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September 物理化学学 ̄(Wu/i Huaxue Xuebao) Acta Phys.一C .Sin.2015,31(9),1771—1779 l771 

[Article】 doi:10.3866/PKU.WHXB201507141 www.whxb.pku.edu.cn Zr的添加对稀燃天然气汽车尾气净化催化剂Pd—Pt/AI203'l生能的影响 胡 伟’ 王 云, 尚鸿燕, 徐海迪z,s 钟 琳11‘ 陈建军 龚茂初 陈耀强 , (・四川大学化学工程学院,成都610064; 四川大学新能源与低碳技术研究院,成都610064; ,四川大学化学学院,绿色化学与技术教育部重点实验室,成都610064) 

摘要:Pd.Pt双金属基甲烷氧化催化剂的催化活性、抗水热老化性和耐硫性在一个通有模拟稀燃天然气汽车 尾气成分的固定床反应器中进行检测.研究发现Zr掺杂的Pd—PffAI2O3(Pd-PUZqA10-x)O【3+州2)提高了催化的催 化活性、抗水热老化性和耐硫性.以共沉淀法制备Zr:AI的摩尔比分别为0:1、0.25:0.75、0.5:0.5、0.75: 0.25gl1:0的材料为载体材料.双金属催化剂的活性组分分别为1.5%(W,质量分数)的Pd和0.3%(w)的Pt,活 性组分Pd、Pt通过共浸渍的方法浸渍到以上载体材料上制备得到一系列整体式催化剂.分别采用低温N2吸脱 附、X射线衍射(XRD)、H2程序升温还原(H -TPR)、O2程序升温氧化(O 一TPD) ̄X射线光电子能谱对制各的 催化剂进行表征.结果显示Zr的加入使催化剂的载体材料结晶度提高,活性组分的分散度也得到了相应的提 高.同时二价Pd物种与周围电子密度分别增加.相比于Pd.Pt/AI203#llPd—Pt/ZrO2催化剂,在不同条件预处理后 Zr的添加对催化剂的性能有明显的提高,其中催化剂Pd_Pt/Zr0 5Al0_5O1 75展现了最好的催化活性、抗水热老化 性以及耐硫性. 

关键词:铝:锆:不同摩尔比:载体:天然气燃料发动机:催化性能 中图分类号:0643 

Effects of Zr Addition on the Performance of the Pd・Pt/AI203 Catalyst for Lean.Burn NaturaI Gas Vehicle Exhaust PUrification 

HU Wei’ WANG Yun’ SHANG Hong-Yan’XU Hai—Di l。 ZHONG Lin’' CHEN Jian—Jun GONG Map-Chu CHEN Yap-Qiang’r ・。, ('CollegeofChemicalEngineering,Sichuan University,Chengdu 610064, R.China;2InstituteofNewEnergyandLow—Carbon Technology,Sichuan University,Chengdu 610064,P.R.China; K Laboratory ofGreen Chemistry&Technology ofMinistry of Education,College ofChemistry,Sichuan University,Chengdu 610064,P.R.China) 

Abstract:The catalytic activity,hydrothermal aging resistance,and sulfur tolerance of a Pd.Pt.based methane oxidation catalyst were evaluated in a fixed fluidized bed reactor containing simulated Iean.burn natural gas vehicle exhaust gases.Zirconium—doped Pd-Pt/AI2O3(Pd-Pt/ZrxAl(1-x)Of3+ 1,2)was found to significantly improve the catalytic activity,hydrothermal aging resistance,and sulfur tolerance.Zr.modified alumina suppoRs were prepared by cO—precipitation with molar ratios of Zr tO A1 0f 0:1,0。25:0.75.O.5: 0.5,0.75:0.25,and 1:0.The Pd—Pt bimetallic catalysts containing 1.5%(W,mass fraction)Pd and 0.3% (w)Pt supposed on the above-modified composite suppo ̄s were prepared by the CO-impregnating method. 

Received:May 4,2015;Revised:July 14,2015;Published on Web:July 14,2015. ’Corresponding authors.CHEN Yao—Qiang,Email:nic7501@sou.edu.on;Tel/Fax:+86—28-85418451.ZHONG Lin,Email:zhonglin@SCU.edu.ca. The projcot was supported by the National Natural Science Foundation ofChina(21 173153),Project from Sichuan Provincial Environment Office, China(2Ol 1HB002),and Science and Technology Support Project ofScience and Technology Department ofSichuan Province,China (2012FZ0008). 国家自然科学基金(21173153),四川省环境保护厅项目(201IHB002)及四川省科技厅科技支撑项目(2012FZ0008)资助 ◎Editorial 0f!fice of Acta Physico—Chimica Sinica 1772 ActaPhys.-Chim.Sin.2015 Vol-31 The catalysts were characterized by N2 ads0rptjon,desorption,X—ray difraction(XRD),H2 temperature. programmed reduction(H2-TPR),O2 temperature-programmed desorption,and X.ray photoelectron spectroscopy(XPS).The results show that the crystallinity of the samples,dispersion of the active component,number of Pd species,and electron density around Pd species increase after addition of ZrO2 to AI2O3 supports.Compared with the activity results of Pd-Pt/AI2O3 and Pd.Pt/ZrO2 catalysts after diferent pretreatment conditions,the performance of the catalyst is greatly enhanced by adding ZrO。in the AI203 supports,and Pd-Pt/Zr0.sA10 5O1 75 shows the best catalytic activity,strongest hydrothermal aging resistance,and highest sulfur tolerance among the investigated catalysts. 

Key Words:Aluminum;Zirconium;Different molar ratios;Support; Natural gas fuelled vehicle Catalytic performance 

1 lntroduction Natural gas【NG)resources are abundant,and used widely as energy source in industry and automotive vehicle owing to their low exhaust emission. , With the development of the natural gas fields,the number of natural gas vehicles is increasing syn— chronously. Besides the economic needs。compressed natural gas vehicles(NGVs)with low CO and low NOx emissions have more eco-friendly advantages than gasoline and diesel vehicles. -一Especially.the operation of NGVs under lCal1.burn conditions could reduce the pollutants more effectively and im— prove thermal efficiency compared with the stoichiometric con. dition. 一 Although engine technologies have been improved to increase combustion emciency and decrease emission.the main ingredients of exhaust still contain HC,CO,and N ;moreover, methane is the main component(90%一95%、of the total hydro. carbon that makes more contributions to global climate warl/1. ing than carbon dioxide when the emission rates are equality. l6 Therefore.it is very urgent to reduce methane emission ef.fect— ively in the NGV exhaust. Noble metal(Pt,Pd,Rh)catalysts,especially palladium cata— lysts.have been recognized as one of the best catalysts to re— duce methane emissions. , 0 The NVG catalysts are usually working in the harsh environment(the high temperature,high water content,and high sulfur content),which makes the active site of catalysts be easy to be poisoned and sintered. About 10%一15%(volume fraction)water vapor which exists in the NVG exhaust would induce sintering of active site.1eading to the decrease of CHd conversion under lean.bum conditions. The sulfides contained in the exhaust gas also cause deactiva— tion of the catalysts. ' ’ In fact,the synergistic effect existing between water and sulfur in the exhaust of NGVs can acceler— ate the deactivation of catalysts. 。t Thus.the hydrothermal aging resistance and sulfur tolerance of palladium—supported catalysts for methane conversion need to be improved. Lapisardi, Persson,”Yang,”Corro, and Narui et a1.repor— ted that the addition of Pt to Pd could improve the catalytic activity,thermostability,and sulfur resistance.Thev found that the addition Of Pt tO the Pd catalysts could weaken the Pd一0 bond and affect the adsorption of methane and oxygen.Also the probability of sulfur dioxide interaction with PdO was