Fe-Cu/ZSM-5催化剂的NH<sub>3</sub>-SCR脱硝性能

胡海鹏; 王学涛; 张兴宇; 苏晓昕; 杨晓东; 史瑞华

Fe-Cu/ZSM-5催化剂的NH₃-SCR脱硝性能

1.
河南科技大学能源与动力工程系, 河南洛阳 471003
2.
山东大学燃煤污染物减排国家工程实验室, 山东济南 250061

基金项目:

国家自然科学基金 50806020

河南省科技创新人才计划(杰出青年) 114100510010

河南省科技攻关项目 152102210280

详细信息

中图分类号: TK229.6;X701
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- 文章访问数: 323
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- 被引次数: 0
出版历程
- 收稿日期: 2017-11-19
- 修回日期: 2018-01-03
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-02-10

Performance of Fe-Cu/ZSM-5 catalyst in the DeNO_x process via NH₃-SCR

1.
Henan University of Science and Technology, Luoyang 471003, China
2.
Shandong University, National Engineering Lab of Coal-fired Pollution Emission Reduction, Jinan 250061, China

Funds:

the National Natural Science Foundation of China 50806020

Henan Science and Technology Innovation Talent Program (Outstanding Youth) 114100510010

Science and Technology Project of Science and Technology Department of Henan Province 152102210280

More Information

Corresponding author: WANG Xue-tao, E-mail:wxt7682@163.com

摘要

摘要: 通过浸渍法制备了Fe和Cu含量比不同的系列Fe-Cu/ZSM-5催化剂, 利用XRD、H₂-TPR、NH₃-TPD和原位DRIFTS等技术对催化剂进行了表征, 并对其NH₃-SCR脱硝性能进行了研究。结果表明, 双金属改性的Fe-Cu/ZSM-5催化剂活性温度窗口拓宽, 其中, Fe-Cu/ZSM-5 1:4催化剂脱硝性能优异, 250-450 ℃下脱硝效率均超过90%, 335 ℃时脱硝效率达到最大值96.46%。铜和铁物种能以无定型氧化物良好分散于载体表面, 双金属负载改性催化剂保留了ZSM-5的晶体结构。Fe-Cu/ZSM-5 1:4催化剂具备丰富的酸性位、良好的氧化还原性能, 一定温度条件下NH₃-SCR反应过程中同时存在E-R机理和L-H机理, 且E-R机理反应起始温度低于L-H机理; 200 ℃为催化脱硝反应的起活温度。
- Fe-Cu/ZSM-5 /
- NH₃-SCR /
- 脱硝 /
- 反应机理 /
- in situ DRIFTS
Abstract: A series of Fe-Cu/ZSM-5 catalysts with different Fe/Cu molar ratios were prepared by impregnation method and characterized by XRD, H₂-TPR, NH₃-TPD and in situ DRIFTS; their performance in the denitrification (de-NO_x) process via NH₃-SCR was investigated.The results showed that the bimetallic modified Fe-Cu/ZSM-5 catalysts have a broad active temperature window.Especially, the Fe-Cu/ZSM-5 1:4 catalyst with a Fe/Cu molar ratio of 1:4 displays the highest activity; over it, the deNO_x efficiency reaches the maximum of 99.46% at 335℃ and keeps above 90% at 250-450℃.Copper and iron species, present as amorphous oxides, are finely dispersed on the catalyst surface and the bimetallic modified catalysts retain the crystal structure of ZSM-5.The Fe-Cu/ZSM-5 1:4 catalyst exhibits abundant acid sites and excellent redox performance.E-R mechanism and L-H mechanism may coexist during the NH₃-SCR reaction under certain temperature; moreover, the onset temperature of E-R mechanism is much lower than that of L-H mechanism and the denitration reaction may be ignited at 200℃.
- Fe-Cu/ZSM-5 /
- NH₃-SCR /
- DeNO_x /
- reaction mechanism /
- in situ DRIFTS

HTML全文

图 1 SCR脱硝催化剂评价装置

Figure 1 Catalytic evaluation device for SCR deNO_x

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图 2 不同Fe/Cu物质的量比催化剂的NO_x转换效率

Figure 2 NO_x conversion over the Fe-Cu/ZSM-5 catalysts with different Fe/Cu molar ratio

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图 3 不同催化剂的XRD谱图

Figure 3 XRD patterns of different catalysts

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图 4 不同催化剂的NH₃-TPD谱图

Figure 4 NH₃-TPD profiles of different catalysts

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图 5 不同催化剂的H₂-TPR谱图

Figure 5 H₂-TPR profiles of different catalysts

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图 6 Fe-Cu/ZSM-5 1 :4催化剂表面NH₃吸附in situ DRIFTS谱图

Figure 6 In situ DRIFTS spectra of NH₃ adsorbed on the Fe-Cu/ZSM-5 1 :4 catalyst

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图 7 NH₃饱和吸附后不同温度下通NO+O₂反应的in situ DRIFTS谱图

Figure 7 In situ DRIFTS spectra of NO+O₂ reacting with pre-adsorbed NH₃ at different temperatures

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图 8 Fe-Cu/ZSM-5 1 :4催化剂表面NO+O₂吸附in situ DRIFTS谱图

Figure 8 In situ DRIFTS spectra of NO+O₂ adsorbed over the Fe-Cu/ZSM-5 1 :4 catalyst

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图 9 Fe-Cu/ZSM-5 1 :4催化剂饱和吸附NO+O₂后通入NH₃ in situ DRIFTS谱图

Figure 9 In situ DRIFTS spectra of NH₃ reacting with pre-adsorbed NO+O₂ over the Fe-Cu/ZSM-5 1 :4 catalyst at different temperatures

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图 10 NO+O₂+NH₃同时通入反应的in situ DRIFTS谱图

Figure 10 In situ DRIFTS spectra of simultaneous reactions among NO+O₂+NH₃

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参考文献(36)

[1]	马腾坤, 房晶瑞, 孙勇, 汪澜.TiO₂载体掺杂对Mn-Ce/TiO₂催化剂低温脱硝性能影响研究[J].燃料化学学报, 2017, 45(4):491-496. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract19017.shtml MA Teng-kun, FANG Jing-rui, SUN Yong, WANG Lan.Study on the modification effect of TiO₂ support on the low temperature denitration activity of Mn-Ce/TiO₂ catalysts[J].J Fuel Chem Technol, 2017, 45(4):491-496. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract19017.shtml
[2]	张相俊, 刘晓刚, 李清雍, 李岩, 魏波, 王虹, 李翠清, 宋永吉.载体对铜基催化剂NH₃-SCR低温脱硝性能的影响[J].燃料化学学报, 2017, 45(2):220-226. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18982.shtml ZHANG Xiang-jun, LIU Xiao-gang, LI Qing-yong, LI Yan, WEI Bo, WANG Hong, LI Cui-qing, SONG Yong-ji.Effect of carrier on the performance of copper based catalyst for selective catalytic reduction of NO with NH₃ at low temperature[J].J Fuel Chem Technol, 2017, 45(2):220-226. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18982.shtml
[3]	ZHANG K K, ZHAO J, ZHU Y C, XU Z H. Model predictive control case study: Selective catalytic reduction (SCR) system in coal-fired power plant[C]. Control Conference, IEEE, 2016: 4300-4305.
[4]	周子健, 刘小伟, 葛振武, 夏永俊, 廖志强, 江盟, 邵海忠.基于失活商业脱硝催化剂制备的再生SCR催化剂性能研究[J].中国电机工程学报, 2017, 37(9):2614-2622. ZHOU Zi-jian, LIU Xiao-wei, GE Zhen-wu, XIA Yong-jun, LIAO Zhi-qiang, JIANG Meng, SHAO Hai-zhong.NO reduction over a novel SCR catalyst regenerated from deactivated commercial DeNO_x catalyst[J].Proc CSEE, 2017, 37(9):2614-2622.
[5]	乔南利, 杨忆新, 宋焕巧, 郭林, 罗明生.低温NH₃-SCR脱硝催化剂的研究现状与进展[J].化工环保, 2017, 37(3):282-288. http://www.hgjz.com.cn/CN/abstract/abstract17900.shtml QIAO Nan-li, YANG Yi-xin, SONG Huan-qiao, GUO Lin, LUO Ming-sheng.Research status and progresses on NH₃-SCR catalysts for low-temperature denitration[J].Environ Prot Chem Ind, 2017, 37(3):282-288. http://www.hgjz.com.cn/CN/abstract/abstract17900.shtml
[6]	梁辉, 查贤斌, 归柯庭.γFe₂O₃的选择性催化还原脱硝性能及其对NH₃和NO的表面吸附行为研究[J].中国电机工程学报, 2014, 34(32):5734-5740. LIANG Hui, ZHA Xian-bin, GUI Ke-ting.A study of selective catalysis reduction denitration performance and adsorption of NH₃ and NO Over Fe₂O₃ catalyst[J].Proc CSEE, 2014, 34(32):5734-5740.
[7]	朱彦涛, 吕刚, 宋崇林, 李博, 陈科.一价铜改性ZSM-5催化剂及其催化碳烟氧化反应性能研究[J].燃料化学学报, 2017, 45(1):106-112. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18968.shtml ZHU Yan-tao, Lü Gang, SONG Chong-lin, LI Bo, CHEN Ke.Catalytic oxidation of soot over monovalent copper modified ZSM-5[J].J Fuel Chem Technol, 2017, 45(1):106-112. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18968.shtml
[8]	LAI S S, SHE Y, ZHAN W C, GUO Y, GUO Y L, WANG L, LU G Z.Performance of Fe-ZSM-5 for selective catalytic reduction of NO_x with NH₃:Effect of the atmosphere during the preparation of catalysts[J].J Mol Catal A:Chem, 2016, 424:232-240. doi: 10.1016/j.molcata.2016.08.026
[9]	RUTKOWSKA M, PACIA I, BASAG S, KOWALCZYK A, PIWOWARSKA Z, DUDA M, TARACH K A, GORAMAREK K, MICHALIK M, DIAZ U.Catalytic performance of commercial Cu-ZSM-5 zeolite modified by desilication in NH₃-SCR and NH₃-SCO processes[J].Microporous Mesoporous Mater, 2017, 246(Supplement C):193-206. https://www.sciencedirect.com/science/article/pii/S1387181117301865
[10]	吕刚, 范啸天, 宋崇林, 李博, 宋金瓯.Cu/ZSM-5催化剂制备及SCR催化性能研究[J].工程热物理学报, 2015, 36(10):2276-2281. http://jetp.iet.cn/CN/abstract/abstract8950.shtml LV Gang, FAN Xiao-tian, SONG Chong-lin, LI Bo, SONG Jin-ou.SCR Catalytic performance of Cu/ZSM-5 catalyst prepared by solid state ion exchange[J].J Eng Thermophysics, 2015, 36(10):2276-2281. http://jetp.iet.cn/CN/abstract/abstract8950.shtml
[11]	KRISHNA K, MAKKEE M.Preparation of Fe-ZSM-5 with enhanced activity and stability for SCR of NO_x[J].Catal Today, 2006, 114(1):23-30. doi: 10.1016/j.cattod.2006.02.002
[12]	DU T Y, QU H X, LIU Q, ZHONG Q, MA W H.Synthesis, activity and hydrophobicity of Fe-ZSM-5@silicalite-1 for NH₃-SCR[J].Chem Eng J, 2015, 262:1199-1207. doi: 10.1016/j.cej.2014.09.119
[13]	SULTANA A, SASAKI M, SUZUKI K, HAMADA H.Tuning the NO_x conversion of Cu-Fe/ZSM-5 catalyst in NH₃-SCR[J].Catal Commun, 2013, 41:21-25. doi: 10.1016/j.catcom.2013.06.028
[14]	LIU F, HE H.Structure-activity relationship of iron titanate catalysts in the selective catalytic reduction of NO_x with NH₃[J].J Phys Chem C, 2010, 114(40):16929-1636. doi: 10.1021/jp912163k
[15]	GÍRA-MAREK K, BRYLEWSKA K, TARACH K A, RUTKOWSKA M, JABLONSKA M, CHOI M, CHMIELARZ L.IR studies of Fe modified ZSM-5 zeolites of diverse mesopore topologies in the terms of their catalytic performance in NH₃-SCR and NH₃-SCO processes[J].Appl Catal B:Environ, 2015, 179:589-598. doi: 10.1016/j.apcatb.2015.05.053
[16]	ZHANG T, LIU J, WANG D X, ZHAO Z, WEI Y C, CHENG K, JIANG G Y, DUAN A J.Selective catalytic reduction of NO with NH₃ over HZSM-5-supported Fe-Cu nanocomposite catalysts:The Fe-Cu bimetallic effect[J].Appl Catal B:Environ, 2014, 148/149:520-531. doi: 10.1016/j.apcatb.2013.11.006
[17]	QI G, YANG R T.Selective catalytic oxidation (SCO) of ammonia to nitrogen over Fe/ZSM-5 catalysts[J].Appl Catal A:Gen, 2005, 287(1):25-33. doi: 10.1016/j.apcata.2005.03.006
[18]	LONG R Q, YANG R T.Temperature-programmed desorption/surface reaction (TPD/TPSR) study of Fe-exchanged ZSM-5 for selective catalytic reduction of nitric oxide by ammonia[J].J Catal, 2001, 198(1):20-28. doi: 10.1006/jcat.2000.3118
[19]	MU W T, ZHU J, ZHANG S, GUO Y Y, SU L Q, LI X Y, LI Z.Novel proposition on mechanism aspects over Fe-Mn/ZSM-5 catalyst for NH₃-SCR of NO_x at low temperature:Rate and direction of multifunctional electron-transfer-bridge and in situ DRIFTS analysis[J].Catal Sci Technol, 2016, 6(20):7532-7548. doi: 10.1039/C6CY01510G
[20]	XIA Y, ZHAN W C, GUO Y, GUO LY, LU G Z.Fe-Beta zeolite for selective catalytic reduction of NO_x with NH₃:Influence of Fe content[J].Chin J Catal, 2016, 37(12):2069-2078. doi: 10.1016/S1872-2067(16)62534-2
[21]	JIN Q J, SHEN Y S, ZHU S M, LI X H, HU M.Promotional effects of Er incorporation in CeO₂(ZrO₂)/TiO₂ for selective catalytic reduction of NO by NH₃[J].Chin J Catal, 2016, 37(9):1521-1529. doi: 10.1016/S1872-2067(16)62450-6
[22]	YU C L, HUANG B C, DONG L F, CHEN F, YANG Y, FAN Y M, YANG Y X, LIU X Q, WANG X N.Effect of Pr/Ce addition on the catalytic performance and SO₂ resistance of highly dispersed MnO_x/SAPO-34 catalyst for NH₃-SCR at low temperature[J].Chem Eng J, 2017, 316:1059-1068. doi: 10.1016/j.cej.2017.02.024
[23]	SONG L Y, ZHAN Z C, LIU X J, HE H, QIU W G, ZI X H.NO_x selective catalytic reduction by ammonia over Cu-ETS-10 catalysts[J].Chin J Catal, 2014, 35(7):1030-1035. doi: 10.1016/S1872-2067(14)60035-8
[24]	DE LA TORRE U, PEREDA-AYO B, ROMERO-S EZ M, ARANZABAL A, GONZALEZ-MARCOS MP, GONZALEZ-MARCOS J A, GONZALEZ-VELASCO J R.Screening of Fe-Cu-Zeolites prepared by different methodology for application in NSR-SCR combined DeNO_x systems[J].Top Catal, 2013, 56(1/8):215-221.
[25]	SERRA R, VECCHIETTI M J, MIRO E, BOIX A.In, Fe-zeolites:Active and stable catalysts for the SCR of NO_x -kinetics, characterization and deactivation studies[J].Catal Today, 2008, 133:480-486.
[26]	YAN Q H, NIE Y, YANG R Y, CUI Y H, O'HARE D, WANG Q.Highly dispersed CuyAlO_x mixed oxides as superior low-temperature alkali metal and SO₂ resistant NH₃-SCR catalysts[J].Appl Catal A:Gen, 2017, 538:37-50. doi: 10.1016/j.apcata.2017.03.021
[27]	FENG B J, WANG Z, SUN Y Y, ZHANG C H, TANG SF, LI X B, HUANG X.Size controlled ZSM-5 on the structure and performance of Fe catalyst in the selective catalytic reduction of NO_x with NH₃[J].Catal Commun, 2016, 80:20-23. doi: 10.1016/j.catcom.2016.02.020
[28]	YAO X J, MA K L, ZOU W X, HE S G, AN J B, YANG F M, DONG L.Influence of preparation methods on the physicochemical properties and catalytic performance of MnO_x -CeO₂ catalysts for NH₃-SCR at low temperature[J].Chin J Catal, 2017, 38(1):146-159. doi: 10.1016/S1872-2067(16)62572-X
[29]	XU L, LI X S, CROCKER M, ZHANG Z S, ZHU A M, SHI C.A study of the mechanism of low-temperature SCR of NO with NH₃ on MnO_x/CeO₂[J].J Mol Catal A:Chem, 2013, 378(11):82-90. http://journal.hep.com.cn/fese/CN/abstract/abstract4885.shtml
[30]	SUN M M, WANG S N, LI Y S, WANG Q, XU H D, CHEN Y Q.Promotion of catalytic performance by adding Cu into Pt/ZSM-5 catalyst for selective catalytic oxidation of ammonia[J].J Taiwan Inst Chem E, 2017, 78:401-408. doi: 10.1016/j.jtice.2017.06.045
[31]	NAM K B, KWON D W, HONG S C.DRIFT study on promotion effects of tungsten-modified Mn/Ce/Ti catalysts for the SCR reaction at low-temperature[J].Appl Catal A:Gen, 2017, 542:55-62. doi: 10.1016/j.apcata.2017.05.017
[32]	CHEN L Q, NIU X Y, LI Z B, DONG Y L, ZHANG Z P, YUAN F L, ZHU Y J.Promoting catalytic performances of Ni-Mn spinel for NH₃-SCR by treatment with SO₂ and H₂O[J].Catal Commun, 2016, 85:48-51. doi: 10.1016/j.catcom.2016.07.013
[33]	张贺, 邹永刚, 彭悦.硫酸化对CeO-ZrO催化剂上NH₃选择催化还原NO反应的影响[J].催化学报, 2017, 38(1):160-167. http://www.cjcatal.org/CN/abstract/abstract21934.shtml ZHANG He, ZHOU Yong-gang, PENG Yue.Influence of sulfation on CeO₂-ZrO₂ catalysts for NO reduction with NH₃[J].Chin J Catal, 2017, 38(1):160-167. http://www.cjcatal.org/CN/abstract/abstract21934.shtml
[34]	LIU J, LI X Y, ZHAO Q D, KE J, XIAO H N, LV X J, LIU S M, TADE M, WANG S B.Mechanistic investigation of the enhanced NH₃-SCR on cobalt-decorated Ce-Ti mixed oxide:In situ FT-IR analysis for structure-activity correlation[J].Appl Catal B:Environ, 2017, 200:297-308. doi: 10.1016/j.apcatb.2016.07.020
[35]	WENG X L, DAI X X, ZENG Q S, LIU Y, WU Z B.DRIFT studies on promotion mechanism of H₃PW₁₂O₄₀ in selective catalytic reduction of NO with NH₃[J].J Colloid Interf Sci, 2016, 461:9-14. doi: 10.1016/j.jcis.2015.09.004
[36]	HADJⅡVANOV K I.Identification of neutral and charged N_x Oy surface species by IR spectroscopy[J].Catal Rev, 2000, 42(1/2):71-144. https://www.sciencedirect.com/science/article/pii/0021916979901260