物理化学学报 >> 2003, Vol. 19 >> Issue (03): 216-220.doi: 10.3866/PKU.WHXB20030306

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杂原子取代型磷酸铝分子筛上丁烯异构化反应

汪哲明;阎子峰   

  1. 石油大学重质油加工国家重点实验室,CNPC催化重点实验室,东营　257061
  • 收稿日期:2002-05-23 修回日期:2002-08-21 发布日期:2003-03-15
  • 通讯作者: 汪哲明 E-mail:zfyancat@hdpu.edu.cn

Skeletal Isomerization of Butene on Si, Zr-substituted Aluminum Phosphate Zeolites

Wang Zhe-Ming;Yan Zi-Feng   

  1. State Key Laboratory for Heavy Oil Processing, CNPC Key Laboratory of Catalysis, University of Petroleum, Dongying　257061
  • Received:2002-05-23 Revised:2002-08-21 Published:2003-03-15
  • Contact: Wang Zhe-Ming E-mail:zfyancat@hdpu.edu.cn

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摘要： 采用水热法合成了Si、Zr杂原子取代的磷酸铝分子筛（APO-11）.研究发现,它们(SAPO-11、ZAPO-11)与APO-11分子筛骨架结构相同（AEL型）；三者表面形貌不同,SAPO-11与APO-11分子筛同为球形颗粒,而ZAPO-11则为棒状晶粒.杂原子的取代能改变APO-11分子筛的酸性质以及微孔分布.反应评价显示,异构化活性SAPO-11>> ZAPO-11 > APO-11；其中SAPO-11分子筛,当Si/Al=0.15时,异构化性能最佳.异构化反应的因子（时间、分压、温度）系统考察发现,主要副产物C3、C5＋与i-C4=的浓度呈现不同的变化趋势,从而证实丁烯选择性异构是通过单分子机理实现的,C3、C5＋是通过双分子历程生成的.

关键词: 杂原子取代, 磷酸铝分子筛, 丁烯异构化反应, 单分子机理, 双分子机理

Abstract: Si, Zr-substituted aluminumphosphate zeolites were synthesized by hydrothermal method. XRD data indicated that they bear the same AEL structure with APO-11 zeolite. Of interest is that the crystal shape of SAPO-11 and APO-11 all are sphere-like, while ZAPO-11 exists as bar-like. Simultaneously, the introduction of heteroatoms in APO-11 skeleton could lead to the positive modification of acidity and micropore features. SAPO-11 showed higher acidity and ZAPO-11 possessed less micropore volume. Of special is that SAPO-11 with Si/Al =0.15 is the optimum shape-selective catalyst of skeletal isomerization of butene. The isomerization effect factors, such as butene partial pressure, temperature, were also extensively investigated. Of special is that the inconsistency in concentration changes between product isobutene and by-product, C3 and C5, was continually occurred while the reaction parameters were accordingly changed. It indicated that isobutene is shape-selectively formed via mono-imolecule mechanism, while the by-products C3 and C5 are mainly formed via bimolecular mechanism.

Key words: Heteroatomic substitution, Aluminumphosphate zeolites, Isomerization of butene, Mono-molecular mechanism, Dimolecular mechanism