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Title: In situ recovery of bio-based carboxylic acids

Abstract

The economics of chemical and biological processes is often dominated by the expense of downstream product separations from dilute product streams. Continuous separation techniques, such as in situ product recovery (ISPR), are attractive in that they can concentrate products from a reactor and minimize solvent loss, thereby increasing purity and sustainability of the process. In bioprocesses, ISPR can have an additional advantage of increasing productivity by alleviating product inhibition on the microorganism. In this work, we developed a liquid–liquid extraction (LLE)-based ISPR system integrated with downstream distillation to selectively purify free carboxylic acids, which were selected as exemplary bioproducts due to their ability to be produced at industrially relevant titers and productivities. Equilibrium constants for the extraction of carboxylic acids into a phosphine-oxide based organic phase were experimentally determined. Complete recovery of acids from the extractant and recyclability of the organic phase were demonstrated through multiple extraction–distillation cycles. Using these data, an equilibrium model was developed to predict the acid loading in the organic phase as a function of the extraction equilibrium constant, initial aqueous acid concentration, pH, organic to aqueous volume ratio, and temperature. A distillation process model was then used to predict the energy input required to distillmore » neat acid from an organic phase as a function of the acid loading in the organic phase feed. The heat integrated distillation train can achieve neat recovery of acetic acid with an energy input of 2.6 MJ kg-1 of acetic acid. This LLE-based ISPR system integrated with downstream distillation has an estimated carbon footprint of less than 0.36 kg CO2 per kg of acetic acid, and provides a green approach to enable both new industrial bioprocesses, and process intensification of existing industrial operations by (1) increasing the productivity and titer of the bioprocess via decreasing end-product inhibition, (2) minimizing downstream separation energy input to less than 20% of the heating value of the product, and (3) generating no waste products.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [2];  [1];  [1];  [1]
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  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Pennsylvania State Univ., University Park, PA (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:
1432608
Alternate Identifier(s):
OSTI ID: 1434342
Report Number(s):
NREL/JA-5100-71279
Journal ID: ISSN 1463-9262; GRCHFJ
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 20; Journal Issue: 8; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; liquid-liquid extraction; in situ product recovery; distillation; carboxylic acids

Citation Formats

Saboe, Patrick O., Manker, Lorenz P., Michener, William E., Peterson, Darren J., Brandner, David G., Deutch, Stephen P., Kumar, Manish, Cywar, Robin M., Beckham, Gregg T., and Karp, Eric M. In situ recovery of bio-based carboxylic acids. United States: N. p., 2018. Web. doi:10.1039/C7GC03747C.
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Saboe, Patrick O., Manker, Lorenz P., Michener, William E., Peterson, Darren J., Brandner, David G., Deutch, Stephen P., Kumar, Manish, Cywar, Robin M., Beckham, Gregg T., & Karp, Eric M. In situ recovery of bio-based carboxylic acids. United States. https://doi.org/10.1039/C7GC03747C
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Saboe, Patrick O., Manker, Lorenz P., Michener, William E., Peterson, Darren J., Brandner, David G., Deutch, Stephen P., Kumar, Manish, Cywar, Robin M., Beckham, Gregg T., and Karp, Eric M. Fri . "In situ recovery of bio-based carboxylic acids". United States. https://doi.org/10.1039/C7GC03747C. https://www.osti.gov/servlets/purl/1432608.
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@article{osti_1432608,
title = {In situ recovery of bio-based carboxylic acids},
author = {Saboe, Patrick O. and Manker, Lorenz P. and Michener, William E. and Peterson, Darren J. and Brandner, David G. and Deutch, Stephen P. and Kumar, Manish and Cywar, Robin M. and Beckham, Gregg T. and Karp, Eric M.},
abstractNote = {The economics of chemical and biological processes is often dominated by the expense of downstream product separations from dilute product streams. Continuous separation techniques, such as in situ product recovery (ISPR), are attractive in that they can concentrate products from a reactor and minimize solvent loss, thereby increasing purity and sustainability of the process. In bioprocesses, ISPR can have an additional advantage of increasing productivity by alleviating product inhibition on the microorganism. In this work, we developed a liquid–liquid extraction (LLE)-based ISPR system integrated with downstream distillation to selectively purify free carboxylic acids, which were selected as exemplary bioproducts due to their ability to be produced at industrially relevant titers and productivities. Equilibrium constants for the extraction of carboxylic acids into a phosphine-oxide based organic phase were experimentally determined. Complete recovery of acids from the extractant and recyclability of the organic phase were demonstrated through multiple extraction–distillation cycles. Using these data, an equilibrium model was developed to predict the acid loading in the organic phase as a function of the extraction equilibrium constant, initial aqueous acid concentration, pH, organic to aqueous volume ratio, and temperature. A distillation process model was then used to predict the energy input required to distill neat acid from an organic phase as a function of the acid loading in the organic phase feed. The heat integrated distillation train can achieve neat recovery of acetic acid with an energy input of 2.6 MJ kg-1 of acetic acid. This LLE-based ISPR system integrated with downstream distillation has an estimated carbon footprint of less than 0.36 kg CO2 per kg of acetic acid, and provides a green approach to enable both new industrial bioprocesses, and process intensification of existing industrial operations by (1) increasing the productivity and titer of the bioprocess via decreasing end-product inhibition, (2) minimizing downstream separation energy input to less than 20% of the heating value of the product, and (3) generating no waste products.},
doi = {10.1039/C7GC03747C},
journal = {Green Chemistry},
number = 8,
volume = 20,
place = {United States},
year = {Fri Mar 16 00:00:00 EDT 2018},
month = {Fri Mar 16 00:00:00 EDT 2018}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1039/C7GC03747C
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Cited by: 49 works
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Figures / Tables:

Fig. 1 Fig. 1: Proposed distillation based in situ product recovery (ISPR) system to recover free acids. Acids present in bioreactor (1) are extracted into an organic phase through a hollow fiber membrane contactor (2). The bioreactor media and cells are recycled (3) and the organic phase is passed into a distillationmore » column (4) where neat free acids are vaporized (5) recovered as a distillate from the heavy organic phase (6).« less
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