Research advances on runaway decomposition of high pressure polyethylene: Reaction mechanism, initiation system and model

doi:10.16085/j.issn.1000-6613.2023-0739

Abstract

Abstract:

High pressure polyethylene, as known as low density polyethylene (LDPE), is the most widely used plastic products in the world. However, LDPE preparation needs to be carried out under high pressure process, and then ethylene will decompose out of control under adiabatic compression condition with a large risk of ignition and explosion. This paper analyzed the causes of LDPE production accidents at home and abroad in recent years, introduced the high pressure polymerization process of LDPE and discussed the polymerization and decomposition mechanism of LDPE synthesis in detail. The main causes of the runaway decomposition of ethylene caused by initiators and hot spots at high temperature were summarized, and the key parameters as well as limit boundary of the runaway decomposition of ethylene under polymerization conditions were also described carefully. In addition, the mathematical model and development of ethylene decomposition were fully introduced and discussed. Finally, this paper put forward the problems that needed to be solved to deal with the essential safety production of LDPE, and proposed the solution and future development direction to provide thinking for the future safety development of LDPE process and capacity improvement.

Key words: high pressure polyethylene, ethylene, initiator, runaway decomposition, model

摘要：

高压聚乙烯又名低密度聚乙烯（LDPE），是当前世界上用途广泛和产量较大的塑料制品。然而LDPE的合成需要在高于150MPa的工艺条件下进行，燃爆风险高。本文对LDPE高压聚合工艺过程进行了介绍，探讨了LDPE合成过程中的聚合与分解机理，分析了引发剂和高温热点导致乙烯失控分解的致灾机制，对聚合条件下乙烯失控分解的关键参数和极限边界进行了阐述。此外，对乙烯分解的数学模型及发展进行了介绍和论述。最后，本文提出了当前应对LDPE本质安全化生产所需解决的问题，并对此提出了解决思路与发展方向，以期为我国自主知识产权的LDPE工艺安全发展提升提供思考。

关键词: 高压聚乙烯, 乙烯, 引发剂, 失控分解, 模型

CLC Number:

TQ32

ZHANG Zhichen, ZHU Yunfeng, CHENG Weishu, MA Shoutao, JIANG Jie, SUN Bing, ZHOU Zichen, XU Wei. Research advances on runaway decomposition of high pressure polyethylene: Reaction mechanism, initiation system and model[J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3979-3989.

张智琛, 朱云峰, 成卫戍, 马守涛, 姜杰, 孙冰, 周子辰, 徐伟. 高压聚乙烯失控分解研究进展：反应机理、引发体系与模型[J]. 化工进展, 2023, 42(8): 3979-3989.

Figures/Tables 12

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项目	化学名称	半衰期为1min时的温度/℃
低温系列	过氧化二碳酸二-2-乙基己酯	91
	过氧癸酸叔丁酯	101
	过氧化十二酰	113
	过氧新戊酸叔丁酯	110
	过氧化异丁酰	113
	过氧化-2-乙基氧甲酸叔丁酯	135
中温系列	叔丁基过氧异丙基碳酸酯	158
	叔丁基过氧乙酸	160
	过氧苯甲酸叔丁酯	170
高温系列	二叔丁基过氧化物	186
	1,1,3,3-四甲基丁基过氧化氢	223

项目	化学名称	半衰期为1min时的温度/℃
低温系列	过氧化二碳酸二-2-乙基己酯	91
	过氧癸酸叔丁酯	101
	过氧化十二酰	113
	过氧新戊酸叔丁酯	110
	过氧化异丁酰	113
	过氧化-2-乙基氧甲酸叔丁酯	135
中温系列	叔丁基过氧异丙基碳酸酯	158
	叔丁基过氧乙酸	160
	过氧苯甲酸叔丁酯	170
高温系列	二叔丁基过氧化物	186
	1,1,3,3-四甲基丁基过氧化氢	223

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