化工学报 ›› 2015, Vol. 66 ›› Issue (10): 3911-3918.DOI: 10.11949/j.issn.0438-1157.20150187

• 催化、动力学与反应器 • 上一篇    下一篇

负载碱催化剂在Prins反应中的应用

王海永, 吕慧, 林晨, 朱振炜, 许康栋, 曹贵平   

  1. 华东理工大学化学工程联合国家重点实验室, 上海 200237
  • 收稿日期:2015-02-05 修回日期:2015-05-25 出版日期:2015-10-05 发布日期:2015-10-05
  • 通讯作者: 曹贵平
  • 基金资助:

    中国博士后科学基金项目(2014M551347)。

Application of supported alkali catalysts in Prins reaction

WANG Haiyong, LÜ Hui, LIN Chen, ZHU Zhenwei, XU Kangdong, CAO Guiping   

  1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
  • Received:2015-02-05 Revised:2015-05-25 Online:2015-10-05 Published:2015-10-05
  • Supported by:

    supported by the China Postdoctoral Science Foundation (2014M551347).

摘要:

分别采用浸渍法和共沉淀法制备了负载金属氧化物的固体碱催化剂MnO/Al2O3 (M=Na,K,Cs,Mg,Ca,Sr;n=1,2)和C-Cs2O/Al2O3,测定了催化剂的碱量和pKa值,分别采用CO2-TPD、X射线衍射、N2物理吸附表征了催化剂的物理化学性质。以异丁烯与多聚甲醛经Prins反应制备3-甲基-3-丁烯-1-醇(MBO)为体系考察催化剂活性。结果表明,催化剂的碱性和结构直接影响其催化活性,采用共沉淀法制备的Cs2O/Al2O3催化剂具有更强的碱性,表现出了优越的反应活性,甲醛的转化率和产物MBO的选择性分别为100.0%和86.0%。探讨了固体碱催化反应的机理,发现碱性位可以活化异丁烯的a-H,促进Prins反应。

关键词: 催化剂, 固体碱, Prins反应, 3-甲基-3-丁烯-1-醇, 机理

Abstract:

Solid base catalysts MnO/Al2O3 (M=Na, K, Cs, Mg, Ca, Sr, n=1 or 2) prepared by impregnation method and C-Cs2O/Al2O3 by co-precipitation method were applied in Prins reaction. Their base amount and pKa in water were determined. The structure and physico-chemical properties of the carrier and prepared catalysts were characterized by CO2-TPD, X-ray diffraction, and nitrogen adsorption. The performance of catalysts was evaluated by condensation reaction of isobutene with paraformaldehyde to produce 3-methyl-3-buten-1-ol. The results showed that the performance of catalysts related directly with their basic property and structure. The C-Cs2O/Al2O3 catalyst had stronger basicity and showed superior catalytic performance, and the conversion of formaldehyde and selectivity to MBO reached up to 100.0% and 86.0% respectively. The mechanism of Prins reaction over solid base catalyst was also discussed. The base sites could active the a-H of isobutene, and so could promote the Prins reaction.

Key words: catalyst, solid base, Prins reaction, 3-methyl-3-butene-1-ol, mechanism

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