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Title: Kinetics and Mechanism for Hydrothermal Conversion of Polyhydroxybutyrate (PHB) for Wastewater Valorization

Abstract

Conventional wastewater treatment processes can be tailored to recover organic carbon from wastewater as intracellular polyhydroxybutyrate (PHB) polymer granules while simultaneously meeting effluent discharge standards. Traditional applications of PHB as a bioplastic are hampered by its suboptimal properties (e.g., brittle), lack of efficient and sustainable approaches for recovering PHB from cells, and concerns about wastewater-derived impurities. In this study, we report on the conversion of PHB and its monomer acids - 3-hydroxybutyric acid (3HBA) and crotonic acid (CA) - under hydrothermal conditions (in condensed water at elevated temperature and pressure) to form propylene, a valuable chemical intermediate that self-separates from water. PHB depolymerization results in a mixture of 3HBA and CA, which can interconvert via (de)hydration reactions that vary with prevailing reaction conditions. Further hydrothermal conversion of the monomer acids yields propylene and CO2. Conversion of 3HBA occurs at lower temperatures than CA, and a new concerted dehydration-decarboxylation pathway is proposed, which differs from the sequential dehydration (3HBA to CA) and decarboxylation (CA to propylene and CO2) pathway reported for dry thermal conversion. A kinetics network model informed by experimental results reveals that CA conversion to propylene and CO2 proceeds predominantly via hydration to 3HBA followed by the concerted dehydration-decarboxylationmore » pathway rather than by direct decarboxylation of CA. Demonstrative experiments using PHB-containing methanotrophic biomass show results consistent with the model, producing propylene at near-theoretical yields at lower temperatures than reported previously.« less

Authors:
 [1];  [2]
  1. Colorado School of Mines
  2. National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1574199
Report Number(s):
NREL/JA-5100-75389
DOE Contract Number:  
AC36-08GO28308
Resource Type:
Journal Article
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 21; Journal Issue: 20
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; wastewater treatment; hydrothermal conversion; valorization

Citation Formats

Li, Yalin, and Strathmann, Timothy. Kinetics and Mechanism for Hydrothermal Conversion of Polyhydroxybutyrate (PHB) for Wastewater Valorization. United States: N. p., 2019. Web. doi:https://dx.doi.org/10.1039/C9GC02507C.
Li, Yalin, & Strathmann, Timothy. Kinetics and Mechanism for Hydrothermal Conversion of Polyhydroxybutyrate (PHB) for Wastewater Valorization. United States. doi:https://dx.doi.org/10.1039/C9GC02507C.
Li, Yalin, and Strathmann, Timothy. Thu . "Kinetics and Mechanism for Hydrothermal Conversion of Polyhydroxybutyrate (PHB) for Wastewater Valorization". United States. doi:https://dx.doi.org/10.1039/C9GC02507C.
@article{osti_1574199,
title = {Kinetics and Mechanism for Hydrothermal Conversion of Polyhydroxybutyrate (PHB) for Wastewater Valorization},
author = {Li, Yalin and Strathmann, Timothy},
abstractNote = {Conventional wastewater treatment processes can be tailored to recover organic carbon from wastewater as intracellular polyhydroxybutyrate (PHB) polymer granules while simultaneously meeting effluent discharge standards. Traditional applications of PHB as a bioplastic are hampered by its suboptimal properties (e.g., brittle), lack of efficient and sustainable approaches for recovering PHB from cells, and concerns about wastewater-derived impurities. In this study, we report on the conversion of PHB and its monomer acids - 3-hydroxybutyric acid (3HBA) and crotonic acid (CA) - under hydrothermal conditions (in condensed water at elevated temperature and pressure) to form propylene, a valuable chemical intermediate that self-separates from water. PHB depolymerization results in a mixture of 3HBA and CA, which can interconvert via (de)hydration reactions that vary with prevailing reaction conditions. Further hydrothermal conversion of the monomer acids yields propylene and CO2. Conversion of 3HBA occurs at lower temperatures than CA, and a new concerted dehydration-decarboxylation pathway is proposed, which differs from the sequential dehydration (3HBA to CA) and decarboxylation (CA to propylene and CO2) pathway reported for dry thermal conversion. A kinetics network model informed by experimental results reveals that CA conversion to propylene and CO2 proceeds predominantly via hydration to 3HBA followed by the concerted dehydration-decarboxylation pathway rather than by direct decarboxylation of CA. Demonstrative experiments using PHB-containing methanotrophic biomass show results consistent with the model, producing propylene at near-theoretical yields at lower temperatures than reported previously.},
doi = {https://dx.doi.org/10.1039/C9GC02507C},
journal = {Green Chemistry},
number = 20,
volume = 21,
place = {United States},
year = {2019},
month = {9}
}

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