适用于丙烯二聚反应非均相催化剂的研究进展

Advances in heterogeneous catalysts for propylene dimerization

丙烯二聚反应是生产4-甲基-1-戊烯、1-己烯等端碳烯烃的重要手段,其产物可作为特种高分子材料单体、汽油添加剂和化工有机中间体,关键技术在于高效催化剂的开发。非均相催化剂相比于均相催化剂因易回收、对环境污染小等优点受到了学者们的广泛关注。本文综述了丙烯二聚非均相催化剂的研究进展,依据固体碱催化剂与固体酸催化剂在丙烯二聚反应中不同的反应机理,比较了两者各自的优缺点。回顾了固体碱催化剂的发展历程及工业化应用,并以碱金属钾为例总结了反应机理。详细介绍了固体酸催化剂中的固体磷酸催化剂、分子筛催化剂和负载型过渡金属催化剂。针对固体碱催化剂制备条件苛刻等问题,提出了改善催化装置的新思路;针对固体酸催化剂选择性不足的劣势,指出了应该进一步完善机理,并合理设计酸性载体与过渡金属相结合的催化剂。

Propylene dimerization is an important reaction for producing terminal alkenes,including 4-methyl-1-pentence and 1-hexene,which are widely used as special polymer monomers,gasoline additives,and organic intermediates in chemical industry.The conversion of propylene and the product selectivity are largely determined by the catalysts used in the propylene dimerization.Heterogeneous catalysts have attracted wide attentions due to their advantages of easy recovery and relatively small environmental pollution,compared with homogeneous catalysts.Based on different reaction mechanisms,the solid base catalysts and solid acid catalysts used in the propylene dimerization have been systematically reviewed.The development and industrial applications of solid base catalysts in propylene dimerization have been introduced and their reaction mechanisms have been summarized by taking alkali metal potassium as an example.The solid acid catalysts of phosphoric acid catalyst,molecular sieve catalyst and transition metal catalyst are introduced in detail.In view of the harsh preparation conditions of solid base catalyst,we proposed a new idea to improve the catalytic unit.To increase the insufficient selectivity of solid acid catalysts,we pointed out that the reaction mechanism should be further studied and the catalyst combining acid carrier and transition metal should be designed reasonably to achieve high selectivity of the dimer products.