Recovery and conversion of acetic acid from a phosphonium phosphinate ionic liquid to enable valorization of fermented wastewater

Ehsan Reyhanitash, Egor Fufachev, Kaspar D. Van Munster, Michael B.M. Van Beek, Lisette M.J. Sprakel, Carmen N. Edelijn, Bert M. Weckhuysen, Sascha R.A. Kersten, Pieter C.A. Bruijnincx, Boelo Schuur*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

3 Citations (Scopus)
23 Downloads (Pure)

Abstract

Production of volatile fatty acids (VFAs) by fermentation is a potential sustainable alternative for conventional petrochemical routes to VFAs. Due to the low VFA content of fermentation broths, robust and economical separation technology has to be devised to recover the VFA. Liquid-liquid extraction of VFAs with the phosphonium phosphinate ionic liquid (IL) [P 666,14 ][Phos] allows good VFA extractability. For an extraction process using [P 666,14 ][Phos] to be green, it is essential to efficiently regenerate the solvent and recover the VFA. To obtain insight into the (strong) intermolecular interactions between [P 666,14 ][Phos] and acetic acid, selected as a model VFA, 1 H NMR, 31 P NMR, FT-IR and isothermal titration calorimetry (ITC) were applied. The observations were used to interpret operations to recover acetic acid from the IL, which included evaporation at elevated temperature under vacuum, possibly assisted by nitrogen stripping, in situ esterification and back-extraction with volatile bases. Through evaporative regeneration with nitrogen stripping, HAc could be removed, but only down to an HAc/IL molar ratio of 1. The remaining molar equivalent of HAc-IL interacts tightly with the IL by partial proton transfer and strong hydrogen bonding interactions with the phosphinate anion. Back-extraction of HAc with trimethylamine (TMA) and subsequent decomposition of the HAc-TMA complexes allowed for successful IL regeneration. This process uses ten times less amine (TMA) than conventional amine-based extraction processes (e.g. tri-n-octyl amine), and provides a sustainable process route to obtain pure carboxylic acids from highly diluted aqueous solutions without generating large streams of byproducts. Further valorization via in-line vaporization/catalytic ketonization or via in-line thermal decomposition and ketonization of the TMA-HAc salt was also demonstrated, showing the potential of the VFAs as a green platform for bio-based chemicals.

Original languageEnglish
Pages (from-to)2023-2034
Number of pages12
JournalGreen chemistry
Volume21
Issue number8
DOIs
Publication statusPublished - 21 Apr 2019

Fingerprint

Volatile fatty acids
Ionic Liquids
Volatile Fatty Acids
Ionic liquids
Acetic acid
Acetic Acid
acetic acid
Wastewater
fatty acid
wastewater
Recovery
Amines
Fermentation
fermentation
nuclear magnetic resonance
Nitrogen
regeneration
Nuclear magnetic resonance
ionic liquid
liquid

Cite this

Reyhanitash, E., Fufachev, E., Van Munster, K. D., Van Beek, M. B. M., Sprakel, L. M. J., Edelijn, C. N., ... Schuur, B. (2019). Recovery and conversion of acetic acid from a phosphonium phosphinate ionic liquid to enable valorization of fermented wastewater. Green chemistry, 21(8), 2023-2034. https://doi.org/10.1039/c9gc00725c
Reyhanitash, Ehsan ; Fufachev, Egor ; Van Munster, Kaspar D. ; Van Beek, Michael B.M. ; Sprakel, Lisette M.J. ; Edelijn, Carmen N. ; Weckhuysen, Bert M. ; Kersten, Sascha R.A. ; Bruijnincx, Pieter C.A. ; Schuur, Boelo. / Recovery and conversion of acetic acid from a phosphonium phosphinate ionic liquid to enable valorization of fermented wastewater. In: Green chemistry. 2019 ; Vol. 21, No. 8. pp. 2023-2034.
@article{757895a0204f47ad96dafa2aaa0310c3,
title = "Recovery and conversion of acetic acid from a phosphonium phosphinate ionic liquid to enable valorization of fermented wastewater",
abstract = "Production of volatile fatty acids (VFAs) by fermentation is a potential sustainable alternative for conventional petrochemical routes to VFAs. Due to the low VFA content of fermentation broths, robust and economical separation technology has to be devised to recover the VFA. Liquid-liquid extraction of VFAs with the phosphonium phosphinate ionic liquid (IL) [P 666,14 ][Phos] allows good VFA extractability. For an extraction process using [P 666,14 ][Phos] to be green, it is essential to efficiently regenerate the solvent and recover the VFA. To obtain insight into the (strong) intermolecular interactions between [P 666,14 ][Phos] and acetic acid, selected as a model VFA, 1 H NMR, 31 P NMR, FT-IR and isothermal titration calorimetry (ITC) were applied. The observations were used to interpret operations to recover acetic acid from the IL, which included evaporation at elevated temperature under vacuum, possibly assisted by nitrogen stripping, in situ esterification and back-extraction with volatile bases. Through evaporative regeneration with nitrogen stripping, HAc could be removed, but only down to an HAc/IL molar ratio of 1. The remaining molar equivalent of HAc-IL interacts tightly with the IL by partial proton transfer and strong hydrogen bonding interactions with the phosphinate anion. Back-extraction of HAc with trimethylamine (TMA) and subsequent decomposition of the HAc-TMA complexes allowed for successful IL regeneration. This process uses ten times less amine (TMA) than conventional amine-based extraction processes (e.g. tri-n-octyl amine), and provides a sustainable process route to obtain pure carboxylic acids from highly diluted aqueous solutions without generating large streams of byproducts. Further valorization via in-line vaporization/catalytic ketonization or via in-line thermal decomposition and ketonization of the TMA-HAc salt was also demonstrated, showing the potential of the VFAs as a green platform for bio-based chemicals.",
author = "Ehsan Reyhanitash and Egor Fufachev and {Van Munster}, {Kaspar D.} and {Van Beek}, {Michael B.M.} and Sprakel, {Lisette M.J.} and Edelijn, {Carmen N.} and Weckhuysen, {Bert M.} and Kersten, {Sascha R.A.} and Bruijnincx, {Pieter C.A.} and Boelo Schuur",
year = "2019",
month = "4",
day = "21",
doi = "10.1039/c9gc00725c",
language = "English",
volume = "21",
pages = "2023--2034",
journal = "Green chemistry",
issn = "1463-9262",
publisher = "Royal Society of Chemistry",
number = "8",

}

Reyhanitash, E, Fufachev, E, Van Munster, KD, Van Beek, MBM, Sprakel, LMJ, Edelijn, CN, Weckhuysen, BM, Kersten, SRA, Bruijnincx, PCA & Schuur, B 2019, 'Recovery and conversion of acetic acid from a phosphonium phosphinate ionic liquid to enable valorization of fermented wastewater', Green chemistry, vol. 21, no. 8, pp. 2023-2034. https://doi.org/10.1039/c9gc00725c

Recovery and conversion of acetic acid from a phosphonium phosphinate ionic liquid to enable valorization of fermented wastewater. / Reyhanitash, Ehsan; Fufachev, Egor; Van Munster, Kaspar D.; Van Beek, Michael B.M.; Sprakel, Lisette M.J.; Edelijn, Carmen N.; Weckhuysen, Bert M.; Kersten, Sascha R.A.; Bruijnincx, Pieter C.A.; Schuur, Boelo.

In: Green chemistry, Vol. 21, No. 8, 21.04.2019, p. 2023-2034.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Recovery and conversion of acetic acid from a phosphonium phosphinate ionic liquid to enable valorization of fermented wastewater

AU - Reyhanitash, Ehsan

AU - Fufachev, Egor

AU - Van Munster, Kaspar D.

AU - Van Beek, Michael B.M.

AU - Sprakel, Lisette M.J.

AU - Edelijn, Carmen N.

AU - Weckhuysen, Bert M.

AU - Kersten, Sascha R.A.

AU - Bruijnincx, Pieter C.A.

AU - Schuur, Boelo

PY - 2019/4/21

Y1 - 2019/4/21

N2 - Production of volatile fatty acids (VFAs) by fermentation is a potential sustainable alternative for conventional petrochemical routes to VFAs. Due to the low VFA content of fermentation broths, robust and economical separation technology has to be devised to recover the VFA. Liquid-liquid extraction of VFAs with the phosphonium phosphinate ionic liquid (IL) [P 666,14 ][Phos] allows good VFA extractability. For an extraction process using [P 666,14 ][Phos] to be green, it is essential to efficiently regenerate the solvent and recover the VFA. To obtain insight into the (strong) intermolecular interactions between [P 666,14 ][Phos] and acetic acid, selected as a model VFA, 1 H NMR, 31 P NMR, FT-IR and isothermal titration calorimetry (ITC) were applied. The observations were used to interpret operations to recover acetic acid from the IL, which included evaporation at elevated temperature under vacuum, possibly assisted by nitrogen stripping, in situ esterification and back-extraction with volatile bases. Through evaporative regeneration with nitrogen stripping, HAc could be removed, but only down to an HAc/IL molar ratio of 1. The remaining molar equivalent of HAc-IL interacts tightly with the IL by partial proton transfer and strong hydrogen bonding interactions with the phosphinate anion. Back-extraction of HAc with trimethylamine (TMA) and subsequent decomposition of the HAc-TMA complexes allowed for successful IL regeneration. This process uses ten times less amine (TMA) than conventional amine-based extraction processes (e.g. tri-n-octyl amine), and provides a sustainable process route to obtain pure carboxylic acids from highly diluted aqueous solutions without generating large streams of byproducts. Further valorization via in-line vaporization/catalytic ketonization or via in-line thermal decomposition and ketonization of the TMA-HAc salt was also demonstrated, showing the potential of the VFAs as a green platform for bio-based chemicals.

AB - Production of volatile fatty acids (VFAs) by fermentation is a potential sustainable alternative for conventional petrochemical routes to VFAs. Due to the low VFA content of fermentation broths, robust and economical separation technology has to be devised to recover the VFA. Liquid-liquid extraction of VFAs with the phosphonium phosphinate ionic liquid (IL) [P 666,14 ][Phos] allows good VFA extractability. For an extraction process using [P 666,14 ][Phos] to be green, it is essential to efficiently regenerate the solvent and recover the VFA. To obtain insight into the (strong) intermolecular interactions between [P 666,14 ][Phos] and acetic acid, selected as a model VFA, 1 H NMR, 31 P NMR, FT-IR and isothermal titration calorimetry (ITC) were applied. The observations were used to interpret operations to recover acetic acid from the IL, which included evaporation at elevated temperature under vacuum, possibly assisted by nitrogen stripping, in situ esterification and back-extraction with volatile bases. Through evaporative regeneration with nitrogen stripping, HAc could be removed, but only down to an HAc/IL molar ratio of 1. The remaining molar equivalent of HAc-IL interacts tightly with the IL by partial proton transfer and strong hydrogen bonding interactions with the phosphinate anion. Back-extraction of HAc with trimethylamine (TMA) and subsequent decomposition of the HAc-TMA complexes allowed for successful IL regeneration. This process uses ten times less amine (TMA) than conventional amine-based extraction processes (e.g. tri-n-octyl amine), and provides a sustainable process route to obtain pure carboxylic acids from highly diluted aqueous solutions without generating large streams of byproducts. Further valorization via in-line vaporization/catalytic ketonization or via in-line thermal decomposition and ketonization of the TMA-HAc salt was also demonstrated, showing the potential of the VFAs as a green platform for bio-based chemicals.

UR - http://www.scopus.com/inward/record.url?scp=85063297990&partnerID=8YFLogxK

U2 - 10.1039/c9gc00725c

DO - 10.1039/c9gc00725c

M3 - Article

AN - SCOPUS:85063297990

VL - 21

SP - 2023

EP - 2034

JO - Green chemistry

JF - Green chemistry

SN - 1463-9262

IS - 8

ER -

Reyhanitash E, Fufachev E, Van Munster KD, Van Beek MBM, Sprakel LMJ, Edelijn CN et al. Recovery and conversion of acetic acid from a phosphonium phosphinate ionic liquid to enable valorization of fermented wastewater. Green chemistry. 2019 Apr 21;21(8):2023-2034. https://doi.org/10.1039/c9gc00725c