Beta分子筛催化桥式双环戊二烯异构反应.docVIP

  Beta 分子筛催化桥式双环戊二烯异构反应# 邹吉军，韩红* （天津大学化工学院，天津 300072） 5 10 摘要：采用 Hβ分子筛为催化剂，在液相体系中将桥式双环戊二烯(endo-DCPD)异构为挂式 双环戊二烯(exo-DCPD)。无催化剂时双环戊二烯主要发生聚合反应，加入催化剂后生成了 大量 exo-DCPD。在分子筛表面沉积 SiO2 可提高反应选择性，说明异构反应发生在分子筛 孔道内，而外表面主要引发聚合副反应。低硅铝比的分子筛含有大量强度较弱的 Lewis 酸性 位，在异构反应中的活性最高，说明弱酸性位是异构的活性中心。对分子筛焙烧温度考察发 现，焙烧温度过低时分子筛的 L 酸位较少，温度过高时 L 酸变强而且结晶度急剧下降，500 °C 焙烧的分子筛异构化性能最佳，证明分子筛异构是孔结构和弱 L 酸性中心协同作用的结 果。 关键词：桥式双环戊二烯；挂式双环戊二烯；H-beta 分子筛；异构反应 中图分类号：O622.1; TQ51 文献标识码：A 15 Beta Zeolite Catalytic Isomerization of endo-Dicyclopentadiene ZOU Jijun, HAN Hong (School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072) 20 Abstract: Hβ-catalytic isomerization of endo-dicyclopentadiene (endo-DCPD) to exo-dicyclopentadiene (exo- DCPD) in liquid phase was studied. With the absence of zeolite, DCPD is converted into oligomers and the formation of exo-DCPD is neglectable. With the presence of Hβ, considerable amount of exo-DCPD is formed. Passivation of the external surface with amorphous silica layer improves the selectivity of isomerization reaction with a little decline 25 30 35 40 in conversion. This means that the isomerization reaction occurs inside the pore of zeolite, meanwhile the external acidity accelerates the undesired oligomerizations. Hβ with low SiO2/Al2O3 ratio contains highest concentration of weak Lewis acid, and exhibits highest activity, confirming that weak L acidity is the active site for the isomerization. The calcination temperature has great influence on the acidity and porous structure of zeolite. The amount of weak L acid is not enough at low temperature, while the framework and pores are destroyed at high temperature. Calcination at 500°C produces enough weak L acid and keeps relatively well crystallinity, thereby providing best catalytic performance. Key words: endo-dicyclopentadiene; exo-dicyclopentadiene; H-beta; isomerization 0 引言 双环戊二烯(DCPD)是石脑油裂解制乙烯的 C5 副产物，具有两种空间构型不同的异构 体：桥式双环戊二烯(endo-DCPD)和挂式双环戊二烯(exo-DCPD)，两种异构体的比例分别是 99.5%和 0.5%[1]。