分析过氧化物的热分解动力学及不同规模下的热危险性,利用同步热分析仪(TG—DSC)测得温升速率分别为3、5、7和9℃/min下的热流率一温度曲线,使用Friedman等转化率法计算出过氧化物分解反应的表观活化能、指前因子,推算出该物质的自加速分解温度tsat及不同规模下的安全指数。结果表明:活化能和指前因子随着转化率的变化而变化,活化能范围为25.2~104.81kJ/mol,指前因子范围为3.3—59.79s^-1。在25kg标准包装下,过氧化物的自加速分解温度为104.6℃,安全指数为0.661;在实验规模、中试规模和生产规模下的安全指数分别为0.995、-0.267、-3.211。
The thermal stability properties of an organic peroxide and thermal hazard on different scales were studied.The curves of thermal decomposition heat flow on the heating rates of 3,5,7,and 9℃/min were obtained by thermogravimetric and differential scanning calorimetry (TG-DSC) heat flux reaction calorimeter.The kinetics parameters of reaction, such as apparent activation energy and pre-exponential factor, were calculated using Friedman isoconversional method based on the thermal decomposition data, and self-accelerating decomposition temperature (tsat ) and the safety index value on different scales were obtained.Results showed that apparent activation energy and pre-exponential factor were not constant, the range of apparent activation energy was 25.2-104. 81 kJ/mol and pre-exponential factor was 3.3-59.79 s-1.Under the standard 25 kg packing,tsat and the safety index values of the peroxide were 104. 6℃ and 0. 661 ,and safety index values of the peroxide were 0. 995,-0. 267 and -3. 211 in the laboratory,pilot and production scale.