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Title: Cleanup and Conversion of Biomass Liquefaction Aqueous Phase to C 3–C 5 Olefins over Zn xZr yO z Catalyst

Abstract

The viability of using a Zn xZr yO z mixed oxide catalyst for the direct production of C 4 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 Zn xZr yO z catalyst for all the feedstocks investigated. The main reaction products from each of the feedstocks include isobutene (>30% selectivity) and CO 2 (>23% selectivity). Activity loss from coking was also observed, thereby rendering deactivation of the Zn xZr yO z catalyst, however, complete recovery of catalyst activity was observed following regeneration. Finally, the presence of H 2 in the feed was found to facilitate hydrogenation of intermediate acetone, thereby increasing propene production and, consequently, decreasing isobutene production.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [1];  [2]; ORCiD logo [3];  [1];  [4]; ORCiD logo [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy and Environment Directorate, Inst. for Integrated Catalysis
  2. USDA-ARS Eastern Regional Research Center, Wyndmoor, PA (United States)
  3. ARCUS Greencycling Technologies GmbH, Ludwigsburg (Germany)
  4. Archer Daniels Midland Co., Decatur, IL (United States). James R. Randall Research Center
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1574663
Report Number(s):
PNNL-SA-148421
Journal ID: ISSN 2073-4344; CATACJ
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Catalysts
Additional Journal Information:
Journal Volume: 9; Journal Issue: 11; Journal ID: ISSN 2073-4344
Publisher:
MDPI
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; biomass-derived aqueous phase upgrading; olefin production; oxide catalyst

Citation Formats

Davidson, Stephen D., Lopez-Ruiz, Juan A., Flake, Matthew D., Cooper, Alan R., Elkasabi, Yaseen, Tomasi Morgano, Marco, Lebarbier Dagle, Vanessa, Albrecht, Karl O., and Dagle, Robert A. Cleanup and Conversion of Biomass Liquefaction Aqueous Phase to C3–C5 Olefins over ZnxZryOz Catalyst. United States: N. p., 2019. Web. doi:10.3390/catal9110923.
Davidson, Stephen D., Lopez-Ruiz, Juan A., Flake, Matthew D., Cooper, Alan R., Elkasabi, Yaseen, Tomasi Morgano, Marco, Lebarbier Dagle, Vanessa, Albrecht, Karl O., & Dagle, Robert A. Cleanup and Conversion of Biomass Liquefaction Aqueous Phase to C3–C5 Olefins over ZnxZryOz Catalyst. United States. doi:10.3390/catal9110923.
Davidson, Stephen D., Lopez-Ruiz, Juan A., Flake, Matthew D., Cooper, Alan R., Elkasabi, Yaseen, Tomasi Morgano, Marco, Lebarbier Dagle, Vanessa, Albrecht, Karl O., and Dagle, Robert A. Wed . "Cleanup and Conversion of Biomass Liquefaction Aqueous Phase to C3–C5 Olefins over ZnxZryOz Catalyst". United States. doi:10.3390/catal9110923. https://www.osti.gov/servlets/purl/1574663.
@article{osti_1574663,
title = {Cleanup and Conversion of Biomass Liquefaction Aqueous Phase to C3–C5 Olefins over ZnxZryOz Catalyst},
author = {Davidson, Stephen D. and Lopez-Ruiz, Juan A. and Flake, Matthew D. and Cooper, Alan R. and Elkasabi, Yaseen and Tomasi Morgano, Marco and Lebarbier Dagle, Vanessa and Albrecht, Karl O. and Dagle, Robert A.},
abstractNote = {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.},
doi = {10.3390/catal9110923},
journal = {Catalysts},
number = 11,
volume = 9,
place = {United States},
year = {2019},
month = {11}
}

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