Kinetic Regime Change in the Tandem Dehydrative Aromatization of Furan Diels-Alder Products

Renewable production of p-xylene from [4 + 2] Diels-Alder cycloaddition of 2,5-dimethylfuran (DMF) and ethylene with H - Y zeolite catalyst in n-heptane solvent is investigated. Experimental studies varying the solid acid catalyst concentration reveal two kinetic regimes for the p-xylene production rate: (i) a linear regime at low acid site concentrations with activation energy E-a = 10.8 kcal/mol and (ii) a catalyst-independent kinetic regime at high acid site concentrations with activation energy E-a = 20.1 kcal/mol. We carry out hybrid QM/MM calculations with a three-layer embedded cluster ONIOM model to compute the energetics along the main reaction pathway, and a microkinetic model is constructed for the interpretation of the experimental kinetic data. At high solid acid concentrations, p-xylene production is limited by the homogeneous Diels-Alder reaction, whereas at low acid concentrations, the overall rate is limited by the heterogeneously catalyzed dehydration of the Diels Alder cydoadduct of DMF and ethylene because of an insufficient number of acid sites, despite the dehydration reaction requiring significantly less activation energy. A reduced kinetic model reveals that the production of p-xylene follows the general kinetics of tandem reactions in which the first step is uncatalyzed and the second step is heterogeneously catalyzed. Reaction orders and apparent activation energies of quantum mechanical and microldnetic simulations are in agreement with experimental values.