Simulation approach to benzoyl peroxide decomposition kinetics by thermal calorimetric technique

• This study shows that BPO behaved an autocatalytic reaction at low temperature.
• The simulation results showed that the Ea value was 124 kJ/mol by VSP2 tests.
• The average Ea value was 91.47 ± 17.69 kJ/mol from the optimal fit approach by DSC tests.
• The r2 showed that both the Kissinger and Ozawa methods did not perform well for Ea of BPO decomposition.

To explore the thermal runaway behavior of benzoyl peroxide (BPO) in industrial processes during upsets situations and to compare the difference of values between simulation and experimentation, two calorimeters, differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2), were employed to measure thermokinetic data of the thermal decomposition of BPO, and to calculate values of parameters by simulation approach, which were based on kinetic models and the thermal safety software. This study shows the novel finding that benzoyl peroxide (BPO) has an autocatalytic reaction at low temperature. The simulation results showed that the Ea value was 124 kJ/mol by VSP2 tests. The Ea value was much closer to Zaman's studies than the Ea values developed by the Kissinger and/or Ozawa methods. The Ea value resulting from the optimal fit approach average was 91.47 ± 17.69 kJ/mol also closer to Zaman's studies than values from the Kissinger and Ozawa methods.