| 381 | 6 | 33 |
| 下载次数 | 被引频次 | 阅读次数 |
高标准排放法规要求汽车尾气净化催化剂在冷启动阶段对碳氢化合物(HC)进行吸附存储,在正常工作温度下脱附并催化净化。汽油车尾气中的HC主要成分为甲苯,因此选用了NaY、USY和ZSM-5分子筛,制备了CeO2改性的不同分子筛材料;利用比表面分析仪(BET)、高分辨透射电子显微镜(HRTEM)、热重分析仪(TG)、化学吸附仪和X射线衍射分析仪(XRD),表征分析了不同分子筛以及CeO2改性后结构与酸碱性的变化对甲苯的吸附与脱附性能。结果表明,未改性前,USY分子筛对甲苯的吸附性能最佳,甲苯的饱和吸附量达到245.9mg/g,甲苯的脱附温度范围为290～360℃;CeO2改性后分子筛的吸附量均有明显的提升,其中CeO2/USY材料对甲苯的吸附量最佳,达到270mg/g,比未改性USY的提升了约10%。
Abstract：High standard emission regulations require that vehicle exhaust gas purification catalyst adsorbs and stores hydrocarbons(HC)during vehicle cold start stage,and then desorbs and purifies them at normal operating temperature.Toluene is main component of HC in tail gas of gasoline vehicles.Therefore,NaY,USY and ZSM-5 molecular sieves were selected to prepare different molecular sieve materials modified by CeO2.Adsorption and desorption properties of toluene were characterized and analyzed by N2 physical adsorption instrument,high resolution transmission electron microscope(TEM),chemical adsorption instrument and X-ray diffraction(XRD)instrument.The results show that adsorption capacity of USY zeolite to toluene is the best before modification,saturated adsorption capacity of toluene is 245.9 mg/g,and toluene desorption temperature range is 290—360 ℃ .Adsorption capacity of molecular sieve is significantly improved after CeO2 modification,among which CeO2/USY material has a best adsorption capacity for toluene,reaching to 270 mg/g,which is about 10% higher than that of unmodified USY.
[1]陈兴,孔维青,张丽丹．汽车尾气催化剂研究进展[J]．广州化工,2015,43(18):5-6,22.CHEN X,KONG W Q,ZHANG L D.Research progress on automobile exhaust catalyst[J].Guangzhou Chemical Industry,2015,43(18):5-6,22．
[2]ZHAO Y L,LAMBE A,SALEH R,et al.Secondary organic aerosol production from gasoline vehicle exhaust:Effects of engine technology,cold start,and emission certification standard[J].Environmental Science&Technology,2018,52(3):1253-1261．
[3]尹伊郡,刘金玉．HC吸附技术在整车排放中的应用[J]．汽车技术,2016(11):44-47.YIN Y J,LIU J Y.Application of HC adsorption technology in vehicle emissions[J].Automobile Technology,2016(11):44-47．
[4]侯亚帮,陈群,刘金玉,等．汽油机冷起动HC排放吸附技术分析研究[C]中国汽车工程学会．2014中国汽车工程学会年会论文集．北京：中国汽车工程学会,2014:4.HOU Y B,CHEN Q,LIU J Y,et al.HC adsorption for reducing gasoline engine cold-start emissions[C]Society of Automotive Engineers of China.Proceedings of 2014Annual Meeting of China Society of Automotive Engineering.Beijing:Society of Automotive Engineers of China,2014:4．
[5]武卫东,王闯,孟晓伟,等．含添加剂沸石分子筛混合吸附剂物理特性及其制冷应用性能[J]．化工进展,2016,35(3):692-699.WU W D,WANG C,MENG X W,et al.Physical properties and refrigeration performance of compound adsorbent composed of additive and zeolite molecular sieve[J].Chemical Industry and Enginering Progress,2016,35(3):692-699
[6]GUO G,ARBOR A,CAVATAIO G,et al.Use of transition metals to reduce cold start emissions:US20170050181A1[P].2017-02-23．
[7]ZHANG L,PENG X X,ZHANG J,et al.Adsorptive and catalytic properties in the removal of volatile organic compounds over zeolite-based materials[J].Chinese Journal of Catalysis,2016,37(6):800-809．
[8]BURKE N R,TRIMM D L,HOWE R F.The effect of silica:Alumina ratio and hydrothermal ageing on the adsorption characteristics of BEA zeolites for cold start emission control[J].Applied Catalysis B:Environmental,2003,46(1):97-104．
[9]刘伟,李立清,刘峥,等．甲苯吸附与活性炭孔隙结构关系的研究[J]．化学工业与工程,2011,28(4):5-10,21.LIU W,LI L Q,LIU Z,et al.Relationship between toluene adsorption capacity and pore structure of activated carbon[J].Chemical Industry and Engineering,2011,28(4):5-10,21．
[10]李文秀,许天行,范俊刚,等．噻吩类硫化物在Ag(I)X分子筛上的选择性吸附[J]．石油学报(石油加工),2013,29(5):870-875.LI W X,XU T X,FAN J G,et al.Selective adsorption of thiophenic sulfur compound on Ag(Ⅰ)X adsorbent[J].Acta Petrolei Sinica(Petroleum Process Section),2013,29(5):870-875．
[11]贾振,王尊海,姜翠玉,等．铈改性Hβ分子筛催化苯酐法合成蒽醌的研究[J]．应用化工,2009,38(9):1330-1334.JIA Z,WANG Z H,JIANG C Y,et al.Study on catalytic synthesis of an thraquinone form phthalic anhydride process over Hβzeolite modified by cerium[J].Applied Chemical Industry,2009,38(9):1330-1334．
[12]BURK P,HOCHMUTH J,ANDERSON D,et al.Cold start hydrocarbon emissions control[J].Automotive Engineering,1995,103(10):124478.https:www.osti.gov/biblio/124478．
[13]梁英,吴德生,毛炯,等．汽油车尾气采样装置的设计及其收集物的成份分析[J]．四川大学学报(工程科学版),2008,40(1):69-73.LIANG Y,WU D S,MAO J,et al.Composition analysis of tail gas emitted by automobile using gasoline as fuel[J].Journal of Sichuan University(Engineering Science Edition),2008,40(1):69-73．
[14]邓起发,时平平．汽油车尾气挥发性有机物成分谱特征研究[J]．环境与发展,2017,29(1):59-62.DENG Q F,SHI P P.Study on the characteristics of VOCs source profiles of gasoline vehicle exhaust[J].Environment and Development,2017,29(1):59-62．
[15]耿尧．沸石分子筛离子交换及其对碳氢化合物的吸附性能研究[D]．北京：北京工业大学,2010.GENG R.Ion exchange modification and hydrocarbon adsorption performance of zeolites[D].Beijing:Beijing University of Technology,2010．
[16]刘伟．活性炭吸附VOCs与其孔结构构效关系研究[D]．长沙：中南大学,2011.LIU W.Relationship between VOCs and activated carbon pore structure[D].Changsha:Central South University,2011．
[17]蔺广森．Ce改性分子筛在机动车HC冷启动中的研究和应用[D]．昆明：昆明理工大学,2012.LIN G S.Study and application of Ce modified molecular sieve in vehicle HC cold start[D].Kunming:Kunming University of Science and Technology,2011．
[18]张子豪,石琎,陈铭夏,等．水热老化温度对Fe-Beta型分子筛NH3-SCR商业催化剂的影响[J]．工业催化,2017,25(8):41-47.ZHANG Z H,SHI J,CHEN M X,et al.Influence of hydrothermal aging temperatures on Fe-Beta zeolite commercial NH3-SCR catalyst[J].Industrial Catalysis,2017,25(8):41-47．
[19]朱子俊,潘再富,杨冬霞,等．改性Pd/USY分子筛甲苯的吸脱附性能研究[J]．贵金属,2020,41(1):10-19.ZHU Z J,PAN Z F,YANG D X,et al.Study on absorption and desorption of toluene on modified Pd/USY molecular sieves[J].Precious Metals,2020,41(1):10-19．
[20]段林海．沸石分子筛的吸附扩散及应用[D]．兰州：兰州大学,2006.DUAN L H.Adsorption and diffusion on zeolite and it′s application[D].Lanzhou:Lanzhou University,2006．
[21]杨小芹,刘雪景,刘海雄,等．白松木屑半焦与褐煤共气化过程中的协同效应[J]．物理化学学报,2014,30(10):1794-1800.YANG X Q,LIU X J,LIU H X,et al.Synergy effect in co-gasification of lignite and char of pine sawdust[J].Acta Physico-Chimica Sinica,2014,30(10),1794-1800．
[22]郝志显,赵海涛,王利军,等．微波辐射法合成SAPO-5分子筛中硅铝比对产物结晶度和甲苯吸附性能的影响[J]．物理化学学报,2009,25(5):829-834.HAO Z X,ZHAO H T,WANG L J,et al.Effects of Si/Al molar ratio on the crystallinity and toluene adsorption of SAPO-5synthesized under microwave radiation[J].Acta Physico-Chimica Sinica,2009,25(5):829-834．
[23]巴晓微,柳翱,刘颖,等．NH3-TPD法表征固体催化剂的酸性[J]．长春工业大学学报(自然科学版),2013,34(3):261-263.BA X W,LIU A,LIU Y,et al.Characterization of the surface acidity of solid catalysts with ammonia temperature-programmed desorption[J].Journal of Changchun University of Technology(Natural Science Edition),2013,34(3):261-263．
[24]郭强胜,毛东森,孟涛．超细HZSM-5分子筛硅/铝比对其催化甲醇制丙烯反应的影响[J]．石油学报(石油加工),2010,26(6):940-945.GUO S Q,MAO D S,MENG T.Effect of silica to alumina ratio superfine ZSM-5zeolite on the catalytic reaction of methanol to propene[J].Acta Petrolei Sinica(Petroleum Process Section),2010,26(6):940-945．
[25]周春何,卢晗锋,曾立,等．沸石分子筛和活性炭吸附/脱附甲苯性能对比[J]．环境污染与防治,2009,31(4):38-41,44.ZHOU C H,LU H F,ZENG L,et al.Relative performance of zeolites and activated carbon in gaseous phase adsorption and desorption of toluene[J].Environmental Pollution&Control,2009,31(4):38-41,44．
[26]GUILLEMOT M,MIJOIN J,MIGANARD S,et al.Volatile organic compounds(VOCs)removal over dual functional adsorbent/catalyst system[J].Applied Catalysis B:Environmental,2007,75(3/4):249-255．
[27]JIN K T,ZHANG T,YUAN S J,et al.Regulation of isobutane/1-butene adsorption behaviors on the acidic ionic liquids-functionalized MCM-22zeolite[J].Chinese Journal of Chemical Engineering,2018,26 (1):127-136．
[28]贾未鸣,秦玉才,张乐,等．Ce改性对Y型分子筛酸中心可接近性及催化活性的影响[J]．石油炼制与化工,2017,48(6):14-19.JIA W M,QIN Y C,ZHANG L,et al.Study on accessibility and catalytic activity of Y zeolite modified by Ce-species[J].Petroleum Processing and Petrochemicals,2017,48(6):14-19.
基本信息:
中图分类号:TQ424;X701
引用信息:
[1]潘再富,黄卫强,张慧峰,等.CeO_2修饰对分子筛吸附甲苯的影响[J].有色金属(冶炼部分),2021(07):83-91.
基金信息:
国家自然科学基金资助项目(21862010,51964032)
2021-07-12
2021-07-12