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

doi:10.16085/j.issn.1000-6613.2020-2443

摘要/Abstract

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。

关键词: 氧化, 自由基, 碳氢化合物, 催化, 选择性

Abstract:

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.

Key words: oxidation, radical, hydrocarbons, catalysis, selectivity

中图分类号:

TQ224.7

周贤太, 薛灿, 纪红兵. 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[J]. 化工进展, 2021, 40(4): 2070-2081.

ZHOU Xiantai, XUE Can, JI Hongbing. Progress on the regulation strategy of free radicals in the selective oxidation of hydrocarbons and its industrial application[J]. Chemical Industry and Engineering Progress, 2021, 40(4): 2070-2081.

图/表 11

表1 典型的烃类液相选择性氧化工艺及反应条件

原料	产物	反应条件			转化率/%	选择性/%	典型工艺
原料	产物	温度/℃	压力/MPa	催化剂	转化率/%	选择性/%	典型工艺
异丁烷	叔丁基过氧化氢	140	3.5	引发剂	25	60	Oxirane
环己烷	环己醇和环己酮	165	1.5	Co和Mn盐	5	85	DuPont
甲苯	苯甲酸	165	1.0	Co和Mn盐	90	95	Amoco
对二甲苯	对二苯甲酸	200	3.0	Co和Mn盐	95	90	Amoco
异丙苯	异丙苯过氧化氢	140	0.5	引发剂	30	95	Oxirane

图1 乙酸铜催化烷烃C—H键氧化

图2 常见有机催化剂和C—H键的键解离能

图3 NHPI参与下的C—H键氧化机理

图4 Co/NHPI催化芳烃侧链的选择性氧化

图5 Au-Pd/MIL-101催化氧化环己烷

图6 金属卟啉仿生催化丙烯液相选择性环氧化的性能与原位紫外表征

图7 铁卟啉仿生催化的氧气活化过程

图8 锰卟啉仿生催化甲苯-环己烯共氧化

图9 仿生催化二苯甲烷氧化中的自由基传递和可能机理

图10 仿生催化氧化制备ε-己内酯300t/a的中试现场及装置

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