Cleanup and Conversion of Biomass Liquefaction Aqueous Phase to C<sub>3</sub>–C<sub>5</sub> Olefins over Zn<i><sub>x</sub></i>Zr<i><sub>y</sub></i>O<i><sub>z</sub></i> Catalyst
Stephen D. Davidson,
Juan A. Lopez-Ruiz,
Matthew Flake,
Alan R. Cooper,
Yaseen Elkasabi,
Marco Tomasi Morgano,
Vanessa Lebarbier Dagle,
Karl O. Albrecht,
Robert A. Dagle
Affiliations
Stephen D. Davidson
Energy and Environment Directorate, Institute for Integrated Catalysis Pacific Northwest National Laboratory, Richland, WA 99352, USA
Juan A. Lopez-Ruiz
Energy and Environment Directorate, Institute for Integrated Catalysis Pacific Northwest National Laboratory, Richland, WA 99352, USA
Matthew Flake
Energy and Environment Directorate, Institute for Integrated Catalysis Pacific Northwest National Laboratory, Richland, WA 99352, USA
Alan R. Cooper
Energy and Environment Directorate, Institute for Integrated Catalysis Pacific Northwest National Laboratory, Richland, WA 99352, USA
Yaseen Elkasabi
USDA-ARS Eastern Regional Research Center, Wyndmoor, PA 19038, USA
The viability of using a ZnxZryOz mixed oxide catalyst for the direct production of C4 olefins from the aqueous phase derived from three different bio-oils was explored. The aqueous phases derived from (i) hydrothermal liquefaction of corn stover, (ii) fluidized bed fast pyrolysis of horse litter, and (iii) screw pyrolysis of wood pellets were evaluated as feedstocks. While exact compositions vary, the primary constituents for each feedstock are acetic acid and propionic acid. Continuous processing, based on liquid−liquid extraction, for the cleanup of the inorganic contaminants contained in the aqueous phase was also demonstrated. Complete conversion of the carboxylic acids was achieved over ZnxZryOz catalyst for all the feedstocks investigated. The main reaction products from each of the feedstocks include isobutene (>30% selectivity) and CO2 (>23% selectivity). Activity loss from coking was also observed, thereby rendering deactivation of the ZnxZryOz catalyst, however, complete recovery of catalyst activity was observed following regeneration. Finally, the presence of H2 in the feed was found to facilitate hydrogenation of intermediate acetone, thereby increasing propene production and, consequently, decreasing isobutene production.