烃类选择氧化过程中自由基的调控策略与工业氧化应用研究进展  

Progress on the regulation strategy of free radicals in the selective oxidation of hydrocarbons and its industrial application

作　　者：周贤太[1] 薛灿 纪红兵[2,3] ZHOU Xiantai;XUE Can;JI Hongbing(Fine Chemical Industry Research Institute,School of Chemical Engineering and Technology,Sun Yat-sen University,Zhuhai 519082,Guangdong,China;Fine Chemical Industry Research Institute,School of Chemistry,Sun Yat-sen University,Guangzhou 510275,Guangdong,China;School of Chemical Engineering,Guangdong University of Petrochemical Technology,Maoming 525000,Guangdong,China)

机构地区：[1]中山大学精细化工研究院,化学工程与技术学院,广东珠海519082 [2]中山大学精细化工研究院,化学学院,广东广州510275 [3]广东石油化工学院化学工程学院,广东茂名525000

出　　处：《化工进展》2021年第4期2070-2081,共12页Chemical Industry and Engineering Progress

基　　金：国家自然科学基金(21938001,21878344,21908256);国家自然科学基金-石油化工联合基金(U1663220);“珠江人才计划”本土创新科研团队项目(2017BT01C102);广东石油化工学院科研团队建设项目;惠州市科技计划(2017X0103003,2017G0516063)。

摘　　要：催化烃类氧化是提供合成树脂、合成纤维和合成橡胶等大宗化学品以及各类精细化学品的基本工艺,在化学工业中具有重要的地位。目前工业上的烃类氧化工艺普遍需要高温高压条件,苛刻条件可以使氧气活化及碳氢键断裂产生自由基。本文从均相催化、非均相催化、仿生催化等方面对近年来催化氧化反应的研究进展进行了回顾,梳理了催化氧化中的自由基机理。总结了仿生催化体系中自由基稳定性和定向性调控机制等方面的研究现状,提出了高效催化剂的设计、自由基的传递及调控机制等方面将是催化氧化领域的重要研究方向。Catalytic oxidation is a basic process for the bulk chemicals production such as synthetic resin,synthetic fiber and synthetic rubber,as well as various fine chemicals,which plays an important role in the chemical industry.At present,the industrial hydrocarbon oxidation process generally in conducted under high temperature and pressure conditions.Molecular oxygen is activated,and free radicals could be generated from the cleavage of C—H bond under such harsh conditions.In this paper,the research progress of catalytic oxidations in recent years were reviewed from homogeneous,heterogeneous and biomimetic catalysis etc.The mechanisms of free radical in catalytic oxidation were analyzed.The developments of free radical stability and directional regulation mechanism in biomimetic catalytic system were summarized.It was proposed that the design of efficient catalyst,the transfer and regulation mechanism of free radical would be the significant research in the field of catalytic oxidation.

关 键 词：氧化 自由基 碳氢化合物 催化 选择性 

分 类 号：TQ224.7[化学工程—有机化工]