基于环己酮路线制备ε-己内酯工艺研究进展及工艺安全分析  

Research Progress and Process Safety Analysis in the Preparation Process of ε-Caprolactone based on Cyclohexanone Route

作　　者：王洪宇 Wang Hongyu(0x09State Key Laboratory of Chemical Safety,Shandong,Qingdao,266104;SINOPEC Research Institute of Safety Engineering Co.,Ltd.,Shandong,Qingdao,266104)

机构地区：[1]化学品安全全国重点实验室,山东青岛266104 [2]中石化安全工程研究院有限公司,山东青岛266104

出　　处：《安全、健康和环境》2023年第10期1-10,共10页Safety Health & Environment

摘　　要：为进一步推进ε-己内酯合成工业化进程,针对环己酮氧化制备ε-己内酯工艺路线存在的副产物多、燃爆风险高、催化剂稳定性差等问题,系统综述了国内外以环己酮为原料制备ε-己内酯工艺路线的研究进展,并分别阐述了过氧酸氧化法、双氧水氧化法、氧气氧化法及生物氧化法在该工艺应用的优势及存在问题。结果表明,过氧酸氧化法是当前工业化大规模生产ε-己内酯的方法,但该法存在副产有机酸及燃爆风险;从原子经济性角度考量,过氧化氢及氧气替代过氧酸作为氧化剂是绿色化工的发展方向;研发高效稳定的催化剂,弥补过氧化氢和氧气氧化能力弱的缺限,是双氧水氧化法及氧气氧化法能否工业化生产的关键,也是ε-己内酯合成领域未来的重要研究方向。In order to further promote the industrialization process ofε-caprolactone synthesis,this study systematically reviews the research progress of both domestic and international processes for preparingε-caprolactone from cyclohexanone.The study focuses on addressing the issues of excessive byproducts,high explosion risks,and poor catalyst stability that arise during the process of cyclohexanone oxidation to produceε-caprolactone.Additionally,it elaborates on the advantages and existing issues associated with the peroxy acid oxidation method,hydrogen peroxide oxidation method,oxygen oxidation method,and biological oxidation method utilized in this process.The results indicate that the peroxy acid oxidation method is currently the preferred method for large-scale industrial production ofε-caprolactone.However,this method generates organic acids as byproducts and poses a risk of explosion.From the perspective of atom economy,the replacement of peroxy acids with hydrogen peroxide and oxygen as oxidants stands as a promising direction for the development of green chemistry.The key to achieving industrial production with the hydrogen peroxide oxidation method and oxygen oxidation method lies in the development of efficient and stable catalysts to compensate for the relatively weaker oxidation ability of hydrogen peroxide and oxygen.This aspect also represents an essential research direction for the future development ofε-caprolactone synthesis.

关 键 词：环己酮 己内酯 BAEYER-VILLIGER氧化 过氧酸 双氧水 

分 类 号：TQ225[化学工程—有机化工]