Insight into the Synthesis of tert-Butyl Hydroperoxide in a Microreactor: Influencing Factors Identification and Reaction Mechanism Revelation

tert-Butyl hydroperoxide (TBHP) is a crucial synthon of organic peroxides extensively used as initiators. However, the complexity of the reaction and instability of the product pose a challenge to both the efficiency and safety during TBHP production. Therefore, it is imperative to undertake a comprehensive investigation of its preparation method and reaction mechanism. In this work, the peroxidation of tert-butanol (TBA) and its regulation mechanism is systematically studied using a microreactor system. For the first time, the key process parameters and a series of olefin-related impurities are identified. The corresponding influences on product quality indices are elucidated to establish effective strategies for enhancing the final product quality. Furthermore, a reaction network is proposed and validated by Density Functional Theory (DFT) calculation and a thermodynamic equilibrium equation. TBHP, di-tert-butyl peroxide (DTBP), and a series of olefins (DDC-1–3) are generated through a carbonium ion route with maximum energy barriers ranging from 3.84 to 4.96 kcal/mol. Notably, DDC-2 is predominately formed through free radical polymerization initiated by the decomposition of DTBP with a dissociation energy of 141.98 kJ/mol. The identified key influencing factors are strongly supported by the highly consistent experimental and theoretical results, aligning well with the distinct characteristics of the microreactors. Consequently, a high TBHP concentration of 79.8% is achieved while reducing catalyst usage, shortening the residence time, and lowering liquid holdup, demonstrating significant improvements in efficiency and productivity.