铜掺杂对Fe/β催化剂NH<sub>3</sub>-SCR催化性能的影响

doi:10.3785/j.issn.1008-9497.2017.04.015

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摘要制备了一系列Cu掺杂量不同的Fe/β（40）催化剂，并采用ICP-AES、XRD、H₂-TPR、UV-vis和XPS等表征技术分析了催化剂的物化性质.结果表明，适量的铜掺杂能大大提高Fe/β（40）催化剂的低温活性，拓宽其活性温度窗口，但过量的Cu掺杂会降低催化剂的N₂选择性.Cu掺杂质量比为1.27% Cu-2% Fe/β（40）的催化剂具有最佳的SCR性能，这与催化剂中存在较多离子交换位的Fe³⁺和Cu²⁺物种有关，而存在较多的CuO物种会促进氨高温氧化，使催化剂的N₂选择性降低且高温窗口变窄.高温水热条件下Cu的存在可能使Cu、Fe物种更容易发生迁移和团聚，导致Cu-Fe/β（40）催化剂的水热稳定性明显变差.

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关键词 ： NH₃-SCR, Cu-Fe/β(40), 铜掺杂, 水热老化

Abstract：The Cu doped Fe/β (40) catalysts were prepared by ion-exchanged/wetness-impregnation methods and characterized using various analytical techniques, including H₂-TPR, XRD, UV-vis and XPS. Appropriate amount of copper enormously improved the low temperature activity of Fe/β (40) and broadened the temperature window of activity. Excessive amount of copper decreased the N₂ selectivity of catalysts. 1.27%Cu-2%Fe/β catalyst obtained the best performance attributed to many ion-exchanged positions of Fe³⁺ and Cu²⁺. However, a large amount of CuO can promote NH₃ oxidation at high temperature, and decrease N₂ selectivity and narrow down the temperature window of activity. Cu doping may make the migration and agglomeration of Cu and Fe species more easily under high-temperature hydrothermal conditions, which leads to hydrothermal stability of Cu-Fe/β (40) catalyst change.

Key words： NH₃-SCR Cu-Fe/β(40) Cu doping hydrothermal aging

收稿日期: 2016-07-08

ZTFLH:

O643

基金资助:浙江省重点科技创新团队计划资助项目.

通讯作者: 周仁贤,ORCID:http://orcid.org/0000-0002-5627-070X,E-mail:zhourenxian@zju.edu.cn. E-mail: zhourenxian@zju.edu.cn

作者简介: 赵茹(1990-),ORCID:http://orcid.org/0000-0001-6295-3008,女,硕士研究生,主要从事柴油车尾气脱硝研究,E-mail:21437079@zju.edu.cn.

引用本文:

赵茹, 姜水燕, 周仁贤. 铜掺杂对Fe/β催化剂NH₃-SCR催化性能的影响[J]. 浙江大学学报（理学版）, 2017, 44(4): 485-492.
ZHAO Ru, JIANG Shuiyan, ZHOU Renxian. The effect of Cu doping on catalytic performance of Fe/β catalyst for NH₃-SCR. Journal of ZheJIang University(Science Edition), 2017, 44(4): 485-492.

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http://www.zjujournals.com/sci/CN/10.3785/j.issn.1008-9497.2017.04.015 或 http://www.zjujournals.com/sci/CN/Y2017/V44/I4/485

[1] BAIKER A, DOLLENMEIER P, GLINSKI M, et al. Selective catalytic reduction of nitric oxide with ammonia:I. monolayer and multilayers of vanadia supported on titania[J]. Applied Catalysis,1987,35(2):351-364.
[2] BOSCH H, JANSSEN F. Formation and control of nitrogen oxides[J]. Catalysis Today,1988(2):369-379.
[3] BUSCA G, LIETTI L, RAMIS G, et al. Chemical and mechanistic aspects of the selective catalytic reduction of NO_x by ammonia over oxide catalysts:A review[J]. Applied Catalysis B:Environmental,1998,18:1-36.
[4] MUTIN P H, POPA A F, VIOUX A, et al. Nonhydrolyticvanadia-titaniaxerogels:Synthesis, cha-racterization, and behavior in the selective catalytic reduction of NO by NH₃[J]. Applied Catalysis B:Environmental,2006,69:49-57.
[5] KANG M, YEON T H, PARK E D, et al. Novel MnO_x catalysts for NO reduction at low temperature with ammonia[J]. Catalysis Letters,2006,106:77-80.
[6] BALLE P, GEIGER B, KURETI S. Selective catalytic reduction of NO_x by NH₃ on Fe/HBEA zeolite catalysts in oxygen-rich exhaust[J]. Applied Catalysis B:Environmental,2009,85:109-119.
[7] DJERAD S, CROCOLL M, KURETI S, et al. Effect of oxygen concentration on the NO_x reduction with ammonia over V₂ O₅-WO₃/TiO₂ catalyst[J]. Catalysis Today,2006,113:208-214.
[8] DUNN J P, KOPPULA P R, STENGER H G, et al. Oxidation of sulfur dioxide to sulfur trioxide over supported vanadia catalysts[J]. Applied Catalysis B:Environmental,1998,19:103-117.
[9] FENG X, HALL W K. FeZSM-5:A durable SCR catalyst for NO_x removal from combustion streams[J]. Journal of Catalysis,1997,166:368-376.
[10] LONG R Q, YANG R T. Superior Fe-ZSM-5 catalyst for selective catalytic reduction of nitric oxide by ammonia[J]. Journal of the American Chemical Society,1999,121:5595-5596.
[11] LONG R Q, YANG R T. Catalytic Performance of Fe-ZSM-5 catalysts for selective catalytic reduction of nitric oxide by ammonia[J]. Journal of Catalysis,1999,188:332-339.
[12] SUBBIAH A, CHO B K, BLINT R J, et al. NO_x reduction over metal-ion exchanged novel zeolite under lean conditions:Activity and hydrothermal stability[J]. Applied Catalysis B:Environmental,2003,42:155-178.
[13] SJÖVALL H, OLSSON L, FRIDELLE, 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,2006,64:180-188.
[14] QI G S, YANG R T. Ultra-active Fe/ZSM-5 catalyst for selective catalytic reduction of nitric oxide with ammonia[J]. Applied Catalysis B:Environmental,2005,60:13-22.
[15] JIANG S Y, ZHOU R X. Ce doping effect on performance of the Fe/β catalyst for NO_x reduction by NH₃[J]. Fuel Process Technol,2015,133:220-226.
[16] TWIGG M V. Catalytic control of emissions from cars[J]. Catalysis Today,2011,163:33-41.
[17] PLÁT F, BÁRTOVÁ S, ŠTěPÁNEK J, et al. Dynamics of a combined DOC-NSRC-SCR exhaust gas after treatment system with periodic regenerations[J]. Industrial & Engineering Chemistry Research,2010,49:10348-10357.
[18] PEREDA-AYO B, DE LA TORRE U, ILLÁN-GÓMEZ M J, et al. Role of the different copper species on the activity of Cu/zeolite catalysts for SCR of NO_x with NH₃[J]. Applied Catalysis B:Environmental,2014,147:420-428.
[19] ZHANG T, LIU J, WANG D, et al. Selective catalytic reduction of NO with NH₃ over HZSM-5-supported Fe-Cu nanocomposite catalysts:The Fe-Cu bimetallic effect[J]. Applied Catalysis B:Environmental,2014,148/149:520-531.
[20] FRANCO R M, MOLINER M, CONCEPCION P, et al. Selective catalytic reduction of NO with NH₃ over HZSM-5-supported Fe-Cu nanocomposite catalysts:The Fe-Cu bimetallic effect[J]. Journal of Catalysis,2014,314:73-82.
[21] SULTANA A, SASAKI M, SUZUKI K, et al. Tuning the NO_x conversion of Cu-Fe/ZSM-5 catalyst in NH₃-SCR[J]. Catalysis Communications,2013,41:21-25.
[22] MAUVEZIN M, DELAHAY G, COQ B, et al. Identification of iron species in Fe-BEA:Influence of the exchange level[J]. The Journal of Physical Chemistry B,2001,105(5):928-935.
[23] XUE J, WANG X, QI G, et al. Characterization of copper species over Cu/SAPO-34 in selective catalytic reduction of NO_x with ammonia:Relationships between active Cu sites and de-NO_x performance at low temperature[J]. Journal of Catalysis,2013,297:56-64.
[24] DE LA TORRE U, PERE-AYO B,GONZÁLEZ-VELASCO J R. Cu-zeolite NH₃-SCR catalysts for NO_x removal in the combined NSR-SCR technology[J]. Chemical Engineering Journal,2012,207/208:10-17.
[25] SHEN K, ZHANG Y, WANG X, et al. Influence of chromium modification on the properties of MnO_x-FeO_x catalysts for the low-temperature selective catalytic reduction of NO by NH₃[J]. Journal of Energy Chemistry,2013,22:617-623.
[26] CHEN B, LIU N, LIU X, et al. Study on the direct decomposition of nitrous oxide over Fe-beta zeolites:From experiment to theory[J]. Catalysis Today,2011,175:245-255.
[27] WEI G L, YU Z, FANG N G, et al. Catalytic degradation of tobacco-specific nitrosamines by ferric zeolite[J]. Applied Catalysis B:Environmental,2013,129:301-308.
[28] PARK J Y, LEE Y J, KHANNA P, et al. Alumina-supported iron oxide nanoparticles as Fischer-Tropsch catalysts:Effect of particle size of iron oxide[J]. Journal of Molecular Catalysis A:Chemical,2010,323:84-90.
[29] TIPPINS H H. Charge-transfer spectra of transition-metal ions in corundum[J]. Physical Review B,1970,1(1):126-135.
[30] LU L, LI L, WANG X, et al. Understanding of the finite size effects on lattice vibrations and electronic transitions of nano α-Fe₂O₃[J]. The Journal of Physical Chemistry B,2005,109:17151-17156.
[31] JANAS J, GURGUL J, SOCHA R P, et al. Effect of Cu content on the catalytic activity of CuSiBEA zeolite in the SCR of NO by ethanol:Nature of the copper species[J]. Applied Catalysis B:Environmental,2009,91(1/2):217-224.
[32] ISMAGILOV Z R, YASHNIK S A, ANUFRIENKO V F, et al. Linear nanoscale clusters of CuO in Cu-ZSM-5 catalysts[J]. Applied Surface Science,2004,226(1/2/3):88-93.
[33] WANG L, GAUDET J R, LI W, et al. Migration of Cu species in Cu/SAPO-34 during hydrothermal aging[J]. Journal of Catalysis,2013,306:68-77.
[34] PESTRYAKOV A N, PETRANOVSKⅡ V P, KRYAZHOV A, et al. Study of copper nanoparticles formation on supports of different nature by UV-Vis diffuse reflectance spectroscopy[J]. Chemical Physics Letters,2004,385:173-176.
[35] YASHNIK S A, ISMAGILOV Z R, ANUFRIENKO V F. Catalytic properties and electronic structure of copper ions in Cu-ZSM-5[J]. Catalysis Today,2005,110(3/4):310-322.
[36] CAMPOS-MARTIN J M, GUERRERO-RUIZ A, FIERRO J L. Changes of copper location in CuY zeolites induced by preparation methods[J]. Catalysis Letters,1996,41:55-61.
[37] WAHLQVIST M, SHCHUKAREW A. XPS spectra and electronic structure of group IA sulfates[J]. Journal of Electron Spectroscopy and Related Phenomena,2007,156/157/158:310-314.
[38] ARAKAWA K, MATSUDA S, KINOSHITA H. SO_x poisoning mechanism of NO_x selective reduction catalysts[J]. Applied Surface Science,1997,121/122:382-386.
[39] MORENO-TOST R, SANTAMARÍA-GONZÁLEZ J, RODRÍGUEZ-CASTELLÓN E, et al. Selective catalytic reduction of nitric oxide by ammonia over Cu-exchanged Cuban natural zeolites[J]. Applied Catalysis B:Environmental,2004,50(4):279-288.
[40] ZHANG L, WANG D, LIU Y, et al. SO₂ poisoning impact on the NH₃-SCR reaction over a commercial Cu-SAPO-34 SCR catalyst[J]. Applied Catalysis B:Environmental,2014,37:156-157.