富氧条件下氢气选择催化还原汽车尾气氮氧化物的研究进展

doi:10.16085/j.issn.1000-6613.2018-0720

摘要/Abstract

摘要：

汽车尾气中的氮氧化物（NO _x ）是大气主要污染物之一，严重危害了环境和人类健康。选择催化还原（SCR）消除技术是一种在富氧条件下能够高选择性消除NO _x 的技术。氢气选择催化还原氮氧化物（H₂-SCR）由于其低温高活性的优势备受关注。目前H₂-SCR研究中以Pt和Pd作活性组分催化剂使用较多，其中Pt基催化剂的研究最为广泛，本文介绍了催化剂载体类型、载体性质（如酸碱性、比表面积、孔道结构）、助剂和预处理方式等对催化活性的影响及影响机制，综述了反应条件参数（如反应气中O₂和NO₂浓度，杂质气体H₂O和SO₂）对催化剂催化活性的影响，认为反应气组分的影响在于各组分在催化剂上的竞争吸附以及对催化剂活性位的影响，最后展望了面向实际应用H₂-SCR技术未来的研究方向。

关键词: 环境, 选择催化还原, 氮氧化物, 催化剂, 活性, 影响因素

Abstract:

Nitrogen oxide (NO _x ) from automobile exhaust is one of the main pollutants in the atmosphere，which is very harmful to environment and human health. Selective catalytic reduction (SCR) of NO _x is a technology for high selective removal of NO _x in presence of excess oxygen. H₂-SCR has attracted much attention due to its advantages of high activity at low temperature. At present, Pt and Pd are widely used as active component of the catalysts used in H₂-SCR. Among them, Pt-supported catalysts have been the most widely studied. The influence and the corresponding mechanism of the types of the catalyst support, carrier properties (such as acid-base properties, BET surface area and pore structure), additive and pretreatment methods on the catalytic performance were summarized. Then, the effect of reaction condition parameters (such as concentration of O₂ and NO₂ in reactant gas mixture, coexisting gas of H₂O and SO₂ in practical processes) on the catalytic activity were reviewed. It was found that the impact of reaction gas component on the catalytic activity is determined by their competitive adsorption on catalyst’s surface and their influence on the active sites. Finally, the future research direction of H₂-SCR for practical application was prospected.

Key words: environment, selective catalytic reduction, nitrogen oxide, catalyst, reactivity, influence factor

中图分类号:

X511

张肖肖. 富氧条件下氢气选择催化还原汽车尾气氮氧化物的研究进展[J]. 化工进展, 2019, 38(03): 1362-1370.

Xiaoxiao ZHANG. Research progresses on selective catalytic reduction of NO _x from automobile exhaust by hydrogen in excess oxygen[J]. Chemical Industry and Engineering Progress, 2019, 38(03): 1362-1370.

图/表 1

参考文献 50

1	LI J H , CHANG H Z , MA L, et al . Low-temperature selective catalytic reduction of NO _x with NH₃ over metal oxide and zeolite catalysts: ａreview[J]. Catalysis Today, 2011, 175: 147-156.
2	YU J , GUO F , WANG Y L , et al . Sulfur poisoning resistant mesoporous Mn-base catalyst for low-temperature SCR of NO with NH₃ [J]. Applied Catalysis B: Environmental, 2010, 95: 160-168.
3	YU Q , WANG X P , XING N , et al . The role of protons in the NO reduction by acetylene over ZSM-5[J]. Journal of Catalysis, 2007, 245: 124-132.
4	LIU Z M , WOO S I, LEE W S . In situ FT-IR studies on the mechanism of selective catalytic reduction of NO _x by propene over SnO₂/Al₂O₃ catalyst[J]. The Journal Physical Chemistry B, 2006, 110: 26019-26023.
5	SATSUMA A , HASHIMOTO M , SHIBATA J , et al . Nitrous oxide free pathway for selective reduction of NO by hydrogen over supported Pt catalysts[J]. Chemical Communications, 2003(14): 1698-1699.
6	COSTA C N , STATHOPOULOS V N , BELESSI V C , et al . An investigation of the NO/H₂/O₂ (lean-deNO _x ) reaction on a highly active and selective Pt/La_0.5Ce_0.5MnO₃ catalyst[J]. Journal of Catalysis, 2001, 197: 350-364.
7	BURCH R , COLEMAN M D . An investigation of promoter effects in the reduction of NO by H₂ under lean-burn conditions[J]. Journal of Catalysis, 2002, 208: 435-447.
8	SCHOTT F J P , BALLE P , ADLER J , et al . Reduction of NO _x by H₂ on Pt/WO₃/ZrO₂ catalysts in oxygen-rich exhaust[J]. Applied Catalysis B: Environmental, 2009, 87: 18-29.
9	SHELEF M , JONES J H , KUMMER J T , et al . Selective catalytic reaction of hydrogen with nitric oxide in the presence of oxygen[J]. Environmental Science & Technology, 1971, 9: 790-798.
10	BURCH R , COLEMAN M D . An investigation of the NO/H₂/O₂ reaction on noble-metal catalysts at low temperatures under lean-burn conditions[J]. Applied Catalysis B: Environmental, 1999, 23: 115-121.
11	COSTA C N , EFSTATHIOU A M . Pt/Mg-Ce-O catalyst for NO/H₂/O₂ lean de-NO _x reaction[J]. Environmental Chemistry Letters, 2004, 2: 55-58.
12	UEDA A , NAKAO T , AZUMA M , et al . Two conversion maxima at 373 and 573K in the reduction of nitrogen monoxide with hydrogen over Pd/TiO₂ catalyst[J]. Catalysis Today, 1998, 45: 135-138.
13	MACLEOD N , CROPLEY R , LAMBERT R M . Efficient reduction of NO _x by H₂ under oxygen-rich conditions over Pd/TiO₂ catalysts: an in situ DRIFTS study[J]. Catalysis Letters, 2003, 86: 69-75.
14	YU Q , RICHTER M , LI L D , et al . The promotional effect of Cr on catalytic activity of Pt/ZSM-35 for H₂-SCR in excess oxygen[J]. Catalysis Communications, 2010, 11: 955-959.
15	LEICHTA M , SCHOTTA F J P , BRUNSB M , et al . NO _x reduction by H₂ on WO _x /ZrO₂-supported Pd catalysts under lean conditions[J]. Applied Catalysis B: Environmental, 2012, 117/118: 275-282.
16	MACHIDA M , IKEDA S , KUROGI D , et al . Low temperature catalytic NO _x -H₂ reactions over Pt/TiO₂-ZrO₂ in an excess oxygen[J]. Applied Catalysis B: Environmental, 2001, 35: 107-116.
17	COSTA C N , EFSTATHIOU A M . Low-temperature H₂-SCR of NO on a novel Pt/MgO-CeO₂ catalyst[J]. Applied Catalysis B: Environmental, 2007, 72: 240-252.
18	COSTA C N , SAVVA P G , FIERRO J L G , et al . Industrial H₂-SCR of NO on a novel Pt/MgO-CeO₂ catalyst[J]. Applied Catalysis B: Environmental, 2007, 75: 147-156.
19	COSTA C N , SAVVA P G , ANDRONIKOU C , et al . An investigation of the NO/H₂/O₂ (lean de-NO _x ) reaction on a highly active and selective Pt/La₀ _. ₇Sr₀ _. ₂Ce₀ _. ₁FeO₃ catalyst at low temperatures[J]. Journal of Catalysis, 2002, 209: 456-471.
20	SHIBATA J , HASHIMOTO M , SHIMIZU K , et al . Factors controlling activity and selectivity for SCR of NO by hydrogen over supported platinum catalysts[J].The Journal of Physical Chemistry B, 2004, 108: 18327-18335.
21	武鹏, 刘运霞, 章福祥, 等 . Pt/SAPO-34在低温H₂选择催化还原NO反应中的催化活性[J]. 催化学报, 2008, 29: 191-196.
	WU P , LIU Y X , ZHANG F X , et al . Catalytic activity of Pt/SAPO-34 for selective catalytic reduction of NO by H₂ at low temperature[J]. Chinese Journal of Catalysis, 2008, 29: 191-196.
22	武鹏, 刘运霞, 章福祥, 等 . Pt/Si-MCM-41介孔结构对低温NO+H₂+O₂反应的影响[J]. 物理化学学报, 2008, 24: 369-374.
	WU P , LIU Y X , ZHANG F X , et al . Influences of mesoporous structure on the NO+H₂+O₂ low temperature reaction over Pt/Si-MCM-41 catalyst[J]. Acta Physico-Chimica Sinica, 2008, 24: 369-374.
23	YU Q , RICHTER M , KONG F X , et al . Selective catalytic reduction of NO by hydrogen over Pt/ZSM-35[J]. Catalysis Today, 2010, 158: 452-458.
24	LI L D , WU P , YU Q , et al . Low temperature H₂-SCR over platinum catalysts supported on Ti-containing MCM-41[J]. Applied Catalysis B: Environmental, 2010, 94: 254-262.
25	YANG S F , WANG X P , CHU W L , et al . An investigation of the surface intermediates of H₂-SCR of NO _x over Pt/H-FER[J]. Applied Catalysis B: Environmental, 2011, 107: 380-385.
26	ZHANG X X , WANG X P , ZHAO X J , et al . Promotion effect of tungsten on the activity of Pt/HZSM-5 for H₂-SCR[J], Chemical Engineering Journal, 2015, 260: 419-426.
27	GAO S , WANG X P , LI M R , et al . Nanofibrous SUZ-4 loading Pt used for selective catalytic reduction of NO _x by hydrogen[J], Microporous and Mesoporous Materials, 2014, 183: 185-191.
28	ITOH M , MOTOKI K , SAITO M , et al . Lean NO _x reduction by hydrogen over Pt-supported rare earth oxide catalysts and their in situ DRIFTs study[J]. Bulletin of the Chemical Society of Japan, 2009, 82: 1197-1202.
29	YOKOTA K , FUKUI M , TANAKA T . Catalytic removal of nitric oxide with hydrogen and carbon monoxide in the presence of excess oxygen[J]. Applied Surface Science 1997, 121/122: 273-277.
30	MILLER D D , CHUANG S S C . In situ infrared study of NO reduction over Pd/Al₂O₃ and Ag-Pd/Al₂O₃ catalysts under H₂-rich and lean-burn conditions[J]. Journal of the Taiwan Institute of Chemical Engineers, 2009, 40: 613-621.
31	MACHIDA M , WATANABE T . Effect of Na-addition on catalytic activity of Pt-ZSM-5 for low-temperature NO-H₂-O₂ reactions[J]. Applied Catalysis B: Environmental 2004, 52: 281-286.
32	QI G , YANG R T , RINALDI F C , et al . Selective catalytic reduction of nitric oxide with hydrogen over Pd-based catalysts[J]. Journal of Catalysis, 2006, 237: 381-392.
33	MERGLER Y J , NIEUWENHUYS B E . NO reduction by H₂ over promoted Pt catalysts[J]. Applied Catalysis B: Environmental, 1997, 12: 95-110.
34	WEN B . NO reduction with H₂ in the presence of excess O₂ over Pd/MFI catalyst[J]. Fuel, 2002, 81: 1841-1846.
35	FRANK B , EMIG G , RENKEN A . Kinetics and mechanism of the reduction of nitric oxides by H₂ under lean-burn conditions on a Pt-Mo-Co/α-Al₂O₃ catalyst[J]. Applied Catalysis B: Environmental, 1998, 19: 45-57.
36	NANBA T , SUGAWARA K , MASUKAWA S , et al . Optimization of physical mixtures of Pt/ZrO₂ and H-form zeolites for catalysis of the NO-H₂-O₂ reaction[J]. Industrial & Engineering Chemistry Research, 2005, 44: 3426-3431.
37	NANBA T , KOHNO C , MASUKAWA S , et al . Improvements in the N₂ selectivity of Pt catalysts in the NO-H₂-O₂ reaction at low temperatures[J]. Applied Catalysis B: Environmental, 2003, 46: 353-364.
38	ZHANG X X , WANG X P , ZHAO X J , et al . An investigation on N₂O formation route over Pt/HY in H₂-SCR[J]. Chemical Engineering Journal, 2014, 252: 288-297.
39	COSTA C N , EFSTATHIOU A M . Transient isotopic kinetic study of the NO/H₂/O₂ (lean de-NO _x ) reaction on Pt/SiO₂ and Pt/La-Ce-Mn-O catalysts[J]. The Journal of Physical Chemistry B, 2004, 108: 2620-2630.
40	GROSSALE A , NOVA I , TRONCONI E , et al . The chemistry of the NO/NO₂-NH₃ “fast” SCR reaction over Fe-ZSM-5 investigated by transient reaction analysis[J]. Journal of Catalysis, 2008, 256: 312-322.
41	ŁAMACZ A , KRZTOŃ A , DJÉGA-MARIADASSOU G . Study on the selective catalytic reduction of NO with toluene over CuO/CeZrO₂. A confirmation for the three-function model of HC-SCR using the temperature programmed methods and in situ DRIFTS[J]. Applied Catalysis B: Environmental, 2013, 142/143: 268-277.
42	于青, 孔凡晓, 李兰冬, 等 . Pd 基催化剂上H₂快速选择催化还原NO _x [J]. 催化学报, 2010, 31: 261-263.
	YU Q , KONG F X , LI L D , et al . Fast catalytic reduction of NO _x by H₂ over Pd-based catalysts[J]. Chinese Journal of Catalysis, 2010, 31: 261-263.
43	RODRÍGUEZ G C M , SARUHAN B . H₂-selective catalytic reduction of NO _x activity and microstructural analysis of new BaTi_0.95Pd_0.05O₃ catalyst[J]. Applied Catalysis A: General, 2010, 387: 173-184.
44	HODJATI S , VAEZZADEH K , PETIT C , et al . Absorption/desorption of NO _x process on perovskites: performances to remove NO _x from a lean exhaust gas[J]. Applied Catalysis B: Environmental, 2000, 26: 5-16.
45	ZHAO X J , ZHANG X X , XU Y Z , et al . The effect of H₂O on the H₂-SCR of NO _x over Pt/HZSM-5[J]. Journal of Molecular Catalysis A: Chemical, 2015, 400: 147-153.
46	ENGELMANN-PIREZ M , GRANGER P , LECLERCQ G . Investigation of the catalytic performances of supported noble metal based catalysts in the NO+H₂ reaction under lean conditions[J]. Catalysis Today, 2005, 107/108: 315-322.
47	YOSHINARI T , SATO K , HANEDA M . Positive effect of coexisting SO₂ on the activity of supported iridium catalysts for NO reduction in the presence of oxygen[J]. Applied Catalysis B: Environmental, 2003, 41: 157-169.
48	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.
	HUANG J , ZHONG Z P , ZHU L , et al . DeNO _x performance and resistance to H₂O and SO₂ of Mn-Ce doped V-W/Ti catalyst at middle-low temperature[J]. Chemical Industry and Engineering Progress, 2018, 37(6): 2242-2248.
49	景有志，杨丽，朱淑维, 等 . 锰钛系低温选择性催化还原催化剂的抗SO₂和抗H₂O性能研究进展[J]. 化工进展, 2018, 37(1): 105-111.
	JING Y Z , YANG L , ZHU S W , et al . Research progress on the SO₂ and H₂O resistance of Mn-Ti catalysts for low-temperature SCR[J]. Chemical Industry and Engineering Progress, 2018, 37(1): 105-111.
50	HONG Z , WANG Z , CHEN D , et al . Hollow ZSM-5 encapsulated Pt nanoparticles for selective catalytic reduction of NO by hydrogen[J]. Applied Surface Science, 2018, 440: 1037-1046.

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