Stability of Pt/γ-Al2O3 Catalysts in Lignin and Lignin Model Compound Solutions under Liquid Phase Reforming Reaction Conditions

The stability of a 1 wt % Pt/gamma-Al2O3 catalyst was tested in an ethanol/water mixture at 225 C and autogenic pressure, conditions at which it is possible to dissolve and depolymerize various kinds of lignin, and structural changes to the catalysts were studied by means of X-ray diffraction (XRD), Al-27 MAS NMR, N-2 physisorption, transmission electron microscopy (TEM), H-2 chemisorption elemental analysis thermogravimetric analysis-mass spectrometry (TGA-MS), and IR. In the absence of reactants the alumina support is found to transform into boehmite within 4 h, leading to a reduction in support surface area, sintering of the supported Pt nanoparticles, and a reduction of active metal surface area. Addition of aromatic oxygenates to mimic the compounds typically obtained by lignin depolymerization leads to a slower transformation of the support oxide. These compounds, however, were not able to slow down the decrease in dispersion of the Pt nanoparticles. Vanillin and guaiacol stabilize the aluminum oxide more than phenol, anisole, and benzaldehyde because of the larger number of oxygen functionalities that can interact with the alumina. Interestingly, catalyst samples treated in the presence of lignin showed almost no formation of boehmite, no reduction in support or active metal surface area, and no Pt nanoparticle sintering. Furthermore, in the absence of lignin-derived aromatic oxygenates, ethanol forms a coke-like layer on the catalyst, while oxygenates prevent this by adsorption on the support by coordination via the oxygen functionalities.