物理化学学报 >> 2014, Vol. 30 >> Issue (8): 1518-1526.doi: 10.3866/PKU.WHXB201405271

催化和表面科学 上一篇    下一篇

介孔ZSM-5沸石微球催化剂上萘的苄基化反应

苗海霞1,2, 马丽1, 马静红1, 李对春1, 李瑞丰1   

  1. 1. 太原理工大学精细化工研究所, 太原 030024;
    2. 晋城职业技术学院化工系, 山西晋城 048000
  • 收稿日期:2014-04-02 修回日期:2014-05-26 发布日期:2014-07-18
  • 通讯作者: 马静红 E-mail:majinghong@tyut.edu.cn
  • 基金资助:

    国家自然科学基金(51272169,21246003)资助项目

Benzylation of Naphthalene over a Mesoporous ZSM-5 Zeolite Microsphere Catalyst

MIAO Hai-Xia1,2, MA Li1, MA Jing-Hong1, LI Dui-Chun1, LI Rui-Feng1   

  1. 1. Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, P. R. China;
    2. Department of Chemistry Engineering, Jincheng Institute of Technology, Jincheng 048000, Shanxi Province, P. R. China
  • Received:2014-04-02 Revised:2014-05-26 Published:2014-07-18
  • Contact: MA Jing-Hong E-mail:majinghong@tyut.edu.cn
  • Supported by:

    majinghong@tyut.edu.cn

摘要:

以有机硅烷化的二氧化硅为硅源,制备了由纳米粒子聚集而成的、具有晶间和晶内介孔的微球状ZSM-5(MMZ-5)沸石. 通过吡啶(Py)和2,6-二叔丁基吡啶(DTBPy)在介孔沸石表面吸附的原位红外测试,对其酸性进行了表征. 与微孔ZSM-5 沸石相比,MMZ-5 沸石上的Lewis 酸位和总酸位增加,特别是探针大分子DTBPy(动力学直径约为1.05 nm)可及的Brönsted 酸位显著提高. 萘在MMZ-5沸石上的苄基化催化结果表明,反应发生在拥有大量活性位的沸石外表面,大的沸石外表面为该催化反应提供了作用空间,从而提高了沸石活性位的有效利用率,使MMZ-5 沸石上萘的苄基化反应活性显著提高,能够生成大分子产物一苄基萘和二苄基萘;其中,一苄基萘的选择性约为79%,且随着反应时间的延长,MMZ-5 沸石大的晶内介孔(3-5 nm)为反应提供了有效反应空间,促进一苄基萘向二苄基萘转化. 异构体α-一苄基萘和β-一苄基萘的摩尔比值约为83:17,该值不随着温度和转化率的变化而改变.

关键词: 萘, 苄基化, 介孔ZSM-5沸石, 酸性, 大分子催化

Abstract:

A microspherical ZSM-5 zeolite aggregated from nanosized zeolite crystals with intra- and intercrystalline mesoporous structures (MMZ- 5) was prepared using presilanized silica as silica source. The acidic properties of this mesoporous zeolite were characterized via Fourier transform infrared spectroscopy (FTIR) in combination with pyridine (Py) and 2,6-di-tert-butylpyridine (DTBPy). Compared with conventional microporous ZSM- 5, the MMZ- 5 zeolite possessed more Lewis acid sites and many more accessible Brönsted acid sites for bulky DTBPy molecule (1.05 nm in diameter). This mesoporous zeolite thus afforded both effective active sites and reaction voids allowing the reaction of larger molecules, resulting in enhanced catalytic activity and stability of the MMZ-5 zeolite during the benzylation of naphthalene with benzyl chloride (BC) to form bulky monobenzylnaphthalenes and dibenzylnaphthalenes, during which the selectivity for monobenzylnaphthalenes was estimated to be about 79%. Moreover, the selectivity for dibenzylnaphthalenes was enhanced with increasing reaction time, owing to the consecutive reactions between monobenzylnaphthalenes and BC occurring at the effective reaction voids of the MMZ-5 zeolite. The distribution of the monobenzylnaphthalene isomers (α-BN and β-BN) was found to be independent of both reaction temperature and extent of BC conversion, the α-BN/β-BN molar ratio being about 83:17.

Key words: Naphthalene, Benzylation, Mesoporous ZSM-5 zeolite, Acidity, Bulky molecular catalysis

MSC2000: 

  • O643