(410g) Renewable Catalytic Process for the Production of p-Xylene From Glucose

A renewable process to p-xylene from biomass-derived sugars provides a new method for sustainable production of plastics including PET [1].  As part of the Catalysis Center for Energy Innovation (CCEI), we demonstrate a three step process: (1) conversion of glucose to 5-hydroxymethylfurfural, (2) hydrodeoxygenation to dimethylfuran, and (3) cycloaddition of dimethylfuran to p-xylene.  This route introduces the possibility for utilizing sugars produced from the saccharification of biopolymers such as cellulose [2].  Initial dehydration of fructose produces an oxygenated furan, which is subsequently reduced to dimethylfuran.  The following reaction to produce p-xylene occurs within a single reactor as a two-part reaction (Diels-Alder cycloaddition followed by dehydration).  This reaction occurs through an oxygenated bicyclic intermediate, which can lead to the desired product of p-xylene or to undesireable dimer side products.  Additionally, dehydration to produce p-xylene produces water which can hydrolyze dimethylfuran and produce ring-opened six-carbon side products.  Through insight into the role catalyst structure and active site, we have designed a catalytic system capable of achieving 75% yield of p-xylene [3].

References:

[1] Climent, M. J.; Corma, A.; Iborra, S. Green Chemistry 2011, 13, 520-540

[2] Vlachos, D. G.; Chen, J. G.; Gorte, R. J.; Huber, G. W.; Tsapatsis, M. Catalysis Letters 2010, 140, 77-84.

[3] Williams, C. L.; Chang, C.-chih; Do, P.; Nikbin, N.; Caratzoulas, S.; Vlachos, D. G.; Lobo, R. F.; Fan, W.; Dauenhauer, P. J. ACS Catalysis 2012, 2, 935-939