铜基催化剂应用于含氨废气选择性催化氧化的研究进展

doi:10.16085/j.issn.1000-6613.2017.01.022

摘要/Abstract

摘要： 含氨废气的排放对人类健康和生态环境有十分严重的影响。采用选择性催化氧化（SCO）技术实现含氨废气污染控制具有良好的应用前景，铜基催化剂因其优良的催化性能而受到广泛的关注。本文总结分析了近期国内外对于铜基催化剂应用于NH₃-SCO体系的研究成果与进展，指出了不同活性组分、载体以及其他因素对催化剂性能的影响；简要阐述了NH₃-SCO的反应机理，重点讨论了以铜为主要活性位的催化剂机理研究；并对未来的研究工作进行了展望，指出采用多种手段对催化剂进行改性、进一步研究催化剂在实际体系中的应用以及采用原位等谱学手段对催化机理进行深入探讨是该领域的研究重点。

关键词: 氨, 催化剂, 氧化, 选择催化还原

Abstract: Exhaust emissions containing ammonia (NH₃) have very serious influence on human health and the environment. Ammonia selective catalytic oxidation (NH₃-SCO) has a good application prospect in pollution control of waste gas containing NH₃. Copper-based catalysts have been widely studied because of their excellent catalytic performance. This paper summarized and analyzed the recent progress of copper-based catalysts in NH₃-SCO. The effects of active component,support and other factors on the performance of the catalysts were discussed respectively. The mechanism of NH₃-SCO was briefly described,with the emphasis on the catalyst with copper as the main active site. Modifying the catalyst by different methods,studying the practical application of catalyst and using in situ spectroscopic techniques to further probe the mechanism will be the hotspots in the field.

Key words: ammonia, catalyst, oxidation, selective catalytic oxidation(SCR)

中图分类号:

李婧颖, 唐晓龙, 易红宏, 张润草, 李晨露, 储超. 铜基催化剂应用于含氨废气选择性催化氧化的研究进展[J]. 化工进展, 2017, 36(01): 174-180.

LI Jingying, TANG Xiaolong, YI Honghong, ZHANG Runcao, LI Chenlu, CHU Chao. Review of Cu-based catalysts in selective catalytic oxidation of ammonia[J]. Chemical Industry and Engineering Progree, 2017, 36(01): 174-180.

参考文献

[1] 胡景丽,唐晓龙,易红宏,等.含NH₃废气选择性催化氧化法研究进展[J].化学世界,2014,55(5):297-300. HU J L,TANG X L,YI H H,et al.Recent progress in selective catalytic oxidation of ammonia[J].Chemical World,2014,55(5):297-300.
[2] CHMIELARZ L,JABŁOŃSKA M.Advances in selective catalytic oxidation of ammonia to dinitrogen:a review[J].RSC Advances,2015,5(54):43408-43431.
[3] SHRESTHA S,HAROLD M P,KAMASAMUDRAM K,et al.Selective oxidation of ammonia on mixed and dual-layer Fe-ZSM-5+ Pt/Al₂O₃ monolithic catalysts[J].Catalysis Today,2014,231:105-115.
[4] ZHANG L,HE H.Mechanism of selective catalytic oxidation of ammonia to nitrogen over Ag/Al₂O₃[J].Journal of Catalysis,2009,268(1):18-25.
[5] JABŁOŃSKA M,KRÓL A,KUKULSKA-ZAJAC E,et al.Zeolite Y modified with palladium as effective catalyst for selective catalytic oxidation of ammonia to nitrogen[J].Journal of Catalysis,2014,316:36-46.
[6] LI Y J,ARMOR J N.Selective NH₃ oxidation to N₂ in a wet stream[J].Applied Catalysis B:Environmental,1997,13(2):131-139.
[7] LIANG C X,LI X Y,QU Z P,et al.The role of copper species on Cu/γ-Al₂O₃ catalysts for NH₃-SCO reaction[J].Applied Surface Science,2012,258(8):3738-3743.
[8] HE S L,ZHANG C B,YANG M,et al.Selective catalytic oxidation of ammonia from MAP decomposition[J].Separation & Purification Technology,2007,58(1):173-178.
[9] LONG R Q,YANG R T.Superior ion-exchanged ZSM-5 catalysts for selective catalytic oxidation of ammonia to nitrogen[J].Chemical Communications,2000,17(17):1651-1652.
[10] LONG R Q,YANG R T.Selective catalytic oxidation of ammonia to nitrogen over Fe₂O₃-TiO₂ prepared with a sol-gel method[J].Journal of Catalysis,2002,207(2):158-165.
[11] AKAH A,CUNDY C,GARFORTH A.The selective catalytic oxidation of NH₃ over Fe-ZSM-5[J].Applied Catalysis B:Environmental,2005,59(3):221-226.
[12] CHMIELARZ L,JABŁOŃSKA M,STRUMIŃSKI A,et al.Selective catalytic oxidation of ammonia to nitrogen over Mg-Al,Cu-Mg-Al and Fe-Mg-Al mixed metal oxides doped with noble metals[J].Applied Catalysis B:Environmental,2013,130:152-162.
[13] CHMIELARZ L,KUŚTROWSKI P,RAFALSKA-ŁASOCHA A,et al.Selective oxidation of ammonia to nitrogen on transition metal containing mixed metal oxides[J].Applied Catalysis B:Environmental,2005,58(3):235-244.
[14] LEE S M,HONG S C.Promotional effect of vanadium on the selective catalytic oxidation of NH₃ to N₂ over Ce/V/TiO₂ catalyst[J].Applied Catalysis B:Environmental,2015,163:30-39.
[15] HU J L,TANG X L.Low-temperature selective catalytic oxidation of ammonia over the CuO_x/C-TiO₂ catalyst[J].Research on Chemical Intermediates,2014,41:1-10.
[16] SONG S Q,JIANG S J.Selective catalytic oxidation of ammonia to nitrogen over CuO/CNTs:the promoting effect of the defects of CNTs on the catalytic activity and selectivity[J].Applied Catalysis B:Environmental,2012,117(1):346-350.
[17] LENIHAN S,CURTIN T.The selective oxidation of ammonia using copper-based catalysts:the effects of water[J].Catalysis Today,2009,145(1):85-89.
[18] CHMIELARZ L,KUŚTROWSKI P,DROZDEK M,et al.Selective catalytic oxidation of ammonia into nitrogen over PCH modified with copper and iron species[J].Catalysis Today,2006,114(2):319-325.
[19] CHMIELARZ L,KUŚTROWSKI P,PIWOWARSKA Z,et al.Natural micas intercalated with Al₂O₃ and modified with transition metals as catalysts of the selective oxidation of ammonia to nitrogen[J].Topics in Catalysis,2009,52(8):1017-1022.
[20] YUE W R,ZHANG R D,LIU N,et al.Selective catalytic oxidation of ammonia to nitrogen over orderly mesoporous CuFe₂O₄ with high specific surface area[J].Chinese Science Bulletin,2014,59(31):3980-3986.
[21] KADDOURI A,DUPONT N,GELIN P,et al.Selective oxidation of gas phase ammonia over copper chromites catalysts prepared by the sol-gel process[J].Catalysis Communications,2011,15(1):32-36.
[22] CHMIELARZ L,WĘGRZYN A,WOJCIECHOWSKA M,et al.Selective catalytic oxidation(SCO) of ammonia to nitrogen over hydrotalcite originated Mg-Cu-Fe mixed metal oxides[J].Catalysis Letters,2011,141(9):1345-1354.
[23] JABŁOŃSKA M,CHMIELARZ L,WĘGRZYN A,et al.Thermal transformations of Cu-Mg (Zn)-Al (Fe) hydrotalcite-like materials into metal oxide systems and their catalytic activity in selective oxidation of ammonia to dinitrogen[J].Journal of Thermal Analysis and Calorimetry,2013,114(2):731-747.
[24] CUI X Z,ZHOU J,YE Z Q,et al.Selective catalytic oxidation of ammonia to nitrogen over mesoporous CuO/RuO₂ synthesized by co-nanocasting-replication method[J].Journal of Catalysis,2010,270(2):310-317.
[25] CUI X Z,CHEN L,WANG Y X,et al. Fabrication of hierarchically porous RuO₂-CuO/Al-ZrO₂ compositeas highly efficient catalyst for ammonia-selective catalytic oxidation[J].ACS Catalysis,2014,4:2195-2206.
[26] HUNG C M.Synthesis,characterization and performance of CuO/La₂O₃ composite catalyst for ammonia catalytic oxidation[J].Powder Technology,2009,196(1):56-61.
[27] WANG Z,QU Z P,QUAN X,et al.Selective catalytic oxidation of ammonia to nitrogen over CuO-CeO₂ mixed oxides prepared by surfactant-templated method[J].Applied Catalysis B:Environmental,2013,134:153-166.
[28] QU Z P,WANG Z,ZHANG X Y,et al.Role of different coordinated Cu and reactive oxygen species on the highly active Cu-Ce-Zr mixed oxides in NH₃-SCO:a combined in situ EPR and O₂-TPD approach[J].Catalysis Science & Technology,2016,6(12):4491-4502.
[29] JABŁOŃSKA M.TPR study and catalytic performance of noble metals modified Al₂O₃,TiO₂ and ZrO₂ for low-temperature NH₃-SCO[J].Catalysis Communications,2015,70:66-71.
[30] CHMIELARZ L,JABŁOŃSKA M,STRUMIŃSKI A,et al.Selective catalytic oxidation of ammonia to nitrogen over Mg-Al,Cu-Mg-Al and Fe-Mg-Al mixed metal oxides doped with noble metals[J]. Applied Catalysis B:Environmental,2013,130:152-162.
[31] GANG L,VAN GRONDELLE J,ANDERSON B G,et al.Selective low temperature NH₃ oxidation to N₂ on copper-based catalysts[J].Journal of Catalysis,1999,186(1):100-109.
[32] GANG L,ANDERSON B G,VAN GRONDELLE J,et al.NH₃ oxidation to nitrogen and water at low temperatures using supported transition metal catalysts[J].Catalysis Today,2000,61(1):179-185.
[33] 杨浩,郑华艳,常瑜,等.以共沉淀法为基础的铜基催化剂制备新技术的研究进展[J].化工进展,2014,33(2):379-386. YANG H,ZHENG H Y,CHANG Y,et al.Research progress of preparation of copper-based catalyst by coprecipitation[J].Chemical Industry and Engineering Progress,2014,33(2):379-386.
[34] LIPPITS M J,GLUHOI A C,NIEUWENHUYS B E.A comparative study of the selective oxidation of NH₃ to N₂ over gold,silver and copper catalysts and the effect of addition of Li2O and CeOx[J].Catalysis Today,2008,137(2):446-452.
[35] HUNG C M.The effect of the calcination temperature on the activity of Cu-La-Ce composite metal catalysts for the catalytic wet oxidation of ammonia solution[J].Powder Technology,2009,191(1):21-26.
[36] SJÖVALL H,OLSSON L,FRIDELL E,et al.Selective catalytic reduction of NO_x with NH₃ over Cu-ZSM-5--the effect of changing the gas composition[J].Applied Catalysis B:Environmental,2006,64(3):180-188.
[37] CURTIN T,LENIHAN S.Copper exchanged beta zeolites for the catalytic oxidation of ammonia[J].Chemical Communications,2003,11:1280-1281.
[38] ROYER S,VAN NESTE A,DAVIDSON R,et al.Methane oxidation over nanocrystalline LaCo_1-xFe_xO₃:resistance to SO₂ poisoning[J].Industrial & Engineering Chemistry Research,2004,43(18):5670-5680.
[39] CHEN W M,MA Y P,QU Z,et al.Mechanism of the selective catalytic oxidation of slip ammonia over Ru-modified Ce-Zr complexes determined by in situ diffuse reflectance infrared fourier transform spectroscopy[J].Environmental Science & Technology,2014,48(20):12199-12205.
[40] OLOFSSON G,WALLENBERG L R,ANDERSSON A.Selective catalytic oxidation of ammonia to nitrogen at low temperature on Pt/CuO/Al₂O₃[J].Journal of Catalysis,2005,230(1):1-13.
[41] ZAWADZKI J.The mechanism of ammonia oxidation and certain analogous reactions[J].Discussions of the Faraday Society,1950,8:140-152.
[42] OFFERMANS W K,JANSEN A P J,VAN SANTEN R A.Ammonia activation on platinum {111}:a density functional theory study[J].Surface Science,2006,600(9):1714-1734.
[43] POPA C,VAN SANTEN R A,JANSEN A P J.Density-functional theory study of NHx oxidation and reverse reactions on the Rh (111) surface[J].The Journal of Physical Chemistry C,2007,111(27):9839-9852.
[44] AMORES J M G,ESCRIBANO V S,RAMIS G,et al.An FT-IR study of ammonia adsorption and oxidation over anatase-supported metal oxides[J].Applied Catalysis B:Environmental,1997,13(1):45-58.
[45] DARVELL L I,HEISKANEN K,JONES J M,et al.An investigation of alumina-supported catalysts for the selective catalytic oxidation of ammonia in biomass gasification[J].Catalysis Today,2003,81(4):681-692.
[46] QU Z P,WANG H,WANG S D,et al.Role of the support on the behavior of Ag-based catalysts for NH₃ selective catalytic oxidation (NH₃-SCO)[J].Applied Surface Science,2014,316:373-379.
[47] GÓRA-MAREK K,TARACH K A,PIWOWARSKA Z,et al.Ag-loaded zeolites Y and USY as catalysts for selective ammonia oxidation[J].Catalysis Science & Technology,2016,6(6):1651-1660.
[48] CHEN W M,QU Z,HUANG W J,et al.Novel effect of SO₂ on selective catalytic oxidation of slip ammonia from coal-fired flue gas over IrO₂ modified Ce-Zr solid solution and the mechanism investigation[J].Fuel,2016,166:179-187.
[49] QI G S,GATT J E,YANG R T.Selective catalytic oxidation(SCO) of ammonia to nitrogen over Fe-exchanged zeolites prepared by sublimation of FeCl₃[J].Journal of Catalysis,2004,226(1):120-128.
[50] LEE S M,LEE H H,HONG S C.Influence of calcination temperature on Ce/TiO₂ catalysis of selective catalytic oxidation of NH₃ to N₂[J].Applied Catalysis A:General,2014,470:189-198.
[51] OLOFSSON G,HINZ A,ANDERSSON A.A transient response study of the selective catalytic oxidation of ammonia to nitrogen on Pt/CuO/Al₂O₃[J].Chemical Engineering Science,2004,59(19):4113-4123.
[52] CURTIN T,O'REGAN F,DECONINCK C,et al.The catalytic oxidation of ammonia:influence of water and sulfur on selectivity to nitrogen over promoted copper oxide/alumina catalysts[J].Catalysis Today,2000,55(1):189-195.