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Title: Ferrous and Ferric Ion-Facilitated Dilute Acid Pretreatment of Lignocellulosic Biomass under Anaerobic or Aerobic Conditions: Observations of Fe Valence Interchange and the Role of Fenton Reaction

Abstract

Ferrous ion co-catalyst enhancement of dilute-acid (DA) pretreatment of biomass is a promising technology for increasing the release of sugars from recalcitrant lignocellulosic biomass. However, due to the reductive status of ferrous ion and its susceptibility to oxidation with exposure to atmosphere, its effective application presumably requires anaerobic aqueous conditions created by nitrogen gas-purging, which adds extra costs. The objective of this study was to assess the effectiveness of oxidative iron ion, (i.e., ferric ion) as a co-catalyst in DA pretreatment of biomass, using an anaerobic chamber to strictly control exposure to oxygen during setup and post-pretreatment analyses. Remarkably, the ferric ions were found to be as efficient as ferrous ions in enhancing sugar release during DA pretreatment of biomass, which may be attributed to the observation that a major portion of the initial ferric ions were converted to ferrous during pretreatment. Furthermore, the detection of hydrogen peroxide in the liquors after DA/Fe ion pretreatment suggests that Fenton reaction chemistry was likely involved in DA/Fe ion pretreatments of biomass, contributing to the observed ferric and ferrous interchanges during pretreatment. These results help define the extent and specification requirements for applying iron ions as co-catalysts in DA pretreatments of biomass.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [1];  [1];  [1];  [1]
  1. 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), Transportation Office. Bioenergy Technologies Office
OSTI Identifier:
1606119
Report Number(s):
NREL-JA-2700-76370
Journal ID: ISSN 1420-3049; MOLEFW
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Molecules
Additional Journal Information:
Journal Volume: 25; Journal Issue: 6; Journal ID: ISSN 1420-3049
Publisher:
MDPI
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; dilute acid pretreatment; metal co-catalyst; ferric ions; ferrous ions; biomass; cellulose; corn stover; hydrogen peroxide; Fenton reaction

Citation Formats

Wei, Hui, Wang, Wei, Ciesielski, Peter N, Donohoe, Bryon S, Zhang, Min, Himmel, Michael E, Chen, Xiaowen, and Tucker, Melvin P. Ferrous and Ferric Ion-Facilitated Dilute Acid Pretreatment of Lignocellulosic Biomass under Anaerobic or Aerobic Conditions: Observations of Fe Valence Interchange and the Role of Fenton Reaction. United States: N. p., 2020. Web. https://doi.org/10.3390/molecules25061427.
Wei, Hui, Wang, Wei, Ciesielski, Peter N, Donohoe, Bryon S, Zhang, Min, Himmel, Michael E, Chen, Xiaowen, & Tucker, Melvin P. Ferrous and Ferric Ion-Facilitated Dilute Acid Pretreatment of Lignocellulosic Biomass under Anaerobic or Aerobic Conditions: Observations of Fe Valence Interchange and the Role of Fenton Reaction. United States. https://doi.org/10.3390/molecules25061427
Wei, Hui, Wang, Wei, Ciesielski, Peter N, Donohoe, Bryon S, Zhang, Min, Himmel, Michael E, Chen, Xiaowen, and Tucker, Melvin P. Sun . "Ferrous and Ferric Ion-Facilitated Dilute Acid Pretreatment of Lignocellulosic Biomass under Anaerobic or Aerobic Conditions: Observations of Fe Valence Interchange and the Role of Fenton Reaction". United States. https://doi.org/10.3390/molecules25061427. https://www.osti.gov/servlets/purl/1606119.
@article{osti_1606119,
title = {Ferrous and Ferric Ion-Facilitated Dilute Acid Pretreatment of Lignocellulosic Biomass under Anaerobic or Aerobic Conditions: Observations of Fe Valence Interchange and the Role of Fenton Reaction},
author = {Wei, Hui and Wang, Wei and Ciesielski, Peter N and Donohoe, Bryon S and Zhang, Min and Himmel, Michael E and Chen, Xiaowen and Tucker, Melvin P},
abstractNote = {Ferrous ion co-catalyst enhancement of dilute-acid (DA) pretreatment of biomass is a promising technology for increasing the release of sugars from recalcitrant lignocellulosic biomass. However, due to the reductive status of ferrous ion and its susceptibility to oxidation with exposure to atmosphere, its effective application presumably requires anaerobic aqueous conditions created by nitrogen gas-purging, which adds extra costs. The objective of this study was to assess the effectiveness of oxidative iron ion, (i.e., ferric ion) as a co-catalyst in DA pretreatment of biomass, using an anaerobic chamber to strictly control exposure to oxygen during setup and post-pretreatment analyses. Remarkably, the ferric ions were found to be as efficient as ferrous ions in enhancing sugar release during DA pretreatment of biomass, which may be attributed to the observation that a major portion of the initial ferric ions were converted to ferrous during pretreatment. Furthermore, the detection of hydrogen peroxide in the liquors after DA/Fe ion pretreatment suggests that Fenton reaction chemistry was likely involved in DA/Fe ion pretreatments of biomass, contributing to the observed ferric and ferrous interchanges during pretreatment. These results help define the extent and specification requirements for applying iron ions as co-catalysts in DA pretreatments of biomass.},
doi = {10.3390/molecules25061427},
journal = {Molecules},
number = 6,
volume = 25,
place = {United States},
year = {2020},
month = {3}
}

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