Hydrodeoxygenation of Phenolic Model Compounds over MoS2 Catalysts with Different Structures

Several MoS2 catalysts of different structure, prepared by in situ decomposition of ammonium heptamolybdate (AHM) and molybdenum naphthenate (MoNaph), and by MoS2 exfoliation (TDM), were characterized by BET, X-ray diffraction (XRD), Energy Dispersive X-ray (EDX) and transmission electron microscopy (TEM). The analysis showed that MoS2 structure was dependant upon the preparation procedure. The activity of the catalysts was determined by measuring the hydrodeoxygenation (HDO) of phenol, 4-methylphenol and 4-methoxyphenol using a batch autoclave reactor operated at 2.8 MPa of hydrogen and temperatures ranging from 320-370 degrees C. By comparing the conversion, the reactivity order of the catalysts was: AHM > TDM-D > MoNaph > thermal > MoS2 powder > TDM-W. Also, the effect of reaction temperature on the HDO conversion was explained in terms of equilibrium of reversible reaction kinetics. The main products of the HDO for phenolic compounds were identified by gas chromatography/mass spectrometry (GC/MS). The results showed that the product distribution and the HDO selectivity were correlated with the reaction temperature. Two parallel reaction routes, direct hydrogenolysis and combined hydrogenation-hydrogenolysis, were confirmed by the analysis of the product distribution. High temperature favored hydrogenolysis over hydrogenation for HDO of phenol and 4-methoxyphenol, whereas for 4-methylphenol the reverse was true.