Efficient self-initiation cracking of decalin by liquid phase pre-oxidation

Cycloalkanes are the main portion of petroleum hydrocarbons, yet their inert reactivity has put considerable technical challenges to efficient utilization. In this study, the liquid phase pre-oxidation process for efficient self-initiation cracking of cycloalkanes is proposed. In this process, a portion of decalin was converted into hydroperoxy-decalins. These hydroperoxy-decalins not only decompose more readily than decalin due to their weak O-O bonds but also continuously generate free radicals to accelerate the chain initiation reactions, thereby promoting the cracking of residue decalin. The experimental results indicate that the liquid phase pre-oxidation process can significantly improve both the conversion of decalin and the yield of high-value chemicals under 630–680 ℃, and the promotion efficiency increases with the oxidation depth. Compared to gas phase oxidative cracking, the liquid phase pre-oxidation cracking of decalin presents remarkably higher overall conversion and lower carbon oxides yield at elevated temperatures. Comprehensive kinetic models were established by the Reaction Mechanism Generator (RMG) and the reaction process was simulated using Chemkin-pro software packages to elucidate the underlying self-initiation mechanism of liquid phase pre-oxidation. This study introduces a novel promising approach for the efficient utilization of cycloalkanes in the production of high-value chemicals.