宏, 李花, 等. 负载型Mn-Fe/γ-Al₂O₃低温脱硝催化剂的性能[J]. 化工进展, 2016,35(4):1107-1112.
[43]	孟刘邦, 管学茂, 房晶瑞, 等. 不同载体Mn-Ce催化剂的制备及其脱硝性能[J]. 材料科学与工程学报, 2018,36(2):7-12.
[44]	Pena D A, Uphade B S, Smirniotis S P G. TiO₂-supported metal oxide catalysts for low-temperature selective catalytic reduction of NO with NH₃:I.Evaluation and characterization of first row transition metals[J]. Catalysis, 2004,221:421-431.
[45]	刘纳, 何峰, 谢峻林, 等. Fe掺杂Mn/TiO₂低温脱硝催化剂的催化性能研究[J].人工晶体学报, 2017(3):103-107.
[46]	Liu Jian, Guo Ruitang, Li Mingyuan, et al. Enhancement of the SO₂ resistance of Mn/TiO₂ SCR catalyst by Eu modification:A mecha-nism study[J]. Journal of Fuel, 2018,223(7):385-393. doi: 10.1016/j.fuel.2018.03.062
[47]	Xu Quan, Su Rigu, Cao Li, et al. Facile preparation of high-perfor-mance Fe-doped Ce-Mn/TiO₂ catalysts for the low-temperature selective catalytic reduction of NO_x with NH₃[J]. RSC Advances, 2017,7(77):48785-48792. doi: 10.1039/C7RA07854D
[48]	Xu Quan, Yang Wenjing, Cui Shitong, et al. Sulfur resistance of Ce-Mn/TiO₂ catalysts for low-temperature NH₃-SCR[J]. Royal So-ciety Open Science, 2018,5(3):171846.
[49]	Xu Yifan, Liu Rong, Ye Fei, et al. MnO_x-CeO₂ catalysts supported by Ti-bearing blast furnace slag for selective catalytic reduction of NO with NH₃ at low temperature[J]. Journal of the Air & Waste Management Association, 2017,67(8):899-909. doi: 10.1080/10962247.2017.1302021 pmid: 28287904
[50]	Li Ge, Wang Baodong, Wang Zhencui, et al. Reaction mechanism of low-temperature selective catalytic reduction of NO_x over Fe-Mn oxides supported on fly ash-derived SBA-15 molecular sieves: structure-activity relationships and in situ DRIFT analysis[J]. The Journal of Physical Chemistry C, 2018,122(35):20210-20231.
[51]	黄增斌, 李翠清, 王振, 等. 不同分子筛负载锰铈催化剂的低温NH₃-SCR脱硝性能[J]. 燃料化学学报, 20\|16,11(44):1388-1393.
[52]	Zhou Guangying, Zhong Biaocheng, Wang Wenhui, et al. In situ DRIFTS study of NO reduction by NH₃ over Fe-Ce-Mn/ZSM-5 catalysts[J]. Catalysis Today, 2011,175(1):157-163.
[53]	Boningari T, Pappas D K, Smirniotis P G. Metal oxide-confined in-terweaved titania nanotubes M/TNT(M=Mn,Cu,Ce,Fe,V,Cr,and Co) for the selective catalytic reduction of NO_x,in the presen-ce of excess oxygen[J]. Journal of Catalysis, 2018,365:320-333.
[54]	Zhang Lei, Zhang Dengsong, Zhang Jianping, et al. Design of meso-TiO₂@MnO_x-CeO_x/CNT with a core-shell structure as DeNO_x cata-lysts:promotion of activity,stability and SO₂-tolerance[J]. The Royal Society of Chemistry, 2013,5:9821-9829.
[55]	Lee T Y, Liou S, Bai H. Comparison of titania nanotubes and tita-nium dioxide as supports of low-temperature selective catalytic re-duction catalysts under sulfur dioxide poisoning[J]. Journal of the Air & Waste Management Association, 2017,67(3):292-305. doi: 10.1080/10962247.2016.1231144 pmid: 27649768

催化剂	制备方法	条件	NO转化率/%
催化剂	制备方法	条件	初始条件	加入SO₂和H₂O	停加SO₂和H₂O
Cu₁Mn_0.5Ti_0.5O_x^[24]	共沉淀法	379 mg/m³ NH₃,643 mg/m³ NO,411 mg/m³ NO₂,286 mg/m³ SO₂, 体积分数5% H₂O和5% O₂ ,Ar作平衡气,200 ℃	90	64.6	73.4
MnNiTiO_x^[25]	共沉淀法	379 mg/m³ NH₃,670 mg/m³ NO,286 mg/m³ SO₂ ,体积分数 10% H₂O 和 5% O₂ ,He作平衡气,300 ℃	85	70~75	85
V-W-Mn-Ce/TiO_x^[26]	浸渍法	379 mg/m³ NH₃,670 mg/m³ NO,1 000 mg/m³ SO₂,体积分数 10% H₂O和5% O₂,N₂作平衡气,240 ℃	100	>80	85
Cu_yMn_zAl_1-zO_x^[27]	共沉淀法	379 mg/m³ NH₃,670 mg/m³ NO,286 mg/m³ SO₂,体积分数 5% H₂O和5% O₂,Ar作平衡气,150 ℃	92.1	64.9	80.7
Mn_0.5W_0.1TiO_x^[28]	共沉淀法	379 mg/m³ NH₃,670 mg/m³ NO,体积分数5% O₂,N₂作平衡气,200 ℃	95%以上	—	—
Fe-Co-Mn-Ce/TiO₂^[29]	浸渍法	379 mg/m³ NH₃,670 mg/m³ NO,571 mg/m³ SO₂,体积分数 10% H₂O和6% O₂,N₂作平衡气,200 ℃	100	85	>90
W-MnO_x-TiO₂^[30]	共沉淀法	759 mg/m³ NH₃,1339 mg/m³ NO,286 mg/m³ SO₂ ,体积分数 10% H₂O 和 5% O₂ ,He作平衡气,140~260 ℃	100	>95	—
W-SnMnCeO_x^[31]	共沉淀法	379 mg/m³ NH₃,670 mg/m³ NO,286 mg/m³ SO₂ ,体积分数 5% H₂O 和 5% O₂ ,N₂作平衡气,200 ℃	100	>80	>90

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过渡金属型锰基低温NH₃-SCR脱硝催化剂研究综述

Summary of transition metal manganese-based denitration catalyst for low temperature NH₃-SCR

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