摘要
为研究环氧乙烷热稳定性及杂质对其影响,利用C600微量量热仪对环氧乙烷进行热分解试验研究,获得了环氧乙烷分解活化能和绝热条件下到达最大反应速率所需时间（TMRad）等动力学参数。研究了氢氧化钾固体、45%氢氧化钾溶液、三氧化二铁和六水三氯化铁对环氧乙烷热分解特性的影响。结果表明：随温升速率的增加,环氧乙烷热分解起始放热温度逐渐增大;分解活化能E在55~90 k J/mol;环氧乙烷在常温下不易发生热失控;但氢氧化钾固体、45%氢氧化钾溶液、三氧化二铁和六水三氯化铁均对环氧乙烷的热分解有一定程度的影响,使其起始放热温度和最大放热温度都有不同程度的降低,且氢氧化钾溶液和氢氧化钾固体的影响最为明显。
The present paper intends to bring about our research on the thermal decomposition kinetics of ethylene oxide. As is known,ethylene oxide is a kind of substance that is inflammable,explosive,poisonous and prone to self-polymerization. It is just for the said features that may lead to the great need for care to be taken in the process of storage,production and industrial application of it particularly in recent years. In this paper,we have conducted a series of ethylene oxide decomposition reactions to test and measure the multi-heating rate and the dynamic scanning measurements with a micro calorimeter of C600 with the purpose to better assess its hazardous liabilities and get rid of such unexpected events. As far as we know,care should be taken of the following thermal hazard factors,such as the initial exothermal temperature,the maximum exothermal temperature,the decomposition activation energy and time to maximum rate under adiabatic conditions（ TMRad）. Moreover,attention has also to be taken to the effects of KOH,45% KOH solution,Fe2O3 and Fe Cl3·6H2O on the thermal stability of ethylene oxide when laboratory observation is done with it. Thus,the results of our laboratory observation and testing with it prove that the initial exothermic temperature of ethylene oxide tends to increase gradually with the increase of the heating rate. The unit output of the thermal energy is＂exothermic and prone to out-burst and explosion＂. In the presence of an external fire or heating conditions,ethylene oxide is likely to get thermal-decomposed or thermal runaway. Its decomposing activation energy E ranks between 55 k J / mol and 90 k J /mol. Since the initial temperature and time to maximum rate under adiabatic conditions（ TMRad） are closely related,care has also to be taken of that,although the thermal runaway reaction with ethylene oxide hardly has taken place at room temperature.KOH,45% KOH solution,Fe2O3 and Fe Cl3·6H2O tend to show positive effect on the thermal decomposition reaction of ethylene oxide,particularly in the case of 45% of KOH solution.Special mention is necessary to make when its initial exothermic temperature reaches 69. 6 ℃ and 83. 9 ℃. As compared with the pure ethylene oxide,greater liability shall be involved with the increase of the hazard of uncontrolled decomposition even when the initial exothermic temperature reduces 286. 6 ℃ and 272. 3 ℃.
出处
《安全与环境学报》
CAS
CSCD
北大核心
2015年第5期123-127,共5页
Journal of Safety and Environment
基金
国家科技支撑计划项目(2012BAK13B00)
关键词
安全科学技术基础学科
环氧乙烷
热危险性
活化能
杂质
basic disciplines of safety science and technology
ethylene oxide
thermal hazard
activation energy
impurity
作者简介
王犇，副教授，从事化工安全研究，wb1970@163．com。
