from first principles PP-I-1

PP-IV-22H 2 -Least Approaches for Deoxygenation of Phenolic CompoundsSooknoi T. 1 , Ausavasukhi A. 21 Department of Chemistry, Faculty of Science, King Mongkut’s Institute of TechnologyLadkrabang, Bangkok 10520, Thailand2 Program in Applied Chemistry, Faculty of Sciences and Liberal Arts,Rajamangala University of Technology Isan, Nakhon Ratchasima 30000, Thailandkstawan@gmail.comDeoxygenation of phenolic compounds has become major concern for upgrading pyrolysisbio-oils due to (i) a large consumption of H 2 for hydrotreating approaches [1,2] and (ii)severe catalyst deactivation [3]. Unlike carbonyl compounds found in the pyrolysis bio-oils,oxygen in phenolics cannot be readily removed via decarbonylation and decarboxylation. Theresonance structure strengthen C-O bond of the phenolics and direct hydrogenolysis cannot besimply achieved over renowned catalysts [4,5]. To avoid excessive H 2 intake, new approachesinvolve weakening of C-O bonds without ring saturation. This can be achieved either by (i)partial hydrogenation-dehydration or (ii) coupling-hydrogenolysis approaches. In the firstcase, phenolics can be partially tautomerized [6] over oxophilic catalysts [7]. The keto-formintermediates can be subsequently hydrogenated and oxygen can then be removed bydehydration of the alcohol formed. For the latter approaches, phenolics can also be coupled tolarger oxygenate species over bifunctional catalysts [8]. Together with H-transfer, activemetal readily promotes hydrogenolysis of larger precursors since cleavage of the C-Obridging in the bulky isolated rings can be easily facilitated, as compared to that in the singlering aromatics. However, coke deposit is largely regulated by coupling/hydrogenolysis rate inthis case.References:[1] C. Zhao, D.M. Camaioni, J.A. Lercher, J. Catal. 288 (2012) 92-103.[2] V.N. Bui, G. Toussaint, D. Laurenti, C. Mirodatos, C. Geantet, Catal.Today 143 (2009) 172-178.[3] E. Furimsky, Catalytic hydrodeoxygenation, App. Catal. A: General 199 (2000) 147-190.[4] C.V. Loricera, B. Pawelec, A. Infantes-Molina, M.C. Álvarez-Galván, R. Huirache-Acuña,R. Nava, J.L.G. Fierro, Catal. Today 172 (2011) 103-110[5] K.L. Deutsch, B.H. Shanks, J. Catal., 285 (2012) 235-241.[6] Stepniewski, Comp. Theo. Chem., 963 (2011) 176–184.[7] M. Chia, Y. J. Pag_n-Torres, D. Hibbitts, Q. Tan, H. N. Pham, A. K. Datye, M. Neurock,R. J. Davis, J. A. Dumesic, J. Amer. Chem. Soc., 133 (2011) 12675-12689.[8] A. Ausavasukhi, T. Sooknoi, D.E. Resasco, J. Catal., 268 (2009) 68-78.307