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Title: Final Report for the Project Characterization and Valorization of Aqueous Phases Derived from Liquefaction and Upgrading of Bio-Oils

Abstract

The Characterization and Valorization of Aqueous Phases Derived from Liquefaction and Upgrading of Bio-Oils project developed processes to extract value from the organics within aqueous streams derived from biomass direct liquefaction processes. The focus of the project was twofold. First, we characterized a diverse set of aqueous streams from numerous processes and feedstocks. The characterization effort served to inform this project toward development around the most prevalent compounds to maximize versatility and impact. We analyzed diverse streams from hydrothermal liquefaction of lignocellulosic, algal, and waste feedstocks; catalytic fast-pyrolysis aqueous phases; fast-pyrolysis aqueous phases; and aqueous phases produced by hydroprocessing of fast-pyrolysis bio-oil. Second, thermochemical catalytic processes were developed to convert aqueous-phase organics into useful products. These processes focused mostly on organic acids and specifically acetic acid, which was found to be ubiquitous from the characterization effort. A La xZr yO z catalyst was discovered and developed for the ketonization of acids to ketones in the condensed aqueous phase. A dual-bed steam reforming process was developed to convert acids and other organics to hydrogen for bio-oil hydroprocessing. The dual-bed reforming process consisted of a ketonization step followed by a steam reforming step with Co as the active metal. The dual-bed processmore » significantly reduced the rate of coke deposition versus direct steam reforming of the organic acids and beneficially produced CH 4 below the equilibrium value. Finally, we demonstrated direct conversion of aqueous-phase organics to olefins over a Zn xZr yO z catalyst. Each thermochemical catalytic process was demonstrated with process-derived aqueous mixtures. Model compounds were used to benchmark performance and optimize conditions, but emphasis was placed on utilizing “real” aqueous streams whenever possible. A liquid-liquid extraction process using methyl tert-butyl ether as the solvent was developed to segregate dissolved inorganic species and sugars from desirable light oxygenates such as acids and alcohols. Furthermore, a carbon treatment to remove color bodies was employed after it was found the presumably heavy organic chromophore species deactivated catalysts. These economic separation processes allowed for the successful demonstration of stable catalytic processing in the condensed-phase ketonization, dual-bed reforming, and direct olefin production processes for tens to hundreds of hours, which were limited only by the quantity of feed available. Techno-economic analysis of these processes demonstrated the impact possible when capturing “waste” organics as valuable products. The condensed-phase ketonization process for converting aqueous stream acids to ketones followed by reduction and dehydration to olefins sold as a co-product resulted in the reduction of the minimum fuel selling price by about 13% compared to the anaerobic-digestion, aqueous-phase treatment base case (3.74 to 4.29/GGE). The dual-bed reforming process was commensurate in price to the anaerobic digestion base case (4.24 versus 4.29/GGE). However, the need for external natural gas to produce hydrogen for bio-oil hydroprocessing was eliminated, thereby lowering the carbon impact of the process.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1478521
Report Number(s):
PNNL-27848
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English

Citation Formats

Albrecht, Karl O., Dagle, Robert A., Howe, Daniel T., Lopez-Ruiz, Juan A., Davidson, Stephen D., Maddi, Balakrishna, Cooper, Alan R., and Panisko, Ellen A. Final Report for the Project Characterization and Valorization of Aqueous Phases Derived from Liquefaction and Upgrading of Bio-Oils. United States: N. p., 2018. Web. doi:10.2172/1478521.
Albrecht, Karl O., Dagle, Robert A., Howe, Daniel T., Lopez-Ruiz, Juan A., Davidson, Stephen D., Maddi, Balakrishna, Cooper, Alan R., & Panisko, Ellen A. Final Report for the Project Characterization and Valorization of Aqueous Phases Derived from Liquefaction and Upgrading of Bio-Oils. United States. https://doi.org/10.2172/1478521
Albrecht, Karl O., Dagle, Robert A., Howe, Daniel T., Lopez-Ruiz, Juan A., Davidson, Stephen D., Maddi, Balakrishna, Cooper, Alan R., and Panisko, Ellen A. Sun . "Final Report for the Project Characterization and Valorization of Aqueous Phases Derived from Liquefaction and Upgrading of Bio-Oils". United States. https://doi.org/10.2172/1478521. https://www.osti.gov/servlets/purl/1478521.
@article{osti_1478521,
title = {Final Report for the Project Characterization and Valorization of Aqueous Phases Derived from Liquefaction and Upgrading of Bio-Oils},
author = {Albrecht, Karl O. and Dagle, Robert A. and Howe, Daniel T. and Lopez-Ruiz, Juan A. and Davidson, Stephen D. and Maddi, Balakrishna and Cooper, Alan R. and Panisko, Ellen A.},
abstractNote = {The Characterization and Valorization of Aqueous Phases Derived from Liquefaction and Upgrading of Bio-Oils project developed processes to extract value from the organics within aqueous streams derived from biomass direct liquefaction processes. The focus of the project was twofold. First, we characterized a diverse set of aqueous streams from numerous processes and feedstocks. The characterization effort served to inform this project toward development around the most prevalent compounds to maximize versatility and impact. We analyzed diverse streams from hydrothermal liquefaction of lignocellulosic, algal, and waste feedstocks; catalytic fast-pyrolysis aqueous phases; fast-pyrolysis aqueous phases; and aqueous phases produced by hydroprocessing of fast-pyrolysis bio-oil. Second, thermochemical catalytic processes were developed to convert aqueous-phase organics into useful products. These processes focused mostly on organic acids and specifically acetic acid, which was found to be ubiquitous from the characterization effort. A LaxZryOz catalyst was discovered and developed for the ketonization of acids to ketones in the condensed aqueous phase. A dual-bed steam reforming process was developed to convert acids and other organics to hydrogen for bio-oil hydroprocessing. The dual-bed reforming process consisted of a ketonization step followed by a steam reforming step with Co as the active metal. The dual-bed process significantly reduced the rate of coke deposition versus direct steam reforming of the organic acids and beneficially produced CH4 below the equilibrium value. Finally, we demonstrated direct conversion of aqueous-phase organics to olefins over a ZnxZryOz catalyst. Each thermochemical catalytic process was demonstrated with process-derived aqueous mixtures. Model compounds were used to benchmark performance and optimize conditions, but emphasis was placed on utilizing “real” aqueous streams whenever possible. A liquid-liquid extraction process using methyl tert-butyl ether as the solvent was developed to segregate dissolved inorganic species and sugars from desirable light oxygenates such as acids and alcohols. Furthermore, a carbon treatment to remove color bodies was employed after it was found the presumably heavy organic chromophore species deactivated catalysts. These economic separation processes allowed for the successful demonstration of stable catalytic processing in the condensed-phase ketonization, dual-bed reforming, and direct olefin production processes for tens to hundreds of hours, which were limited only by the quantity of feed available. Techno-economic analysis of these processes demonstrated the impact possible when capturing “waste” organics as valuable products. The condensed-phase ketonization process for converting aqueous stream acids to ketones followed by reduction and dehydration to olefins sold as a co-product resulted in the reduction of the minimum fuel selling price by about 13% compared to the anaerobic-digestion, aqueous-phase treatment base case (3.74 to 4.29/GGE). The dual-bed reforming process was commensurate in price to the anaerobic digestion base case (4.24 versus 4.29/GGE). However, the need for external natural gas to produce hydrogen for bio-oil hydroprocessing was eliminated, thereby lowering the carbon impact of the process.},
doi = {10.2172/1478521},
url = {https://www.osti.gov/biblio/1478521}, journal = {},
number = ,
volume = ,
place = {United States},
year = {2018},
month = {7}
}