Continuous flow synthesis of di‐tert‐butyl peroxide in microreactors and kinetic study

Abstract

Di‐tert‐butyl peroxide (DTBP) is a widely used organic peroxide. Its synthesis using tert‐butyl alcohol (TBA) and H2O2 via traditional batch processes has suffered from low space–time yield, uncontrollable product distribution, and safety issues. An efficient continuous‐flow microreaction system was proposed to enhance DTBP synthesis. Optimal reaction conditions were determined: a molar ratio of 1.5 (H2SO4/TBA) and 0.5 (H2O2/TBA), a reaction temperature of 50°C, and concentrations of 75 wt% H2SO4, 85 wt% TBA, and 50 wt% H2O2. A kinetic model was established, indicating that reducing local H2O2 concentration is key to increasing space‐time yield. Consequently, a novel two‐stage H2O2 feeding strategy was proposed, which improved the DTBP selectivity from 94.7% to 97.6% compared to the single‐stage feeding process. The maximum TBA conversion reached upto 98.7% within only 410 s, with a DTBP yield of 96.3%. With proper design and optimization, this microreaction system could be further applied to continuously synthesize other dialkyl peroxides.