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Bio-oil upgrading via vapor-phase ketonization over nanostructured FeOx and MnOx: catalytic performance and mechanistic insight

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Abstract

In this study, nanostructured FeOx and MnOx were prepared by two synthetic routes, nanocasting and hydrothermal, and evaluated for bio-oil upgrading via vapor-phase ketonization. Catalytic performance measurements in the ketonization of representative model compounds, acetic and propionic acid, at 335 °C showed high activity for the hydrothermal MnOx and nanocast FeOx (conversion >90%) with high selectivity to the respective ketones. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) studies followed by temperature-programmed thermogravimetric analysis (TGA) and MS showed that the reactive intermediates are bidentate acetate species that desorb as acetone over FeOx and unreacted acetic acid over MnOx (in contradiction to its associated catalysis). Powder X-ray diffraction and X-ray photoelectron spectroscopy analysis of used samples revealed that MnO2 was reduced to MnO during reaction. The relative surface concentrations of adsorbed acetate for the used MnOx catalysts (from DRIFTS) correlated with their corresponding acetic acid conversion (from ketonization studies), indicating that MnO is the active phase for acetic acid ketonization, with MnO2 a precursor which is reduced in situ at temperatures >300 °C. Vapor-phase ketonization of the aqueous phase of a real thermal bio-oil, produced from the fast pyrolysis of lignocellulosic biomass, was demonstrated successfully over MnOx prepared by the hydrothermal route, highlighting this as an attractive approach for the upgrading of pyrolysis bio-oils.

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Acknowledgements

The work was conducted with support from the EU under the frame of the FP7-funded “CAScade deoxygenation process using tailored nanoCATalysts for the production of BiofuELs from lignocellullosic biomass (CASCATBEL)” project (Grant Agreement No. 604307).

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Authors and Affiliations

  1. Chemical Process & Energy Resources Institute (CPERI), Centre for Research and Technology Hellas (CERTH), 6th km Charilaou, Thermi Road, P.O. Box 361, 57001, Thessaloniki, Greece

    Eleni Heracleous & Angelos A. Lappas

  2. School of Science & Technology, International Hellenic University (IHU), 14th km Thessaloniki, Moudania, 57001, Thessaloniki, Greece

    Eleni Heracleous

  3. Max-Planck-Institut für Kohlenforschung, D-45470, Mülheim an der Ruhr, Germany

    Dong Gu & Ferdi Schüth

  4. European Bioenergy Research Institute, Aston University, B4 7ET, Birmingham, UK

    James A. Bennett, Mark A. Isaacs, Adam F. Lee & Karen Wilson

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  1. Eleni Heracleous
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  2. Dong Gu
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  3. Ferdi Schüth
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Correspondence to Eleni Heracleous.

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Heracleous, E., Gu, D., Schüth, F. et al. Bio-oil upgrading via vapor-phase ketonization over nanostructured FeOx and MnOx: catalytic performance and mechanistic insight. Biomass Conv. Bioref. 7, 319–329 (2017). https://doi.org/10.1007/s13399-017-0268-4

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  • DOI: https://doi.org/10.1007/s13399-017-0268-4

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