多级孔β分子筛在噻吩烷基化反应中的催化性能
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摘要
将β分子筛用NaOH溶液处理后得到多级孔β分子筛,采用XRD、SEM、FTIR、N_2吸附-脱附、XRF和NH_3-TPD方法对处理前后的β分子筛进行表征,并研究了它在噻吩烷基化反应中的催化性能。表征结果显示,NaOH溶液处理在保持β分子筛微孔骨架结构的同时,增加了它的介孔比表面积和介孔体积,并调变了酸性。实验结果表明,在反应压力0.85 MPa、反应温度160℃、反应时间2 h、催化剂质量1 g的条件下,以0.1 mol/L NaOH溶液处理60 min得到的多级孔β分子筛作为催化剂时,噻吩转化率和烷基化选择性最高,分别为94.6%和70.1%。
Hierarchical β zeolites were obtained by β zeolites treated with NaOH solutions. The hierarchical β zeolites were characterized by XRD,SEM,FTIR,XRF,N_2 adsorption-desorption and NH_3-TPD techniques. The catalytic performances of β zeolites in thiophene alkylation reaction were investigated. The results showed that the mesoporous surface area and mesoporous volume of the β zeolites were enhanced through NaOH treatment and the acidity was modulated without altering the microporous structure of β zeolites.Under the conditions of reaction pressure 0.85 MPa,reaction temperature 160 ℃,reaction time 2 h and catalyst 1 g,the conversion of thiophene and alkylation selectivity could reach 94.6% and 70.1% respectively,when the hierarchical β zeolite was treated with 0.1 mol/L NaOH for 60 min.
Hierarchical β zeolites were obtained by β zeolites treated with NaOH solutions. The hierarchical β zeolites were characterized by XRD,SEM,FTIR,XRF,N_2 adsorption-desorption and NH_3-TPD techniques. The catalytic performances of β zeolites in thiophene alkylation reaction were investigated. The results showed that the mesoporous surface area and mesoporous volume of the β zeolites were enhanced through NaOH treatment and the acidity was modulated without altering the microporous structure of β zeolites.Under the conditions of reaction pressure 0.85 MPa,reaction temperature 160 ℃,reaction time 2 h and catalyst 1 g,the conversion of thiophene and alkylation selectivity could reach 94.6% and 70.1% respectively,when the hierarchical β zeolite was treated with 0.1 mol/L NaOH for 60 min.
引文
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[24]Groen J C,AbellóS,Villaescusa L A,et al.Mesoporous beta zeolite obtained by desilication[J].Microporous Mesoporous Mater,2008,114(1/3):93-102.
[25]Groen J C,Peffer L A A.On the introduction of intracrystalline mesoporosity in zeolites upon desilication in alkaline medium[J].Microporous Mesoporous Mater,2004,69(1/2):29-34.
[26]刘冬梅,翟玉春,马健,等.碱改性ZSM-5分子筛及脱硫性能的研究[J].中国稀土学报,2015,33(1):39-47.
[27]Ogura M,Shinomiya S Y,Tateno J,et al.Alkali-treatment technique—New method for modification of structural and acid-catalytic properties of ZSM-5 zeolites[J].Appl Catal,A,2001,219(1/2):33-43.
[2]柯明,周爱国,赵振盛,等.FCC汽油烷基化脱硫技术进展[J].化工进展,2006,25(4):357-361.
[3]马健,刘冬梅,王海彦,等.烷基化脱除FCC汽油中噻吩硫研究进展[J].当代化工,2013(9):1288-1290.
[4]BP Amoco Corporation.Sulfur removal process:US6024865[P].2000-02-15.
[5]常振勇.汽油噻吩硫的烷基化脱除技术[J].炼油技术与工程,2002,32(5):44-46.
[6]Davis M E.Ordered porous materials for emerging applications[J].Nature,2002,417(6891):813-821.
[7]Jaimes L,Lasa H D.Catalytic conversion of thiophene under mild conditions over a ZSM-5 catalyst.A kinetic model[J].Ind Eng Chem Res,2009,48(16):7505-7516.
[8]Jaimes L,Badillo M,de Lasa H.FCC gasoline desulfurization using a ZSM-5 catalyst interactive effects of sulfur containing species and gasoline components[J].Fuel,2011,90(5):2016-2025.
[9]Hu Linyan,Zhang Zekai,Xie Sujuan,et al.Effect of grain size of zeolite Y on its catalytic performance in olefin alkylation thiophenic sulfur process[J].Catal Commun,2009,10(6):900-904.
[10]Zheng Xuedong,Dong Hongjun,Wang Xin,et al.Study on olefin alkylation of thiophenic sulfur in FCC gasoline using La2O3-modified HY zeolite[J].Catal Lett,2009,127(1):70-74.
[11]魏书梅,徐亚荣,徐新良,等.HY分子筛催化噻吩类硫化物的烷基化反应动力学[J].化学反应工程与工艺,2012,28(2):159-163.
[12]范立,沈健.USY分子筛催化FCC汽油烷基化脱硫工艺条件的研究[J].应用化工,2014(7):1303-1306.
[13]Dupuy B,Laforge S,Bachmann C,et al.Desulfurization of model FCC feedstocks by alkylation:Transformation of thiophenic compounds in presence of 2-methyl-1-pentene over acidic zeolites[J].J Mol Catal A:Chem,2012,363/364:273-282.
[14]郭晓野,张泽凯,刘盛林,等.汽油在钾修饰MCM-22分子筛上的烷基化脱硫[J].工业催化,2008,16(6):31-34.
[15]张泽凯,刘盛林,杜喜研,等.芳烃烷基化反应性能对烷基化脱除汽油中硫化物过程的影响[J].石油化工,2006,35(2):113-117.
[16]Zhang Zekai,Liu Shenglin,Zhu Xiangxue,et al.Modification of Hβzeolite by fluorine and its influence on olefin alkylation thiophenic sulfur in gasoline[J].Fuel Process Technol,2008,89(1):103-110.
[17]Hartmann M.Hierarchical zeolites:A proven strategy to combine shape selectivity with efficient mass transport[J].Angew Chem,Int Ed,2004,43(44):5880-5882.
[18]Pérez-Ramírez J,Christensen C H,Egeblad K,et al.Hierarchical zeolites:Enhanced utilisation of microporous crystals in catalysis by advances in materials design[J].Chem Soc Rev,2008,37(11):2530-2542.
[19]Fang Nagu,Feng Wei,Jia Yuanyang,et al.New strategy to synthesis of hierarchical mesoporous zeolites[J].Chem Mater,2010,22(8):2442-2450.
[20]赵岑,刘冬梅,魏民,等.多级孔ZSM-5分子筛的制备及催化噻吩烷基化性能研究[J].燃料化学学报,2013,41(10):1256-1261.
[21]刘冬梅,铁大兴,高晨义,等.混合碱处理制备微介孔催化剂及其噻吩烷基化催化性能[J].燃料化学学报,2017,45(2):200-212.
[22]毛艳红,刘冬梅,魏民,等.碱处理ZSM-5分子筛催化噻吩烷基化反应性能及其反应动力学[J].石油学报:石油加工,2017,33(4):746-756.
[23]Tang Yanting,Liu Xiufeng,Nai Shifeng,et al.Templatefree synthesis of beta zeolite membranes on porousα-Al2O3support[J].Chem Commun,2014,50(64):8834-8837.
[24]Groen J C,AbellóS,Villaescusa L A,et al.Mesoporous beta zeolite obtained by desilication[J].Microporous Mesoporous Mater,2008,114(1/3):93-102.
[25]Groen J C,Peffer L A A.On the introduction of intracrystalline mesoporosity in zeolites upon desilication in alkaline medium[J].Microporous Mesoporous Mater,2004,69(1/2):29-34.
[26]刘冬梅,翟玉春,马健,等.碱改性ZSM-5分子筛及脱硫性能的研究[J].中国稀土学报,2015,33(1):39-47.
[27]Ogura M,Shinomiya S Y,Tateno J,et al.Alkali-treatment technique—New method for modification of structural and acid-catalytic properties of ZSM-5 zeolites[J].Appl Catal,A,2001,219(1/2):33-43.