载体对铜基催化剂NH<sub>3</sub>-SCR低温脱硝性能的影响

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

张相俊¹,
刘晓刚¹,
李清雍¹,
李岩¹,
魏波^{1, 2},
王虹^1, ,,
李翠清¹,
宋永吉¹

1.
北京石油化工学院化学工程学院燃料清洁化及高效催化减排技术北京市重点实验室, 北京 102617
2.
北京化工大学化学工程学院, 北京 100029

基金项目:

国家自然科学基金 21343009, 21673290

重质油国家重点实验室开放基金 SKLHOP201501

国家级大学生创新创业训练计划项目 2016J00073

详细信息

通讯作者:
E-mail:wanghong@bipt.edu.cn

中图分类号: O643
计量
- 文章访问数: 94
- HTML全文浏览量: 60
- PDF下载量: 14
- 被引次数: 0
出版历程
- 收稿日期: 2016-08-24
- 修回日期: 2016-11-22
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-02-10

Effect of carrier on the performance of copper based catalyst for selective catalytic reduction of NO with NH₃ at low temperature

1.
Beijing Key Laboratory of Clean Fuel and Advanced Catalytic Pollution Reduction Technology, Department Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China
2.
Department Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Funds:

National Natural Science Foundation of China 21343009, 21673290

the State Key Laboratory of Heavy Oil Processing SKLHOP201501

the National College Students Innovation and Entrepreneurship Training Program 2016J00073

摘要

摘要: 采用浸渍法制备载体负载铜氧化物催化剂。通过XRD、TG-MS、XPS、NO-TPD、NH₃-TPD和H₂-TPR等手段对催化剂进行表征，考察了有氧条件下载体对催化剂NH₃-SCR低温脱硝性能的影响。结果表明，铜物种在载体上以CuO和Cu₂O形式共存，载体影响铜物种的分散性和氧化态，影响催化剂酸性、氧化还原性和对反应物的吸脱附能力。Cu/HZSM-5催化剂，铜物种分散度高，氧化还原性能好，具有适宜的酸性和酸量，对反应物有良好的吸附-脱附性能，在NH₃-SCR脱硝反应中具有较好的催化活性，反应温度低，T₅₀和T₉₀分别为137和165℃，活性窗口温度宽，NO转化率高于90%的温度为165-358℃。
- 载体 /
- 铜氧化物 /
- NH₃-SCR /
- 低温脱硝
Abstract: The catalysts of supported copper oxide were prepared by impregnation method, which were characterized by XRD, TG-MS, XPS, NO-TPD, NH₃-TPD and H₂-TPR and the effect of carrier on the performance of catalysts for the selective catalytic reduction of NO with NH₃ at low-temperature in the presence of oxygen was investigated.The results show that the copper species exist in the form of CuO and Cu₂O on carriers.The dispersion and oxidation state of copper species, the acidity and redox ability of the catalysts and the performance of adsorption/desorption are affected by the carriers.The Cu/HZSM-5 catalyst with highly dispersed copper speicies has excellent redox properties, suitable acidity and acid capacity, and good adsorption/desorption performance for reactants, which shows a good catalytic activity in the NH₃-SCR denitrification reaction.The reaction temperature is lower, T₅₀ and T₉₀ is 137 and 165℃, respectively, and the active window temperature is wide.The temperature range for the NO conversion of over 90% is 165-358℃.
- carrier /
- copper oxide /
- NH₃-SCR /
- low-temperature denitrification

HTML全文

图 1 载体和催化剂的XRD谱图

Figure 1 XRD patterns of the carriers and catalysts

下载: 全尺寸图片幻灯片

图 2 Cu/HZSM-5催化剂前驱体的TG-MS曲线

Figure 2 TG-MS curves of the Cu/HZSM-5 catalyst precursor

下载: 全尺寸图片幻灯片

图 3 催化剂的Cu 2p态XPS谱图

Figure 3 XPS spectra of Cu 2p state in the catalysts

下载: 全尺寸图片幻灯片

图 4 催化剂的O 1s态XPS谱图

Figure 4 XPS spectra of O 1s state in the catalysts

下载: 全尺寸图片幻灯片

图 5 催化剂的NO-TPD谱图

Figure 5 NO-TPD profiles of the catalysts

下载: 全尺寸图片幻灯片

图 6 催化剂NH₃-TPD谱图

Figure 6 NH₃-TPD profiles of the catalysts

下载: 全尺寸图片幻灯片

图 7 催化剂H₂-TPR谱图

Figure 7 H₂-TPR profiles of the catalysts

下载: 全尺寸图片幻灯片

图 8 催化剂的脱硝活性评价

Figure 8 Denitration activity tests over the catalysts reaction conditions: 600 μL/L NH₃ ,600 μL/L NO, 5%O₂ and Ar balance; flow rate: 300 cm³/min; weight of catalyst: 0.4 g

下载: 全尺寸图片幻灯片

表 1 催化剂的XPS和BET表征

Table 1 XPS and BET data of the catalysts

Sample	Specific surface area A/(m²·g^-1)	Percentage of oxygen species derived from O 1s analysis /%		Binding energy E/eV		Cu²⁺/Cu⁺
Sample	Specific surface area A/(m²·g^-1)	O_α	O_β	Cu⁺	Cu²⁺	Cu²⁺/Cu⁺
HZSM-5	388	73.31	26.69	-	-	-
ZRP-5	360	70.24	29.76	-	-	-
γ-Al₂O₃	294	64.05	35.95	-	-	-
Cu/HZSM-5	328	76.61	23.39	932.85	934.99	0.489 7
Cu/ZRP-5	290	71.93	28.07	932.50	934.25	0.825 2
Cu/γ-Al₂O₃	249	64.82	35.18	932.95	934.65	1.023 8

下载: 导出CSV

表 2 催化剂上H₂还原峰面积和温度

Table 2 Peak area and peak temperature of H₂ reduction with the catalysts

Peak	Area/(a.u.)(Temperature t/℃)
Peak	Cu/HZSM-5	Cu/ZRP	Cu/γ-Al₂O₃
1	3.4(204)	1.7(215)	4.0(290)
2	2.1(270)	7.4(280)	9.8(338)
3	2.8(328)	3.5(348)	9.0(430)
4	5.2(474)	0.75(430)	1.3(556)
Total	13.5	13.4	24.1

下载: 导出CSV

参考文献(34)

[1]	王虹, 李滨, 卢学斌, 李翠清, 丁福臣, 宋永吉. 富氧条件下Co/MOR催化剂上甲烷选择催化还原NO[J]. 燃料化学学报, 2015, 43(9):1106-1112. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18696.shtml (WANG Hong, LI Bin, LU Xue-bin, LI Cui-qing, DING Fu-chen, SONG Yong-ji. Selective catalytic reduction of NO by methane over the Co/MOR catalysts in the presence of oxygen[J]. J Fuel Chem Technol, 2015, 43(9):1106-1112.) http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18696.shtml
[2]	任翠涛, 胡颖智, 魏浩宇, 李滨, 王虹, 丁福臣, 李翠清, 宋永吉. SO₂存在条件下M/REY催化剂NH₃选择性还原NO性能研究[J]. 燃料化学学报, 2013, 41(10):1241-1247. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18280.shtml (REN Cui-tao, HU Ying-zhi, WEI Hao-yu, LI Bin, WANG Hong, DING Fu-chen, LI Cui-qing, SONG Yong-ji. NH₃ selective catalytic reduction of NO over M/REY catalysts in presence of SO₂[J]. J Fuel Chem Technol, 2013, 41(10):1241-1247.) http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18280.shtml
[3]	PANAHI P N, SALARI D, NIAEI A, MOUSAVI S M. NO reductionover nanostructure M-Cu/ZSM-5 (M:Cr, Mn, Co and Fe)bimetallic catalysts and optimization of catalyst preparationby RSM[J]. J Ind Eng Chem, 2013, 19(6):1793-1799. doi: 10.1016/j.jiec.2013.02.022
[4]	YU T, FAN D Q, HAO T. The effect of various templates on the NH₃-SCR activities over Cu/SAPO-34 catalysts[J]. J Chem Eng, 2014, 243:159-168. doi: 10.1016/j.cej.2014.01.008
[5]	LIU Q, LIU Z, SU J. Al₂O₃-coated cordierite honeycomb supported CuO catalyst for selective catalytic reduction of NO by NH₃:Surface properties and reaction mechanism[J]. Catal Today, 2010, 158(3/4):370-376. https://www.researchgate.net/publication/289381620_Simultaneous_removal_of_SO2_and_NO_from_flue_gas_using_CuOg-Al2O3_catalyst
[6]	LEI Z G, LONG A B, JIA M R, LIU X Y. Experimental and kineticstudy of selective catalytic reduction of NO with NH₃ over CuO/Al₂O₃/cordierite catalyst[J]. Chin J Chem Eng, 2010, 18(5):721-729. doi: 10.1016/S1004-9541(09)60120-8
[7]	VENNESTROM P N R, JANSSENS T V W, KUSTOV A, GRILL M, PUIG-MOLINA A, LUNDEGAARD L F, TIRUVALAM R R, CONCEPCION P, CORMA A. Influence of lattice stability on hydrothermal deactivation of Cu-ZSM-5 and Cu-IM-5 zeolites for selective catalytic reduction of NO_x, by NH₃[J]. J Catal, 2014, 309(6):477-490.
[8]	PEREDA-AYO B, DE LA TORRE U, ILLAN-GOMEZ M J, BUENO-LOPEZ A, GONZALEZ-VELASCO J R. Role of the different copper species on the activity of Cu/zeolite catalysts for SCR of NO_x, with NH₃[J]. Appl Catal B:Environ, 2014, 147(7):420-428.
[9]	CHEN B H, XU R N, ZHANG R D, LIU N. Economical way to synthesize SSZ-13 with abundant ion-exchanged Cu⁺ for an extraordinary performance in selective catalytic reduction (SCR) of NO_x, by ammonia[J]. Environ Sci Technol, 2014, 48(23):13909-13916. doi: 10.1021/es503707c
[10]	SI Z C, WENG D, WU X D, LI J, LI G. Structure, acidity and activity of CuO_x, /WO_x, -ZrO₂ catalyst for selective catalytic reduction of NO by NH₃[J]. J Catal, 2010, 271(1):43-51. doi: 10.1016/j.jcat.2010.01.025
[11]	BONINGARI T, PAPPAS D K, ETTIREDDY P R, KOTRBA A, SMIRNIOTIS P G. Influence of SiO₂ on M/TiO₂ (M=Cu, Mn, and Ce) formulations for low-temperature Selective catalytic reduction of NO_x, with NH₃:Surface properties and key components in relation to the activity of NO_x, reduction[J]. Ind Eng Chem Res, 2015, 54(8):2261-2273. doi: 10.1021/ie504709j
[12]	王栋, 吴惊坤, 牛胜利, 路春美, 徐丽婷, 于贺伟, 李婧. Sn、Ti 掺杂改性γ, -Fe₂O₃催化剂结构及NH₃-SCR 脱硝活性研究[J]. 燃料化学学报, 2015, 43(7):876-883. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18666.shtml (WANG Dong, WU Jing-kun, NIU Sheng-li, LU Chun-mei, XU Li-ting, YU He-wei, LI Jing. Structural property of γ, -Fe₂O₃ catalysts doped with Sn and Ti and their activity in the selective catalytic reduction of NO_x,[J]. J Fuel Chem Technol, 2015, 43(7):876-883.) http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18666.shtml
[13]	YANG S J, LI J H, WANG C Z, CHEN J H, MA L, CHANG H Z, CHEN L, PENG P, YAN N Q. Fe-Ti spinel for the selective catalytic reduction of NO with NH₃:Mechanism and structure-activity relationship[J]. Appl Catal B:Environ, 2012, 117-118(18):73-80. https://www.researchgate.net/publication/257370778_Fe-Ti_spinel_for_the_selective_catalytic_reduction_of_NO_with_NH3_Mechanism_and_structure-activity_relationship
[14]	MOUSAVI S M, NIAEI A, GÓEZ M J I, SALARI D, PANAHI P N, ABALADEJO-FUENTES V. Characterization and activity of alkaline earthmetals loaded CeO₂-MO_x, (M=Mn, Fe) mixed oxides in catalytic reduction of NO[J]. Mater Chem Phys, 2014, 143(3):921-928. doi: 10.1016/j.matchemphys.2013.09.017
[15]	LIU F, HE H, ZHANG C, SHAN W P, SHI X Y. Mechanism of the selective catalytic reduction of NO_x, with NH₃ over environmental-friendly iron titanate catalyst[J]. Catal Today, 2011, 175(1):18-25. doi: 10.1016/j.cattod.2011.02.049
[16]	BRANDENBERGER S, KRÖCHER O, CASAPU M, TISSLER A, ALTHOFF R. Hydrothermal deactivation of Fe-ZSM-5 catalysts for the selective catalytic reduction of NO with NH₃[J]. Appl Catal B:Environ, 2011, 101(3):649-659. https://www.researchgate.net/publication/251617491_Hydrothermal_deactivation_of_Fe-ZSM-5_catalysts_for_the_selective_catalytic_reduction_of_NO_with_NH_3
[17]	ELLMERS I, VÉEZ R P, BENTRUP U, BRVCKNER A, GRVNERT W. Oxidation and selective reduction of NO over Fe-ZSM-5-How related are these reactions[J]. J Catal, 2014, 311:199-211. doi: 10.1016/j.jcat.2013.11.024
[18]	TANG X L, HAO J M, XU W G, LI J H. Low temperature selective catalytic reduction of NO_x, with NH₃ over amorphous MnO_x, catalysts prepared by three methods[J]. Catal Commun, 2007, 8(3):329-3341. doi: 10.1016/j.catcom.2006.06.025
[19]	JIANG B Q, LIU Y, WU Z B. Low-temperature selective catalytic reduction of NO on MnO_x, /TiO₂ prepared by different methods[J]. J Hazard Mater, 2009, 162(2/3):1249-12541.
[20]	KIM M S, CHUNG S H, YOO C J, LEE M S, CHO I H, LEE D W, LEE K Y. Catalytic reduction of nitrate in water over Pd-Cu/TiO₂ catalyst:Effect of the strong metal-support interaction (SMSI) on the catalytic activity[J]. Appl Catal B:Environ, 2013, 142-143(5):354-361. https://koreauniv.pure.elsevier.com/en/publications/catalytic-reduction-of-nitrate-in-water-over-pd-cutiosub2sub-cata
[21]	ZHANG G Q, LI Z, ZHENG H Y, FU T J, JU Y B, WANG Y C. Influence of the surface oxygenated groups of activated carbon on preparation of a nano Cu/AC catalyst and heterogeneous catalysis in the oxidative carbonylation of methanol[J]. Appl Catal B:Environ, 2015, 179:95-105. doi: 10.1016/j.apcatb.2015.05.001
[22]	CHARY K V R, SAGAR G V, NARESH D, SEELA K K, SRIDHAR B. Characterization and reactivity of copper oxide catalysts supported on TiO₂-ZrO₂[J]. J Phys Chem B, 2005, 109(19):9437-9444. doi: 10.1021/jp0500135
[23]	ZOU H B, CHEN S Z, LIN W M. Effect of pretreatment methods on the performance of Cu-Zr-Ce-O catalyst for CO selective oxidation[J]. J Nat Gas Chem, 2008, 17(2):208-211. doi: 10.1016/S1003-9953(08)60053-5
[24]	LALITHA K, SADANANDAM G, KUMARI V D, SUBRAHMANYAM M, SREEDHAR B, HEBALKAR N Y. Highly stabilized and finely dispersed Cu₂O/TiO₂:Apromising visible sensitive photocatalyst for continuous production of hydrogen from glycerol:Water mixtures[J]. J Phys Chem C, 2010, 114(50):22181-22189. doi: 10.1021/jp107405u
[25]	XIN B F, WANG P, DING D D, LIU J, REN Z Y, FU H G. Effect of surface species on Cu-TiO₂ photocatalytic activity[J]. Appl Surf Sci, 2008, 254(9):2569-2574. doi: 10.1016/j.apsusc.2007.09.002
[26]	BAGHRICHE O, RTIMI S, PULGARIN C, SANJINES R, KIWI J. Innovative TiO₂/Cu nanosurfaces inactivating bacteria in the minute range under low-intensity actinic light[J]. ACS Appl Mater Inter, 2012, 4(10):5234-5240. doi: 10.1021/am301153j
[27]	YAOX J, ZHANG L, LI L, LIU L C, CAOY, DONG X, GAO F, DENG Y, TANG J, CHEN Z, DONG L, CHEN Y. Investigation of the structure, acidity, and catalytic performance of CuO/Ti_0.95Ce_0.05O₂ catalyst for the selective catalytic reduction of NO by NH₃ at low temperature[J]. Appl Catal B:Environ, 2014, 150-151(11):315-329.
[28]	SIZ C, WENG D, WUX D, JIANG Y, WANG B. Synergistic effects between copper and tungsten on the structural and acidic properties of CuO_x,/WO_x, -ZrO₂ catalyst[J]. Catal Sci Technol, 2011, 1(3):453-461. doi: 10.1039/c0cy00086h
[29]	ČAPEK L, DĚDEČEK J, WICHTERLOVÁ B, CIDER L, JOBSON E, TOKAROVÁ V. Cu-ZSM-5 zeolite highly active in reduction of NO with decane:Effect of zeolite structural parameters on the catalyst performance[J]. Appl Catal B:Environ, 2005, 60(3/4):147-153.
[30]	NDONGL B B, IBONDOU M P, GU X G, LU S G, QIU Z F, SUI Q, MBADINGA S M. Enhanced photocatalytic activity of TiO₂nanosheetsby doping with Cu for chlorinated solvent pollutants degradation[J]. Ind Eng Chem Res, 2014, 53(4):1368-1376. doi: 10.1021/ie403405z
[31]	LANDI G, LISI L, PIRONE R, TORTORELLI M, RUSSO G. NO decomposition over La-doped Cu-ZSM5 monolith under adsorption-reaction conditions[J]. Appl Catal A:Gen, 2013, 464-465(16):61-67. https://www.researchgate.net/publication/257374248_NO_decomposition_over_La-doped_Cu-ZSM5_monolith_under_adsorption-reaction_conditions
[32]	MA L, CHENG Y S, CAVATAIO G, MCCABE R W, FU L X, LI J H. Characterization of commercial Cu-SSZ-13 and Cu-SAPO-34 catalysts with hydrothermal treatment for NH₃-SCR of NO_x, in diesel exhaust[J]. Chem Eng J, 2013, 225(3):323-330.
[33]	OCHONSKA J, MCCLYMONT D, JODŁOWSKI P J, KNAPIK A, GIL B, MAKOWSKI W, ŁASOCHA W, KOŁODZIEJ A, KOLACZKOWSKI S T, ŁOJEWSKA J. Copper exchanged ultrastable zeolite Y-A catalyst for NH₃-SCR of NO_x, from stationary biogas engines[J]. Catal Today, 2012, 191(1):6-11. doi: 10.1016/j.cattod.2012.06.010
[34]	NEYLON M K, MARSHALL C L, KROPF A J. In situ EXAFS analysis of the temperature-programmed reduction of Cu-ZSM-5[J]. J Am Chem Soc, 2002, 124(19):5457-5465. doi: 10.1021/ja0176696