The decomposition of organic peroxides by their relatively weak oxygen linkage and hydroperoxide radical in the presence of reaction solution is one of the thermal hazards for triggering a runaway reaction. Runaway incidents may occur in oxidation reactors, vacuum condensation reactors, tank lorries, or storage tanks. In NFPA 432 organic peroxides in NFPA 432 are classified as flammable. The exothermic behaviors of solid organic peroxides, dicumene peroxide, benzoyl peroxide, and lauroyl peroxide, were determined by differential scanning calorimetry (DSC), and vent sizing package 2 (VSP2). Relevant data detected by DSC provided thermal stability information, such as exothermic onset temperature (T0), maximum heat-releasing peak (Tmax), and heat of decomposition (ΔHd). VSP2 was used to perform the bench scale situation for pushing the expected or unexpected reaction to undergo runaway reaction. Onset temperature, maximum pressure, self-heating rate ((dT dt−1)max), and pressure-release rate ((dP dt−1)max) were therefore obtained and explained. These results are essentially crucial in process design for an inherently safer approach.
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