Green synthesis of tert‐butyl hydroperoxide via oxidation of tert‐butanol in various reactors

Abstract BACKGROUND In this study, tert‐butyl hydroperoxide (TBHP) was prepared by the oxidation of TBA via the catalysis of sulfuric acid by the green and environmentally‐friendly hydrogen peroxide oxidant sustainable method using micro‐channel reactor ‐ Corning Advanced‐Flow Reactors (AFR), AFR connected pipe, tubular reactor, and batch reactor. The effects of process parameters such as temperature, molar ratio of catalyst, molar ratio of oxidant, and residence time to TBHP on the reaction performance were systematically investigated to explore the conversion and the ratio of main and by‐products. The reliability of this method at a certain temperature was verified with a kinetic study. RESULTS The reaction temperature was 70 °C, the optimum molar ratio of TBA to H 2 SO 4 was determined to be 1:1, and the optimum molar ratio of H 2 O 2 to TBA was determined to be 0.8. AFR and AFR connected pipe process significantly improved the efficiency and safety of the reaction and greatly increased TBA conversion and TBHP yield compared with the tubular and batch reactor. In the range of 60 to 70 °C, a second order kinetic expression characterizes the tert‐butyl alcohol conversion well (R 2 = 0.9499). CONCLUSIONS Our findings revealed that the observed correlation is a practical tool to figure the TBA conversion and TBHP and di‐tert‐butyl peroxide (DTBP) production. The activation energies of the corresponding reactions AFR and AFR external pipeline were 45.26 and 86.98 kJ mol −1 , respectively. The overall heat transfer coefficient achieved in the Corning AFR was validated as scalable. © 2025 Society of Chemical Industry (SCI).