Kinetics Study of the Peroxidation of tert-Butyl Alcohol to tert-Butyl Hydrogen Peroxide in a Microreactor

tert-Butyl hydroperoxide (TBHP), an organic peroxide, is mainly used as a polymer initiator and is typically synthesized by the thermal reaction of tert-butyl alcohol (TBA) with hydrogen peroxide (H2O2). In this study, we adopted sulfuric acid (H2SO4) as the homogeneous catalyst to promote the peroxidation reaction of TBA in a microchannel reactor. The reaction conditions for the synthesis of TBHP were optimized, and the kinetic model of the synthesis was subsequently established. The results show that byproducts exist during the reaction as well, such as di-tert-butyl peroxide (DTBP). The reaction temperature was 50 °C, the optimum molar ratio of TBA to H2O2 was determined to be 1:1, and the optimum molar ratio of H2SO4 to TBA was determined to be 0.95. Kinetics studies showed that the pre-exponential factors for producing TBHP and DTBP were 1 × 1019 and 3.12 × 1025, respectively, while the activation energies of the corresponding reactions were 131.72 and 179.33 kJ/mol, respectively. The calculation results of the kinetic model fit well with the concentration of the products measured during the microreactor experiments.