催化学报

催化学报 ›› 2018, Vol. 39 ›› Issue (1): 181-189.DOI: 10.1016/S1872-2067(17)62985-1

• 论文 • 上一篇    

氧化铈改性多级孔Hβ分子筛催化对二甲苯与苯乙炔烯基化反应

郭永乐a, 张钰b, 赵忠奎a   

  1. a 大连理工大学化工与环境生命学部精细化工国家重点实验室, 辽宁大连 116024;
    b 大连理工大学体育教学部, 辽宁大连 116024
  • 收稿日期:2017-10-12 修回日期:2017-11-24 出版日期:2018-01-18 发布日期:2018-01-19
  • 通讯作者: 赵忠奎
  • 基金资助:

    国家自然科学基金（21276041，U1610104）；教育部新世纪优秀人才支持计划（NCET-12-0079）.

Ceria-modified hierarchical Hβ zeolite as a robust solid acid catalyst for alkenylation of p-xylene with phenylacetylene

Yongle Guoa, Yu Zhangb, Zhongkui Zhaoa   

  1. a State Key Laboratory of Fine Chemicals, Department of Catalysis Chemistry and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China;
    b Department of Physical Education, Dalian University of Technology, Dalian 116024, Liaoning, China
  • Received:2017-10-12 Revised:2017-11-24 Online:2018-01-18 Published:2018-01-19
  • Contact: 10.1016/S1872-2067(17)62985-1
  • Supported by:

    This work was supported by the National Natural Science Foundation of China (21276041, U1610104) and the Chinese Ministry of Education via the Program for New Century Excellent Talents in University (NCET-12-0079).

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摘要：

烯基芳香化合物是重要的精细化学品及中间体，在医药、染料、农药、香料、新型高分子材料和天然产品等化学工业领域得到广泛应用.传统工艺采用芳香化合物与烯基化合物的反应合成烯基芳香化合物.但是，传统过程存在许多不足：（1）芳环需预活化，如卤代等；（2）伴生氢卤酸等废物，污染环境；（3）原子经济性差.因此，研究烯基芳香化合物的清洁、高原子经济性合成备受关注.采用芳香化合物与炔基化合物的烯基化，可以100%原子经济性地合成烯基芳香化合物，且芳环无需预活化，不产生废弃物.因此，通过芳香化合物与炔的烯基化路线来合成烯基芳香化合物引起了人们的极大兴趣.尤其是固体酸催化烯基化，工艺成本低，清洁无污染，颇具工业前景.然而，固体酸催化烯基化不同于烷基化，烯基阳离子稳定性很差，比碳正离子易于聚合，进而导致催化剂积碳失活.微孔沸石分子筛用于烯基化存在底物适用范围窄、催化效率低、选择性差和炔聚合严重的问题.本研究组开展了硫酸化的镧锆氧化物介孔固体超强酸、担载磷钨酸介孔固体酸催化烯基化.采用前者，合成有序的介孔镧锆氧化物较为困难；而采用后者，催化剂的再生需要大量有机溶剂，会造成环境污染.硅铝分子筛固体酸易于制备，且可以通过简单的焙烧来再生.多级孔分子筛具有微孔分子筛和介孔分子筛的双重优势，用于烯基化反应可望获得良好效果.
本文采用碱、酸对商业微孔β沸石分子筛进行处理，通过脱硅、脱铝过程来合成多级孔β分子筛，并进行稀土金属铈改性，从而制备了氧化铈改性的多级孔β分子筛，研究了其催化对二甲苯与苯乙炔的烯基化反应.通过改变碱浓度和酸浓度，对所制备的多级孔β分子筛的织构性质和酸性质进行调控，在优化的条件下获得了良好的烯基化催化性能，得到95.8%的苯乙炔转化率和95.1%的目标产物α-2，5-二甲苯基苯乙烯的选择性，总的烯基化产物（α-和β-烯基芳香化合物）的选择性达到98%.相对于微孔β分子筛，所制备的多级孔β分子筛展示了显著增强的催化活性和稳定性，目标产物选择性也有所提高.显著提高的催化性能归因于多级孔分子筛的传质强化和酸性位的增多.氧化铈的改性使得多级孔β分子筛的弱、中等和强酸中心的数目减少，可能源于减少了表面暴露的B酸位，从而导致了催化稳定性的显著提高.可见，本文所制备的氧化铈改性多级孔β分子筛用于烯基化反应具有一定前景.

关键词: 多级孔分子筛, 烯基化, 清洁合成, 烯基芳香化合物, 多相催化

Abstract:

A ceria-modified hierarchical Hβ zeolite was prepared by a desilication-dealumination procedure followed by ceria modification. The catalytic performance of the ceria-modified and unmodified hierarchical Hβ zeolite catalysts for alkenylation of p-xylene with phenylacetylene was investigated. Various characterization techniques, including X-ray diffraction, X-ray fluorescence, nitrogen adsorption-desorption, and NH3 temperature-programmed desorption, were used to examine the structure-performance relationships. Our results show that the optimized ceria-modified hierarchical Hβ zeolite catalyst demonstrated higher catalytic activity, selectivity, and stability for alkenylation of p-xylene with phenylacetylene than those of pristine Hβ zeolite. This performance was attributed to more acidic sites and improved accessibility to active sites through larger pores, together with a higher mesoporous surface area and volume resulting from the hierarchical pore architecture and ceria modification. Thus, our 5 wt% CeO2-Hβ-B0.2A0.2 catalyst shows great potential for producing alkenyl aromatics through solid acid catalyzed alkenylation.

Key words: Hierarchical beta zeolite, Desilication and dealumination, Ceriamodification, Heterogeneous catalysis, Alkenylation