以硅溶胶、硫酸铝、氢氧化钠、四丙基溴化铵以及硼酸和九水硝酸铁为原料,采用EU-1晶种,通过水热法合成了2种含杂原子的微孔结构ZSM-5/EU-1复合分子筛.采用XRD、SEM、N2吸附-脱附和NH3-TPD对合成样品进行了表征,并在连续流动固定床反应器上考察了该分子筛催化剂对甲醇制二甲苯反应的催化性能.结果表明:含杂原子微孔结构的ZSM-5/EU-1复合分子筛同时具有ZSM-5和EU-1的特征衍射峰,结晶度较好,平均孔径明显增大,当催化剂的酸强度和酸量增大时,有利于甲醇芳构化趋势以及二甲苯优先扩散.B-ZSM-5/EU-1催化产物中芳烃在油相中的选择性达到84.70％; B-ZSM-5/EU-1和Fe-ZSM-5/EU-1两种分子筛催化产物的芳香烃中二甲苯的含量最高,分别为41.32％～45.88％和33.88％～39.16％.由于B-ZSM-5/EU-1较高的酸性、酸量和相对较小的孔道内径(0.8060 nm),较Fe-ZSM-5/EU-1更有利于产物中二甲苯的生成;不仅如此,B-ZSM-5/EU-1复合分子筛催化产物中对二甲苯在二甲苯中选择性范围为29.75％～47.47％;不过,Fe-ZSM-5/EU-1产物中对二甲苯在二甲苯中的含量最高可达53.75％,这是由于Fe-ZSM-5/EU-1复合分子筛的粒径较大,为催化反应提供了较长的孔道结构,易使产物中邻、间二甲苯在扩散过程中异构化转化为对二甲苯的缘故.
参考文献
| [1] | ZAIDI H A,PANT K K.Catalytic conversion of methanol to gasoline range hydrocarbons.Catalysis Today,2004,96(3):155-160. |
| [2] | FRANZ SCHMIDT,MARTIN LOHE R,BERND B(U)CHNER,et al.Improved catalytic performance of hierarchical ZSM-5 synthesized by desilication with surfactants.Microporous and Mesoporous Materials,2013,165(1):148-157. |
| [3] | ONO Y,ADACHI H.Selective conversion of methanol into aromatic hydrocarbon over zinc exchanged ZSM-5 zeolites.J.Chem.Soc.Faraday Trans.,1988,84:1091-1099. |
| [4] | GABRIELE M,JOHANNES A L.Transport and isomerization of xylenes over HZSM-5 zeolites.J Catal,1993,139:24-33. |
| [5] | NI YOU-MING,SUN AI-MING,WU XIAO-LING,et al.Aromatization of methanol over La/Zn/HZSM-5 catalysts.Chinese Journal of Chemical Engineering,2011,19(3):439-445. |
| [6] | BRISCOE N A,JOHNSON D W,SHANNON M D.The framework topology of zeolite EU-1.Zeolites,1988,8(1):74-76. |
| [7] | MARTINS J,BIROT E,GUILLON E,et al.Sodium exchange over H-EU-1 zeolite.Part Ⅱ:Catalytic properties.Microporous and Mesoporous Materials,2013,171(1):238-245. |
| [8] | MIHINDOU-KOUMBA P C,COMPAROT J D,LAFORGE S,et al.Methylcyclohexane transformation over H-EU-1 zeolite:Selectivity and catalytic role of the acid sites located at the pore mouths.J.Catal.,2008,255(2):324-334. |
| [9] | MOREAU F,MOREAU P,GNEP N S,et al.Ethylbenzene isomerization over bifunctional platinum alumina-EUO catalysts:location of the active sites.Microporous and Mesoporous Materials,2006,90(1/3):327-338. |
| [10] | MARLER B,DANIELS P,SA(N)(E)I MUN(E) J.Synthesis and structure of RUB-35,a disordered material of the EUO-NES-NON family.Microporous and Mesoporous Mater,2003,64(1/3):185-201. |
| [11] | 徐如人,庞文琴.分子筛与多孔材料化学.科学出版社,2004:269. |
| [12] | REN YONG-LI,LIU GUO-ZHU,MI ZHEN-TAO.Spectroscopic criteria of heteroatom into the zeolite framework structure.Chinese Journal of Chemistry,2004(6):433-438. |
| [13] | LIU YANG-QIAO,GAO LIAN.Study on inhibition of nano Y-TZP suspension reunion.Journal of Inorganic Materials,2002,17(6):1292-1296. |
| [14] | XIAO QI,WANG PING-HUA,JI LING-LING,et al.Influence of dispersant CTAB on dispersion of carbon nanotube suspensions.Journal of Inorganic Materials,2007,22(6):1123-1126. |
| [15] | ZHAO GUO-LIANG,TENG JIA-WEI,XIE ZAI-KU,et al.Characterization and carbon four olefin cracking catalytic properties of ammonium fluorosilicate modified HZSM-5 catalyst.Chinese Journal of Catalysis,2005,26(12):1083-1087. |
| [16] | ZHAO JUN-QIAO,SHEN ZHI-HONG,JU YA-NA,et al.Effects of boron atoms on the performances of Y molecular sieves.Journal of Petroleum Chemical Industry,2005,34(7):648-651. |
| [17] | ZHANG YING-ZHEN,XU HENG-YONG,ZHEN LU-SHAN,et al.Study on removal aluminum of faujasite.Chinese Journal of Catalysis,1988,9(4):366-372. |
| [18] | SONG YUE-QIN,ZHU XIANG-XUE,XU LONG-YA.Study on the process of transformation of olefin into aromatics over HZSM-5.Catal.Comm.,2006,7(4):218-223. |
| [19] | GUISNET M,GNEP N S.Mechanism of short-chain alkane transformation over protonic zeolites.Alkylation,disproportionation and aromatization.Appl.Catal.A:Gen.,1996,146(1):33-64. |
| [20] | CHANG FU-XIANG,WEI YING-XU.A mechanistic investigation of the coupled reaction of n-hexane and methanol over HZSM-5.Appl.Catal.A:Gen.,2007,328(2):163-173. |
| [21] | ROZANSKA X,VAN SANTEN R A,HUTSCHK F,et al.15-P-20-A DFT study of the isomerization reactions of aromatics catalyzed by acidic zeolites.Studies in Surface Science and Catalysis,2001,135:260-273. |
| [22] | GUISNET M,GNEP N S,MORIN S.Mechanisms of xylene isomerization over acidic solid catalysts.Microporous Mesoporous Mat.,2000,35-36:47-59. |
| [23] | CORTES A,CORMA A,NEBOT I.The mechanism of catalytic isomerization of xylenes:kinetic and isotopic studies.J.Catal.,1978,51(3):338-344. |
| [24] | ZENG ZHAO-HUAI,PAN GUI-SHENG.The adsorption and diffusion of xylene in ZSM-5 molecular sieve.Chinese Journal of Chemical Physics,1989,5(2):145-149. |
| [25] | HIROKI KONNO,TERUOKI TAGO,YUTA NAKASAKA,et al.Effectiveness of nano-scale ZSM-5 zeolite and its deactivation mechanism on catalytic cracking of representative hydrocarbons of naphtha.Microporous and Mesoporous Materials,2013,175(15):25-33. |
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