Thermal hazard evaluation of tert-butyl hydroperoxide mixed with four acids using calorimetric approaches

Abstract

Possessing thermal instability inherently, organic peroxides have caused many severe accidents in chemical industries all over the world. tert-Butyl hydroperoxide (TBHP) is usually used as initiator or oxidant because of its strong oxidizing ability in the chemical process. In this study, the thermal hazard analysis of TBHP mixed with various acids was investigated. Differential scanning calorimetry (DSC) and vent sizing package 2 were used to figure out the thermal runaway behaviors of TBHP. Thermokinetic parameters, such as exothermic onset temperature (T0), maximum temperature (Tmax), and enthalpy (ΔH), were obtained from thermal curves. In addition, the activation energy (Ea) and rate constant (k) were calculated by the Arrhenius equation. Therefore, the T0 was determined to be 91.6 °C for exothermic reaction using DSC under 4 °C min−1 of heating rate. The Ea for exothermic reaction was calculated to be 92.38 kJ mol−1 by DSC in this study. As far as loss prevention is concerned, thermokinetic parameters are crucial to the relevant processes in the chemical industries, particularly under process upsets.