金属氧化物催化CO还原NO的研究进展

doi:10.16085/j.issn.1000-6613.2019-0195

摘要/Abstract

摘要：

一氧化碳（CO）广泛存在于烧结/球团/焦化烟气或汽车尾气中，应用CO-选择性催化还原（SCR）技术同时脱除烟气中CO和NO是烟气治理的理想方案之一。目前，在NO-CO反应研究中较多的是贵金属催化剂，但由于其价格昂贵、高温失活、易中毒等问题难以在工业中实现应用。本文将近几年来金属氧化物催化CO还原NO的研究成果进行了系统的梳理与总结，重点介绍Fe基、Ce基、Co基、Cu基这4种金属氧化物催化剂的研究进展，分析催化剂的制备方法、掺杂助剂种类和比例、NO-CO反应条件等因素与催化活性之间的关系，总结催化剂抗水抗硫性能及可能的CO-SCR反应机理，并探讨O₂存在的条件下对催化剂活性的影响，为提高金属氧化物催化剂抗氧性研究提供理论参考。

关键词: 一氧化碳, 选择催化还原, 脱硝, 金属氧化物, 催化剂, 反应机理, 抗氧性

Abstract:

Carbon monoxide as one of the potential reducing agents for removing nitrogen oxides, is widely present in sintering, pellet, coking flue gas and automobile exhaust. The application of CO-SCR technology to simultaneously remove CO and NO is one of the ideal scheme for flue gas treatment. At present, the catalysts studied in the NO-CO reaction are noble metal catalysts, but they are difficult to apply in industry due to their high price, high temperature deactivation and poisoning. In this paper, the recent researches of NO reduction by CO over metal oxide catalysts are systematically reviewed and summarized. The research progress of preparation methods, doping modification and reaction conditions of Fe based, Ce based, Co based and Cu based catalysts are analyzed, and the capability of water and sulfur resistance have been investigated. Analyzing the mechanism of CO-SCR reaction, and researching the influence of the presence of O₂, which are evaluated on the NO reduction performance of the catalysts, in order to providing theoretical reference for the study of metal oxide catalysts.

Key words: carbon monoxide, selective catalytic reduction（SCR）, de-NO_x, metal oxide, catalyst, reaction mechanism, oxygen resistance

中图分类号:

X511

周远松,高凤雨,唐晓龙,易红宏,孟婧轩. 金属氧化物催化CO还原NO的研究进展[J]. 化工进展, 2019, 38(11): 4941-4948.

Yuansong ZHOU,Fengyu GAO,Xiaolong TANG,Honghong YI,Jingxuan MENG. Research progress on NO reduction by CO over metal oxide catalysts[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 4941-4948.

图/表 7

参考文献 51

1	YAOXiaojiang, TANGChangjin, GAOFei, et al. Research progress on the catalytic elimination of atmospheric molecular contaminants over supported metal-oxide catalysts[J]. Catalysis Science & Technology, 2014, 4(9): 2814-2829.
2	SKALSKAK, MILLERJ S, LEDAKOWICZS. Trends in NO_x abatement: a review[J]. Science of the Total Environment, 2010, 408(19): 3976-3989.
3	ROY S, HEGDEM S, MADRASG. Catalysis for NO_xabatement[J]. Applied Energy, 2009, 86(11): 2283-2297.
4	TWIGGM V. Progress and future challenges in controlling automotive exhaust gas emissions[J]. Applied Catalysis B: Environmental, 2007, 70(1/2/3/4): 2-15.
5	WANGLuyuan, CHENGXingxing, WANGZhiqiang, et al. Investigation on Fe-Co binary metal oxides supported on activated semi-coke for NO reduction by CO[J]. Applied Catalysis B:Environmental, 2017, 201: 636-651.
6	CHENGX X, BIX T. A review of recent advances in selective catalytic NO_x reduction reactor technologies[J]. Particuology, 2014, 16: 1-18.
7	IsabellaNOVA, CristianCIARDELLI, EnricoTRONCONI, et al. NH₃-SCR of NO over a V-based catalyst: low-T redox kinetics with NH₃ inhibition[J]. AIChE Journal, 2006, 52(9): 3222-3233.
8	CHENGX X, BIX T. Reaction kinetics of selective catalytic reduction of NO_x by propylene over Fe/ZSM-5[J]. Chemical Engineering Journal, 2012, 211: 453-462.
9	YANGT T, BIH T, CHENGX X. Effects of O₂, CO₂ and H₂O on NO_x adsorption and selective catalytic reduction over Fe/ZSM-5[J]. Applied Catalysis B: Environmental, 2011, 102(1/2): 163-171.
10	CHENGX X, BIX T. Modeling NO_xadsorption onto Fe/ZSM-5 catalysts in a eixed bed reactor[J]. International Journal of Chemical Reactor Engineering, 2013, 11(1):19-30.
11	LIULianjun, YAOZhijian, LIUBin, et al. Correlation of structural characteristics with catalytic performance of CuO/Ce_xZr_1-_xO₂ catalysts for NO reduction by CO[J]. Journal of Catalysis, 2010, 275(1): 45-60.
12	ILIOPOULOUE F, EFTHIMIADISE A, NALBANDIANL, et al. Ir-based additives for NO reduction and CO oxidation in the FCC regenerator: evaluation, characterization and mechanistic studies[J]. Applied Catalysis B: Environmental, 2005, 60(3/4): 277-288.
13	SUNChuanzhi, TANGYingjie, GAOFei, et al. Effects of different manganese precursors as promoters on catalytic performance of CuO-MnO_x/TiO₂ catalysts for NO removal by CO[J]. Physical Chemistry Chemical Physics, 2015, 17(24): 15996-16006.
14	KACIMIM, ZIYADM, LIOTTAL F. Cu on amorphous AlPO₄: preparation, characterization and catalytic activity in NO reduction by CO in presence of oxygen[J]. Catalysis Today, 2015, 241: 151-158.
15	YAOXiaojiang, XIONGYan, ZOUWeixin, et al. Correlation between the physicochemical properties and catalytic performances of Ce_xSn_1-_xO₂ mixed oxides for NO reduction by CO[J]. Applied Catalysis B: Environmental, 2014, 144: 152-165.
16	YAOXiaojiang, TANGChangjin, JIZeyang, et al. Investigation of the physicochemical properties and catalytic activities of Ce_0.67M_0.33O₂ (M = Zr⁴⁺, Ti⁴⁺, Sn⁴⁺) solid solutions for NO removal by CO[J]. Catalysis Science & Technology, 2013, 3(3): 688-698.
17	YUQiang, YAOXiaojiang, ZHANGHongliang, et al. Effect of ZrO₂ addition method on the activity of Al₂O₃-supported CuO for NO reduction with CO: impregnation vs. coprecipitation[J]. Applied Catalysis A: General, 2012, 423: 42-51.
18	孟婧轩, 高凤雨, 唐晓龙, 等. Ir基催化剂用于CO选择性催化还原 NO的研究进展[J]. 化工进展, 2019, 38(6): 2746-2755.
	MENGJingxuan, GAOFengyu, TANGXiaolong, et al. Review of Ir-based catalyst in selective catalytic reduction of NO with CO[J] Chemistry Industry and Engineering Progress, 2019, 38(6): 2746-2755.
19	CHAFIKT, KONDARIDESD I, VERYKIOSX E. Catalytic reduction of NO by CO over rhodium catalysts 1. Adsorption and displacement characteristics investigated by insitu FTIR and transient-MS techniques[J]. Journal of Catalysis, 2000, 190(2): 446-459.
20	ZHANGXingyu, MAChunyuan, CHENGXingxing, et al. Performance of Fe-Ba/ZSM-5 catalysts in NO+O₂ adsorption and NO+CO reduction[J]. International Journal of Hydrogen Energy, 2017, 42(10): 7077-7088.
21	LIUTangkang, QIANJunning, YAOYanyan, et al. Research on SCR of NO with CO over the Cu_0.1La_0.1Ce_0.8O mixed-oxide catalysts: effect of the grinding[J]. Molecular Catalysis, 2017, 430: 43-53.
22	SALKERA V, DESAIM S F. Catalytic activity and mechanistic approach of NO reduction by CO over M_0.05Co_2.95O₄(M = Rh, Pd & Ru) spinel system[J]. Applied Surface Science, 2016, 389: 344-353.
23	SALKERA V, DESAIM S F. CO-NO/O₂ redox reactions over Cu substituted cobalt oxide spinels[J]. Catalysis Communications, 2016, 87: 116-119.
24	SALKERA V, DESAIM S F. Low-temperature nitric oxide reduction over silver-substituted spinels cobalt oxide [J]. Catalysis Science & Technology, 2016, 6(2): 430-433.
25	DENGChangshun, HUANGQingqing, ZHUXiying, et al. The influence of Mn-doped CeO₂ on the activity of CuO/CeO₂ in CO oxidation and NO+CO model reaction[J]. Applied Surface Science, 2016, 389: 1033-1049.
26	DENGChangshun, LIBin, DONGLihui, et al. NO reduction by CO over CuO supported on CeO₂-doped TiO₂: the effect of the amount of a few CeO₂[J]. Physical Chemistry Chemical Physics, 2015, 17(24): 16092-16109.
27	GEChengyan, LIULichen, LIUZhuotong, et al. Improving the dispersion of CeO₂ on gamma-Al₂O₃ to enhance the catalytic performances of CuO/CeO₂/gamma-Al₂O₃ catalysts for NO removal by CO[J]. Catalysis Communications, 2014, 51: 95-99.
28	XIONGYan, YAOXiaojiang, TANGChangjin, et al. Effect of CO-pretreatment on the CuO-V₂O₅/gamma-Al₂O₃catalyst for NO reduction by CO[J]. Catalysis Science & Technology, 2014, 4(12): 4416-4425.
29	GEChengyan, LIULianjun, YAOXiaojiang, et al. Treatment induced remarkable enhancement of low-temperature activity and selectivity of copper-based catalysts for NO reduction[J]. Catalysis Science & Technology, 2013, 3(6): 1547-1557.
30	DONGLihui, ZHANGBing, TANGChangjin, et al. Influence of CeO₂ modification on the properties of Fe₂O₃-Ti_0.5Sn_0.5O₂ catalyst for NO reduction by CO[J]. Catalysis Science & Technology, 2014, 4(2): 482-493.
31	LUOMengfei, CHENJun, CHENLinshen, et al. Structure and redox properties of Ce_xTi_1-_xO₂ solid solution[J]. Chemistry of Materials, 2001, 13(1): 197-202.
32	BAIDYAT, GUPTAA, DESHPANDEYP A, et al. High oxygen storage capacity and high rates of CO oxidation and NO reduction catalytic properties of Ce_1-_xSn_xO₂ and Ce_0.78Sn_0.2Pd_0.02O₂-delta[J]. Journal of Physical Chemistry C, 2009, 113(10): 4059-4068.
33	NGUYENT B, DELOUMEJ P, PERRICHONV. Study of the redox behaviour of high surface area CeO₂-SnO₂ solid solutions[J]. Applied Catalysis A: General, 2003, 249(2): 273-284.
34	LIUTangkang, QIANJunning, YAOYangyan, et al. Research on SCR of NO with CO over the Cu_0.1La_0.1Ce_0.8O mixed-oxide catalysts: effect of the grinding[J]. Molecular Catalysis, 2017, 430: 43-53.
35	DAIXiaoxia, JIANGWeiyu, WANGWanglong, et al. Supercritical water syntheses of transition metal-doped CeO₂ nano-catalysts for selective catalytic reduction of NO by CO: an in situ diffuse reflectance fourier transform infrared spectroscopy study[J]. Chinese Journal of Catalysis, 2018, 39(4): 728-735.
36	郭磊, 张涛, 常化振, 等. Ce掺杂改性Ni-Al-O_x催化剂CO-NO反应性能[J]. 中国环境科学, 2018, 38(9): 3313-3321.
	GUOLei, ZHANGTao, CHANGHuazhen, et al. Study on Ce-doped Ni-Al-O_x catalysts for reduction by CO[J]. China Environmenal Science, 2018, 38(9): 3313-3321.
37	SONGW Q, POYRAZA S, MENGY T, et al. Mesoporous Co₃O₄ with controlled porosity: inverse micelle synthesis and high-performance catalytic CO oxidation at-60 degrees C[J]. Chemistry of Materials, 2014, 26(15): 4629-4639.
38	WANGLei, ZHANGShiran, ZHUYuan, et al. Catalysis and in situ studies of Rh-1/Co₃O₄ nanorods in reduction of NO with H-2[J]. ACS Catalysis, 2013, 3(5): 1011-1019.
39	ZHOUMinjie, CAILili, MichalBAJDICH, et al. Enhancing catalytic CO oxidation over Co₃O₄ nanowires by substituting Co²⁺ with Cu²⁺[J]. ACS Catalysis, 2015, 5(8): 4485-4491.
40	SamiBARKAOUI, HassounaDHAOUADI, SalahKOUASS, et al. Structural and optical proprieties of doped cobalt oxide: Cu_xCO_3-_xO₄ (x=0.0; 0.1; 0.2; 0.4; and 0.6)[J]. Optik, 2015, 126(9/10): 1047-1051.
41	NICKOLOVR, STANKOVAN, KHRISTOVAM, et al. Copper oxide supported on carbon modified alumina as catalyst for reduction of NO with CO[J]. Journal of Colloid and Interface Science, 2003, 265(1): 121-128.
42	KHRISTOVAM, IVANOVB, SPASSOVAI, et al. NO reduction with CO on copper and ceria oxides supported on alumina[J]. Catalysis Letters, 2007, 119(1/2): 79-86.
43	WANHaiqin, LIDan, DAIYue, et al. Catalytic behaviors of CuO supported on Mn₂O₃ modified gamma-Al₂O₃ for NO reduction by CO[J]. Journal of Molecular Catalysis A: Chemical, 2010, 332(1/2): 32-44.
44	CHENGXingxing, ZHANGXingyu, SUDexin, et al. NO reduction by CO over copper catalyst supported on mixed CeO₂ and Fe₂O₃: catalyst design and activity test[J]. Applied Catalysis B:Environmental, 2018, 239: 485-501.
45	孔令朋, 苗杰, 李明航, 等. CuMnCeLa-O/γ-Al₂O₃催化剂助燃脱硝性能研究[J]. 分子催化, 2018, 32(4): 295-304.
	KONGLingpeng, MIAOJie, LIMinghang, et al. Performances of selective catalytic reduction of NO with CO over CuMnCeLa-O/γ-Al₂O₃ catalyst[J]. Journal of Molecular Catalysis, 2018, 32(4): 295-304.
46	WENBin, HEMingyuan, EthanSCHRUM, et al. NO reduction and CO oxidation over Cu/Ce/Mg/Al mixed oxide catalyst in FCC operation[J]. Journal of Molecular Catalysis A:Chemical, 2002, 180(1/2): 187-192.
47	LIJun, WANGShan, ZHOULi, et al. NO reduction by CO over a Fe-based catalyst in FCC regenerator conditions[J]. Chemical Engineering Journal, 2014, 255: 126-133.
48	ZahraGHOLAMI, LUOGuohua. Low-temperature selective catalytic reduction of NO by CO in the presence of O₂ over Cu∶Ce catalysts supported by multiwalled carbon nanotubes[J]. Industrial & Engineering Chemistry Research, 2018, 57(27): 8871-8883.
49	SREEKANTHP M, SMIRNIOTISP G. Selective reduction of NO with CO over titania supported transition metal oxide catalysts[J]. Catalysis Letters, 2008, 122(1/2): 37-42.
50	BONINGARIT, PAVANIS M, ETTIREDDYP R, et al. Mechanistic investigations on NO reduction with CO over Mn/TiO₂ catalyst at low temperatures[J]. Molecular Catalysis, 2018, 451: 33-42.
51	付玉秀, 仲雪梅, 常化振, 等. 铈钴复合氧化物催化剂催化CO-SCR反应机理研究 [J]. 中国环境科学, 2018, 38(8): 2934-2940.
	FUYuxiu, ZHONGXuemei, CHANGHuazhen, et al. Mechanism study on CO-SCR over Ce-Co-O_x mixed oxides catalysts[J]. China Enverimantal Science, 2018, 38(8): 2934-2940.

催化剂	反应条件					反应温度/℃	NO 转化率/%	CO 转化率/%	参考文献
催化剂	NO/%	CO/%	O₂/%	SO₂/μg?g^-1	H₂O/%	反应温度/℃	NO 转化率/%	CO 转化率/%	参考文献
Fe-Ba/ZSM-5	0.1	0.2	0	0	0	325	100	—	[20]
Fe_0.8Co_0.2/ASC	0.1	0.2	0	0	0	200	100	—	[5]
Ce_0.67Sn_0.33O₂	5	10	0	0	0	325	70	—	[16]
Cu_0.1La_0.1Ce_0.8O	5	10	0	0	10	250	90	42	[21]
Rh_0.05Co_2.95O₄	5	5	2.5	0	2	250	80	—	[22]
Co_2.9Cu_0.1O₄	5	5	2.5	0	2.5	200	70	—	[23]
Ag_0.3Co_2.7O₄	5	5	2.5	0	2.5	120	90	—	[24]
Cu/CeMn-10∶1	5	5	0	0	0	225	98	48	[25]
Cu/TC-60∶1	5	10	0	0	0	300	99	53	[26]
CuO/CeO₂/γ-Al₂O₃	5	10	0	0	0	350	100	—	[27]
CuO-V₂O₅/γ-Al₂O₃	5	10	0	0	0	350	100	—	[28]
CuO/Ni_xO_y/γ-Al₂O₃	5	10	0	0	0	200	90	—	[29]

催化剂	反应条件					反应温度/℃	NO 转化率/%	CO 转化率/%	参考文献
催化剂	NO/%	CO/%	O₂/%	SO₂/μg?g^-1	H₂O/%	反应温度/℃	NO 转化率/%	CO 转化率/%	参考文献
Fe-Ba/ZSM-5	0.1	0.2	0	0	0	325	100	—	[20]
Fe_0.8Co_0.2/ASC	0.1	0.2	0	0	0	200	100	—	[5]
Ce_0.67Sn_0.33O₂	5	10	0	0	0	325	70	—	[16]
Cu_0.1La_0.1Ce_0.8O	5	10	0	0	10	250	90	42	[21]
Rh_0.05Co_2.95O₄	5	5	2.5	0	2	250	80	—	[22]
Co_2.9Cu_0.1O₄	5	5	2.5	0	2.5	200	70	—	[23]
Ag_0.3Co_2.7O₄	5	5	2.5	0	2.5	120	90	—	[24]
Cu/CeMn-10∶1	5	5	0	0	0	225	98	48	[25]
Cu/TC-60∶1	5	10	0	0	0	300	99	53	[26]
CuO/CeO₂/γ-Al₂O₃	5	10	0	0	0	350	100	—	[27]
CuO-V₂O₅/γ-Al₂O₃	5	10	0	0	0	350	100	—	[28]
CuO/Ni_xO_y/γ-Al₂O₃	5	10	0	0	0	200	90	—	[29]

[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.
[9]	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.
[10]	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.
[11]	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.
[12]	李东泽, 张祥, 田键, 胡攀, 姚杰, 朱林, 卜昌盛, 王昕晔. 基于水泥窑脱硝的碳基还原NO _x 研究进展[J]. 化工进展, 2023, 42(9): 4882-4893.
[13]	朱传强, 茹晋波, 孙亭亭, 谢兴旺, 李长明, 高士秋. 固体高分子脱硝剂选择性非催化还原NO _x 特性[J]. 化工进展, 2023, 42(9): 4939-4946.
[14]	白志华, 张军. 二乙烯三胺五亚甲基膦酸/Fenton体系氧化脱除NO[J]. 化工进展, 2023, 42(9): 4967-4973.
[15]	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.