Hydrodeoxygenation of guaiacol in the presence of 1-octanol was studied in a fixed-bed reactor under mild conditions (50-250 °C) over platinum particles supported on silica (Pt/SiO2) and a zeolite with framework type MFI at a Si/Al-ratio of 45 (Pt/H-MFI-90). The deoxygenation selectivity strongly depended on the support and the temperature. Both guaiacol and octanol were rapidly deoxygenated in the presence of hydrogen over Pt/H-MFI-90 at 250 °C to cyclohexane and octane, respectively. In contrast, Pt/SiO2 mostly showed hydrogenation, but hardly any deoxygenation activity. The acidic sites of the MFI-90 support lead to improved deoxygenation performance at the mild temperature conditions of this study. Significant conversions under reaction conditions applied already occurred at temperatures of 200 °C. However, during long-term stability tests, the Pt/H-MFI-90 catalyst deactivated after more than 30 h, probably due to carbon deposition, whereas Pt/SiO2 was more stable. The catalytic activity of the zeolite catalyst could only partly be regained by calcination in air, as some of the acidic sites were lost.
OPEN ACCESSCatalysts 2015, 5 1153
Second generation biofuels are produced in the bioliq process at the Karlsruhe Institute of Technology via gasification of pyrolysis oil and synthesis of gasoline from the emerging synthesis gas. An alternative strategy is the direct upgrading of the pyrolysis oil by hydrodeoxygenation (HDO). The present study reports on the HDO of guaiacol as one of the phenolic compounds strongly abundant in such mixtures. Special focus was laid on the solvent influence using Pt-based catalysts. Higher HDO ability was seen using nonpolar solvents and acidic supports. Characterization of the catalysts before and after the test showed that the solvent did not only influence the reactivity, but also the catalyst stability.
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