Chemistry of Alkylaromatics Reconsidered

To investigate upgrading crude oil, alkylaromatic compounds are often chosen as model compounds to better understand their reactivity. In recent kinetic models of this chemistry, the main reaction consuming the alkylaromatic is a four-membered ring “retro-ene” reaction. Here, the transition state of that reaction is discovered to be inconsistent with six-membered ring retroene reactions reported in the literature, leading to inaccurate conclusions. A new detailed kinetic model is constructed using Reaction Mechanism Generator (RMG), and thermodynamic parameters of key compounds and radicals are identified to limit model accuracy. Thermochemistry for key species in the chemistry of hexylbenzene, including hexylbenzene, alkylbenzenes, alkylbenzene radicals, aliphatic radicals, and styrene, was calculated using the CBS-QB3 quantum chemistry method to improve the accuracy of the hexylbenzene pyrolysis model. The kinetics of a key beta scission reaction were also calculated. The results of these calculations have led to an overall improvement in hexylbenzene pyrolysis model predictions.