Process safety evaluation and reaction mechanism of two step synthesis of tert-butyl hydrogen peroxide

Background: The synthesis of tert-butyl hydrogen peroxide (TBHP) is a two-step strong exothermic reaction. In this paper, the exothermic and mechanism of the reaction process were studied by combining experiments with theoretical calculation. Method: The exothermic characteristic for the synthesis of tert-butyl hydrogen peroxide was investigated by reaction calorimeter. The thermal decomposition characteristics of reactants and products in the reaction system were analyzed by differential scanning calorimeter (DSC) and adiabatic calorimeter (Phi-TEC Ⅱ). The reaction mechanism was analyzed by combining the results of reaction calorimeter, gas chromatography (GC) and the density functional theory method (DFT). Finally, the risk level of the reaction process was evaluated by the risk matric and the Stoessel critical diagram. Significant Findings: TBHP is the main product of the oxidation process and its mass production corresponds to the main exothermic stage of this process. The second step reaction product is thermally unstable and hydrogen peroxide is a hidden danger in the oxidation reaction system. The thermal hazard of the two-step synthesis reaction was unacceptable. Thus, the operation conditions of the reaction need to redesign for reducing hazards. The results can provide reference for further improving the intrinsic safety design of the process.