SO2对Zr掺杂Mn-Ce/GR催化剂低温脱硝性能的影响

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Effect of SO2 on de-NOx performance of Zr doping Mn-Ce/GR catalyst at low temperature

LI Shujian^1,,
YOU Xiaochen¹,
SHENG Zhongyi^1,2,
XIAO Xiang²,
YU Danqing³,
ZHOU Pengfei¹,
YANG Liu¹
1.School of Environment, Nanjing Normal University, Nanjing 210023, China
2.Suzhou Industrial Technology Research Institute of Zhejiang University, Suzhou 215163, China
3.School of Chemistry and Chemical Engineering, Wuhan University of Science and Technology, Wuhan 430081, China

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摘要:通过水热法分别制备掺杂Zr、Sb、Sn和Si的Mn-Ce/石墨烯（Mn-Ce/GR）催化剂，考察了其在低温氨气选择性催化还原（NH3-SCR）过程中对NOx的去除效率和抗SO2中毒性能。结果显示，掺杂Zr后，催化剂具有良好的低温脱硝活性，在120 ℃时，其NOx转化率和N2选择性分别达到97.26%和98.97%，且当进气中SO2的体积分数为200×10-6时，其抗硫性明显优于掺杂其他3种元素的催化剂，原因是硫酸盐在掺杂Zr催化剂表面的沉积速率有所减缓。通过Raman、XRD、HRTEM、SEM、BET、XPS、FT-IR、H2-TPR以及NH3-TPD等表征手段对掺杂Zr的Mn-Ce/GR新鲜催化剂和失活样品进行表征分析。发现，SO2对掺杂Zr催化剂的毒化作用主要有4个方面：Oα大量减少，还原能力减弱；活性组分CeO2含量减少，储氧能力减弱；催化剂表面Zr含量减少，酸性位点减少；硫酸盐和硝酸盐在催化剂表面大量沉积，减少了催化剂的比表面积。
关键词: 锆掺杂/
锰铈石墨烯复合型催化剂/
低温氮气选择性催化还原/
二氧化硫

Abstract:Zr, Sb, Sn and Si were used to modify the Mn-Ce/graphene(Mn-Ce/GR) catalyst, respectively. SO2 resistance of these catalysts prepared by hydrothermal method for low-temperature selective catalytic reduction(SCR) of NOx with NH3 was investigated in this study. The results indicated that Zr doping Mn-Ce/GR catalyst showed superior activity. NOx conversion and N2 selectivity were 97.26% and 98.97%, respectively at 120 °C. And it had higher SO2 resistance than the others when SO2 with a volume fraction of 200×10-6 was fed in. One possible reason was that the deposition rate of sulfates reduced. The fresh and deactivated Zr doping Mn-Ce/GR catalysts were characterized by Raman spectroscopy, XRD, HRTEM, SEM, BET, XPS, FT-IR, H2-TPR and NH3-TPD. The characterized results indicated that the deactivation of Zr doping catalysts was mainly caused by the four reasons. Firstly, the decrease of Oα concentration on the surface weakened the reduction ability. Secondly, the decrease of CeO2 content led the reduction of oxygen storage capacity. Thirdly, with the decrease of Zr content on catalysts surface, the acid sites were reduced. Finally, the deposion of sulfates and nitrates decreasedthe specific surface area of the catalysts.
Key words:Zr-doping/
Mn-Ce/GR catalyst/
low-temperature NH3-SCR/
SO2.

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[1]	刘亭. 锰铈基低温选择性催化还原(SCR)脱硝催化剂的研究[D]. 天津:南开大学,2011
[2]	余艳, 袁博, 周松.NH₃-SCR钒系催化剂的制备及脱硝性能研究[J]. 车用发动机,2015,38(3):37-40
[3]	刘福东, 单文坡, 石晓燕, 等. 用于NH₃选择性催化还原NO的非钒基催化剂研究进展[J]. 催化学报,2011,32(7):1113-1128
[4]	喻成龙, 黄碧纯,杨颖欣. 分子筛应用于低温 NH₃-SCR 脱硝催化剂的研究进展[J]. 华南理工大学学报（自然科学版）,2015,59(3):143-151
[5]	李晨露, 唐晓龙, 易红宏, 等.Mn基低温SCR催化剂的抗H₂O、抗SO₂研究进展[J]. 化工进展,2017,36(3):934-943
[6]	KAPTEIJN F, SINGOREDJO L, ANDREINI A, et al.Activity and selectivity of pure manganese oxides in the selective catalytic reduction of nitric oxide with ammonia[J].Applied Catalysis B:Environmental,1994, 3(3): 173-189 10.1016/0926-3373(93)E0034-9
[7]	孙亮, 许悠佳, 曹青青, 等. 氧化锰基催化剂低温NH₃选择性还原NO_x反应及其机理[J]. 化学进展,2010, 22(10):1882-1891
[8]	QI G, YANG R T, CHANG R, et al.MnO_x-CeO₂ mixed oxides prepared by co-precipitation for selective catalytic reduction of NO with NH₃ at low temperatures[J].Applied Catalysis B:Environmental,2004,51(2): 93-106 10.1016/j.apcatb.2004.01.023
[9]	QI G, YANG R T.Performance and kinetics study for low-temperature SCR of NO with NH₃ over MnO_x-CeO₂ catalyst[J].Journal of Catalysis,2003,217(2):434-441 10.1016/S0021-9517(03)00081-2
[10]	QI G, YANG R T.Characterization and FTIR studies of MnO_x-CeO₂ catalyst for low-temperature selective catalytic reduction of NO with NH₃[J].Journal of Physical Chemistry B,2004,108(40):15738-15747 10.1021/jp048431h
[11]	XIAO X, SHENG Z Y, YANG L, et al.Low-temperature selective catalytic reduction of NO_x with NH₃ over a manganese and cerium oxide/graphene composite prepared by a hydrothermal method[J].Catalysis Science & Technology,2016,6(5):1507-1514 10.1039/C5CY01228G
[12]	SHEN B X, WANG Y Y, WANG F M, et al.The effect of Ce-Zr on NH₃-SCR activity over MnO_x (0.6)/Ce_0.5Zr_0.5O₂ at low temperature[J].Chemical Engineering Journal,2014,236:171-180 10.1016/j.cej.2013.09.085
[13]	LI W, GUO R T, WANG S X, et al.The enhanced performance of a CeSiO_x support on a Mn/CeSiO_x catalyst for selective catalytic reduction of NO_x with NH₃[J].RSC Advances,2016,6(86):82707-82715 10.1039/C6RA18821D
[14]	HUANG B J, YU D Q, SHENG Z Y, et al.Novel CeO₂@TiO₂ core-shell nanostructure catalyst for selective catalytic reduction of NO_x with NH₃[J].Journal of Environmental Sciences,2017,29(5):129-136 10.1016/j.jes.2016.05.038
[15]	GAO G, SHI J W, LIU C, et al.Mn/CeO₂ catalysts for SCR of NO_x with NH₃：Comparative study on the effect of supports on low-temperature catalytic activity[J].Applied Surface Science,2017,411:338-346 10.1016/j.apsusc.2017.03.164
[16]	杨超, 刘小青, 黄碧纯, 等.Zr改性MnO_x/MWCNTs催化剂的结构特征与低温SCR活性[J]. 物理化学学报,2014,30(10):1895-1902 10.3866/PKU.WHXB201407162
[17]	孙传智.Sm、Zr共掺杂对MnO_x-TiO₂催化剂N₂选择性及抗水抗硫性能作用研究[C]//中国稀土学会.中国稀土学会2017学术年会摘要集,2017
[18]	ZHU Z P, LIU Z Y, NIU H X, et al.Mechanism of SO₂ promotion for NO reduction with NH₃ over activated carbon-supported vanadium oxide catalyst[J].Journal of Catalysis,2001,197(1):6-16 10.1006/jcat.2000.3052
[19]	陶建忠,李国祥,佟德辉.H₂O和SO₂在NH₃选择性催化还原NO_x过程中的影响[J].内燃机工程,2008,29(3):56-58
[20]	ETTIREDDY P R, ETTIREDDY N, MAMEDOV S, et al.Surface characterization studies of TiO₂ supported manganese oxide catalysts for low temperature SCR of NO with NH₃[J].Applied Catalysis B:Environmental,2007,76(1):123-134 10.1016/j.apcatb.2007.05.010
[21]	SU Y X, FAN B X, WANG L S, et al.MnO_x supported on carbon nanotubes by different methods for the SCR of NO with NH₃[J].Catalysis Today,2013,201:115-121 10.1016/j.cattod.2012.04.063
[22]	SUN Z P, HASAN T, TORRISI F, et al.Graphene mode-locked ultrafast laser[J].ACS Nano,2010,4(2):803-810 10.1021/nn901703e
[23]	焦金珍, 李时卉, 黄碧纯. 石墨烯负载MnO_x催化剂的制备及其低温NH₃-SCR活性[J]. 物理化学学报,2015,31(7):1383-1390 10.3866/PKU.WHXB201504292
[24]	张晓鹏. 基于Mn/Ce-ZrO₂催化剂的低温NH₃-SCR脱硝性能研究[D]. 天津:南开大学. 2013
[25]	张晓鹏, 沈伯雄.Mn/Ce-ZrO₂催化剂低温NH₃-SCR脱硝性能研究[J]. 燃料化学学报, 2013,41(1):123-128
[26]	张呈祥.Mn-Ce/Al₂O₃低温SCR脱硝催化剂抗SO₂中毒性能研究[D]. 大连:大连理工大学. 2015
[27]	束航.SCR烟气脱硝过程中硫酸（氢）铵细颗粒生成及分解特性研究[D]. 南京:东南大学. 2015
[28]	闫东杰, 玉亚, 黄学敏, 等.SO₂对Mn-Ce/TiO₂低温SCR催化剂的毒化作用研究[J]. 燃料化学学报,2016,44(2):232-238
[29]	何余生, 李忠, 奚红霞, 等. 气固吸附等温线的研究进展[J]. 离子交换与吸附,2004,20(4):376-384
[30]	SHENG Z Y, HU Y F, XUE J M, et al.SO₂ poisoning and regeneration of Mn-Ce/TiO₂ catalyst for low temperature NO_x reduction with NH₃[J].Journal of Rare Earths,2012,30(7):676-682 10.1016/S1002-0721(12)60111-2
[31]	JARRIGE J, VERVISCH P.Plasma-enhanced catalysis of propane and isopropyl alcohol at ambient temperature on a MnO₂-based catalyst[J].Applied Catalysis B: Environmental,2009,90(1):74-82 10.1016/j.apcatb.2009.02.015
[32]	YE Q, ZHAO J S, HUO F F, et al.Nanosized Ag/α-MnO₂ catalysts highly active for the low-temperature oxidation of carbon monoxide and benzene[J].Catalysis Today,2011,175(1):603-609 10.1016/j.cattod.2011.04.008
[33]	GU T T, LIU Y, WENG X L, et al.The enhanced performance of ceria with surface sulfation for selective catalytic reduction of NO by NH₃[J].Catalysis Communications,2010,12(4):310-313 10.1016/j.catcom.2010.10.003
[34]	XU W Q, HE H, YU Y B, et al.Deactivation of a Ce/TiO₂ catalyst by SO₂ in the selective catalytic reduction of NO by NH₃[J].Journal of Physical Chemistry C,2009,113(11):4426-4432 10.1021/jp8088148
[35]	ROMANO E, SCHULZ K H.A XPS investigation of SO₂ adsorption on ceria-zirconia mixed-metal oxides[J].Applied Surface Science,2005,246(1):262-270 10.1016/j.apsusc.2004.11.017
[36]	SU W, LU X N, JIA S H, et al.Catalytic reduction of NO_x over TiO₂-graphene oxide supported with MnO_x at low temperature[J].Catalysis Letters,2015,145(7):1446-1456 10.1007/s10562-015-1550-3
[37]	冯云桑.Co-Ce氧化物对Mn/TiO₂系低温脱硝催化剂结构与性能的影响[D].镇江:江苏科技大学. 2013
[38]	WANG L S, HUANG B C, SU Y X, et al.Manganese oxides supported on multi-walled carbon nanotubes for selective catalytic reduction of NO with NH₃: Catalytic activity and characterization[J].Chemical Engineering Journal,2012,192:232-241 10.1016/j.cej.2012.04.012
[39]	龙恩艳, 王云, 张晓玉, 等.Zr基载体负载Pd催化剂用于贫燃天然气汽车尾气净化[J]. 催化学报, 2010,31(3):313-316
[40]	SHEN B X, MA H Q, HE C, et al.Low temperature NH₃-SCR over Zr and Ce pillared clay based catalysts[J].Fuel Processing Technology,2014, 119:121-129 10.1016/j.fuproc.2013.10.026
[41]	SHEN B X, ZHANG X P, MA H Q, et al.A comparative study of Mn/CeO₂, Mn/ZrO₂ and Mn/Ce-ZrO₂ for low temperature selective catalytic reduction of NO with NH₃ in the presence of SO₂ and H₂O[J].Journal of Environmental Sciences,2013,25(4):791-800 10.1016/S1001-0742(12)60109-0
[42]	DONG F, ZHAO W R, WU Z B, et al.Band structure and visible light photocatalytic activity of multi-type nitrogen doped TiO₂ nanoparticles prepared by thermal decomposition[J].Journal of Hazardous Materials, 2009,162(2):763-770 10.1016/j.jhazmat.2008.05.099
[43]	胡宇峰, 薛建明, 王小明, 等.Mn-Ce/TiO₂低温选择性催化还原催化剂二氧化硫中毒及再生特性[J]. 工业催化,2013,22(4):27-33 10.3969/j.issn.1008-1143.2013.04.006
[44]	BUCIUMAN F, PATCAS F, CRACIUN R, et al.Vibrational spectroscopy of bulk and supported manganese oxides[J].Physical Chemistry Chemical Physics,1999,1(1):185-190 10.1039/A807821A
[45]	艳莉, 李晓晓, 詹亮, 等. 金属助剂对蜂窝状MnO_x-CeO₂/ACH催化剂低温脱硝行为的影响[J]. 燃料化学学报,2014,59(11):1365-1371
[46]	马建蓉, 黄张根, 刘振宇, 等. 再生方法对V₂O₅/AC催化剂同时脱硫脱硝活性的影响[J]. 催化学报, 2005,26(6):463-469
[47]	ZHANG J B, ZHONG Z P, SHEN D K, et al.Preparation of bamboo-based activated carbon and its application in direct carbon fuel cells[J].Energy & Fuels,2011,25(5):2187-2193 10.1021/ef200161c
[48]	付孟帆.Mn-Ce-CuO_x/ACF低温选择催化还原NO的实验研究[D]. 长沙:湖南大学. 2014
[49]	SHEN B X, LIU T.Deactivation of MnO_x-CeO_x/ACF catalysts for low-temperature NH₃-SCR in the presence of SO₂[J]．Acta Physico-Chimica Sinica,2010,26(11):3009-3016 10.3866/PKU.WHXB20101120
[50]	HOU Y Q, HUANG Z G, GUO S J, et al.Effect of SO₂ on V₂O₅/ACF catalysts for NO reduction with NH₃ at low temperature[J].Catalysis Communications,2009,10(11):1538-1541 10.1016/j.catcom.2009.04.003
[51]	ZHANG X P, SHEN B X, WANG K, et al.A contrastive study of the introduction of cobalt as a modifier for active components and supports of catalysts for NH₃-SCR[J].Journal of Industrial and Engineering Chemistry, 2013,19(4):1272-1279 10.1016/j.jiec.2012.12.028
[52]	YANG S J, GUO Y F, CHANG H Z, et al.Novel effect of SO₂ on the SCR reaction over CeO₂: Mechanism and significance[J].Applied Catalysis B:Environmental,2013,136:19-28 10.1016/j.apcatb.2013.01.028
[53]	SUN M J, ZOU G J, XU S, et al.Nonaqueous synthesis, characterization and catalytic activity of ceria nanorods[J].Materials Chemistry and Physics,2012,134(2):912-920 10.1016/j.matchemphys. 2012.03.089
[54]	PICASSO G, GUTIERREZ M, PINA M P, et al.Preparation and characterization of Ce-Zr and Ce-Mn based oxides for n-hexane combustion: Application to catalytic membrane reactors[J].Chemical Engineering Journal,2007,126(2):119-130 10.1016/j.cej.2006.09.005
[55]	AGUILERA D A, PEREZ A, MOLINA R, et al.Cu-Mn and Co-Mn catalysts synthesized from hydrotalcites and their use in the oxidation of VOCs[J].Applied Catalysis B:Environmental,2011,104(1):144-150 10.1016/j.apcatb.2011.02.019
[56]	LIU F D, HE H.Selective catalytic reduction of NO with NH₃ over manganese substituted iron titanate catalyst: Reaction mechanism and H₂O/SO₂ inhibition mechanism study[J].Catalysis Today,2010,153(3): 70-76 10.1016/j.cattod.2010.02.043
[57]	SULTANA A, SASAKI M, HAMADA H, et al.Influence of support on the activity of Mn supported catalysts for SCR of NO with ammonia[J].Catalysis Today,2012,185(1):284-289 10.1016/j.cattod.2011.09.018
[58]	PENG Y, LIU Z, NIU X W, et al.Manganese doped CeO₂-WO₃ catalysts for the selective catalytic reduction of NO_x with NH₃: An experimental and theoretical study[J].Catalysis Communications,2012,19:127-131 10.1016/j.catcom.2011.12.034
[59]	CHANG H Z, LI J H, CHEN X Y, et al.Effect of Sn on MnO_x-CeO₂ catalyst for SCR of NO_x by ammonia: Enhancement of activity and remarkable resistance to SO₂[J].Catalysis Communications,2012,27:54-57 10.1016/j.catcom.2012.06.022

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