Cleanup and Conversion of Biomass Liquefaction Aqueous Phase to C3–C5 Olefins over ZnxZryOz Catalyst
Abstract
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.
- Authors:
-
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy and Environment Directorate, Inst. for Integrated Catalysis
- USDA-ARS Eastern Regional Research Center, Wyndmoor, PA (United States)
- ARCUS Greencycling Technologies GmbH, Ludwigsburg (Germany)
- 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}
}
Web of Science
Works referenced in this record:
Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering
journal, September 2006
- Huber, George W.; Iborra, Sara; Corma, Avelino
- Chemical Reviews, Vol. 106, Issue 9, p. 4044-4098
Production of renewable jet fuel range alkanes and commodity chemicals from integrated catalytic processing of biomass
journal, January 2014
- Bond, Jesse Q.; Upadhye, Aniruddha A.; Olcay, Hakan
- Energy Environ. Sci., Vol. 7, Issue 4
Synergies between Bio- and Oil Refineries for the Production of Fuels from Biomass
journal, September 2007
- Huber, George W.; Corma, Avelino
- Angewandte Chemie International Edition, Vol. 46, Issue 38, p. 7184-7201
Techno-economic analysis of liquid fuel production from woody biomass via hydrothermal liquefaction (HTL) and upgrading
journal, September 2014
- Zhu, Yunhua; Biddy, Mary J.; Jones, Susanne B.
- Applied Energy, Vol. 129
Liquid-Phase Catalytic Processing of Biomass-Derived Oxygenated Hydrocarbons to Fuels and Chemicals
journal, September 2007
- Chheda, Juben N.; Huber, George W.; Dumesic, James A.
- Angewandte Chemie International Edition, Vol. 46, Issue 38, p. 7164-7183
Characterization of the aqueous fractions from hydrotreatment and hydrothermal liquefaction of lignocellulosic feedstocks
journal, March 2015
- Panisko, Ellen; Wietsma, Thomas; Lemmon, Teresa
- Biomass and Bioenergy, Vol. 74
Review of biomass pyrolysis oil properties and upgrading research
journal, January 2007
- Zhang, Qi; Chang, Jie; Wang, Tiejun
- Energy Conversion and Management, Vol. 48, Issue 1, p. 87-92
Developments in direct thermochemical liquefaction of biomass: 1983-1990
journal, May 1991
- Elliott, D. C.; Beckman, D.; Bridgwater, A. V.
- Energy & Fuels, Vol. 5, Issue 3
Hydrothermal liquefaction of biomass: Developments from batch to continuous process
journal, February 2015
- Elliott, Douglas C.; Biller, Patrick; Ross, Andrew B.
- Bioresource Technology, Vol. 178, p. 147-156
Experimental comparison of two bench scale units for fast and intermediate pyrolysis
journal, March 2017
- Funke, Axel; Tomasi Morgano, Marco; Dahmen, Nicolaus
- Journal of Analytical and Applied Pyrolysis, Vol. 124
Bench-Scale Fluidized-Bed Pyrolysis of Switchgrass for Bio-Oil Production †
journal, March 2007
- Boateng, Akwasi A.; Daugaard, Daren E.; Goldberg, Neil M.
- Industrial & Engineering Chemistry Research, Vol. 46, Issue 7
An overview of aqueous-phase catalytic processes for production of hydrogen and alkanes in a biorefinery
journal, January 2006
- Huber, George W.; Dumesic, James A.
- Catalysis Today, Vol. 111, Issue 1-2
Oligomerization of ethanol-derived propene and isobutene mixtures to transportation fuels: catalyst and process considerations
journal, January 2019
- Saavedra Lopez, Johnny; Dagle, Robert A.; Dagle, Vanessa Lebarbier
- Catalysis Science & Technology, Vol. 9, Issue 5
Integrated process for the catalytic conversion of biomass-derived syngas into transportation fuels
journal, January 2016
- Dagle, Vanessa Lebarbier; Smith, Colin; Flake, Matthew
- Green Chemistry, Vol. 18, Issue 7
Trimerization of isobutene over a zeolite beta catalyst
journal, January 2007
- Yoon, J.; Chang, J.; Lee, H.
- Journal of Catalysis, Vol. 245, Issue 1
Light olefins dimerization to high quality gasoline components
journal, February 2001
- Marchionna, Mario; Di Girolamo, Marco; Patrini, Renata
- Catalysis Today, Vol. 65, Issue 2-4
Zirconocenes as Initiators for Carbocationic Isobutene Homo- and Copolymerizations
journal, April 1998
- Carr, Andrew G.; Dawson, David M.; Bochmann, Manfred
- Macromolecules, Vol. 31, Issue 7
A study of ZnxZryOz mixed oxides for direct conversion of ethanol to isobutene
journal, October 2013
- Liu, Changjun; Sun, Junming; Smith, Colin
- Applied Catalysis A: General, Vol. 467
Key Roles of Lewis Acid–Base Pairs on Zn x Zr y O z in Direct Ethanol/Acetone to Isobutene Conversion
journal, December 2015
- Sun, Junming; Baylon, Rebecca A. L.; Liu, Changjun
- Journal of the American Chemical Society, Vol. 138, Issue 2
Direct Conversion of Bio-ethanol to Isobutene on Nanosized Zn x Zr y O z Mixed Oxides with Balanced Acid–Base Sites
journal, July 2011
- Sun, Junming; Zhu, Kake; Gao, Feng
- Journal of the American Chemical Society, Vol. 133, Issue 29
Conversion of syngas-derived C2+ mixed oxygenates to C3–C5 olefins over ZnxZryOz mixed oxide catalysts
journal, January 2016
- Smith, Colin; Dagle, Vanessa Lebarbier; Flake, Matthew
- Catalysis Science & Technology, Vol. 6, Issue 7, p. 2325-2336
Single‐step Conversion of Methyl Ethyl Ketone to Olefins over Zn x Zr y O z Catalysts in Water
journal, June 2019
- Dagle, Vanessa L.; Dagle, Robert A.; Kovarik, Libor
- ChemCatChem, Vol. 11, Issue 15
Cascade Reactions for the Continuous and Selective Production of Isobutene from Bioderived Acetic Acid Over Zinc-Zirconia Catalysts
journal, October 2014
- Crisci, Anthony J.; Dou, Herui; Prasomsri, Teerawit
- ACS Catalysis, Vol. 4, Issue 11
Production of Deoxygenated Biomass Fast Pyrolysis Oils via Product Gas Recycling
journal, June 2013
- Mullen, Charles A.; Boateng, Akwasi A.; Goldberg, Neil M.
- Energy & Fuels, Vol. 27, Issue 7
Mobile demonstration unit for fast- and catalytic pyrolysis: The combustion reduction integrated pyrolysis system (CRIPS)
journal, January 2019
- Boateng, Akwasi A.; Schaffer, Mark A.; Mullen, Charles A.
- Journal of Analytical and Applied Pyrolysis, Vol. 137
Screw pyrolysis with integrated sequential hot gas filtration
journal, May 2015
- Tomasi Morgano, Marco; Leibold, Hans; Richter, Frank
- Journal of Analytical and Applied Pyrolysis, Vol. 113
Screw pyrolysis technology for sewage sludge treatment
journal, March 2018
- Tomasi Morgano, Marco; Leibold, Hans; Richter, Frank
- Waste Management, Vol. 73
Liquid-Phase Catalytic Processing of Biomass-Derived Oxygenated Hydrocarbons to Fuels and Chemicals
journal, December 2007
- Chheda, Juben N.; Huber, George W.; Dumesic, James A.
- ChemInform, Vol. 38, Issue 50
Strategies To Valorize the Hydrothermal Liquefaction-Derived Aqueous Phase into Fuels and Chemicals
journal, November 2019
- Davidson, Stephen D.; Lopez-Ruiz, Juan A.; Zhu, Yunhua
- ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 24