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Title: Ammonia pretreatment of corn stover enables facile lignin extraction

Abstract

Thermochemical pretreatment of lignocellulose is often employed to render polysaccharides more digestible by carbohydrate-active enzymes to maximize sugar yields. The fate of lignin during pretreatment, however, is highly dependent on the chemistry employed and must be considered in cases where lignin valorization is targeted alongside sugar conversion—an important feature of future biorefinery development. Here, a two-step process is demonstrated in which anhydrous ammonia (AA) pretreatment is followed by mild NaOH extraction on corn stover to solubilize and fractionate lignin. As known, AA pretreatment simultaneously alters the structure of cellulose with enhanced digestibility while redistributing lignin. The AA-pretreated residue is then extracted with dilute NaOH at mild conditions to maximize lignin separation, resulting in a digestible carbohydrate-rich solid fraction and a solubilized lignin stream. Lignin removal of more than 65% with over 84% carbohydrate retention is achieved after mild NaOH extraction of AA-pretreated corn stover with 0.1 M NaOH at 25 °C. Two-dimensional nuclear magnetic resonance (2D-NMR) spectroscopy of the AA-pretreated residue shows that ammonolysis of ester bonds occurs to partially liberate hydroxycinnamic acids, and the AA-pretreated/NaOH-extracted residue exhibits a global reduction of all lignin moieties caused by reduced lignin content. A significant reduction (~70%) in the weight-average molecular weight (Mw)more » of extracted lignin is also achieved. Imaging of AA-pretreated/NaOH extracted residues show extensive delamination and disappearance of coalesced lignin globules from within the secondary cell walls. Glycome profiling analyses demonstrates ultrastructural level cell wall modifications induced by AA pretreatment and NaOH extraction, resulting in enhanced extractability of hemicellulosic glycans, indicating enhanced polysaccharide accessibility. The glucose and xylose yields from enzymatic hydrolysis of AA-pretreated/NaOH-extracted corn stover were higher by ~80% and ~60%, respectively, compared to untreated corn stover at 1% solids loadings. For digestions at 20% solids, a benefit of NaOH extraction is realized in achieving ~150 g/L of total monomeric sugars (glucose, xylose, and arabinose) in the enzymatic hydrolysates from AA-pretreated/NaOH-extracted corn stover. Altogether, this process enables facile lignin extraction in tandem with a leading thermochemical pretreatment approach, demonstrating excellent retention of highly digestible polysaccharides in the solid phase and a highly depolymerized, soluble lignin-rich stream.« less

Authors:
 [1];  [1];  [1];  [2];  [3];  [1];  [1]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Univ. of Georgia, Athens, GA (United States); Mascoma LLC (Lallemand Inc.), Lebanon, NH (United States)
  3. Univ. of Georgia, Athens, GA (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:
1346537
Report Number(s):
NREL/JA-2700-68056
Journal ID: ISSN 2168-0485
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Volume: 5; Journal Issue: 3; Journal ID: ISSN 2168-0485
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ammonia; biofuels; fractionation; ligninocellulose; pretreatment

Citation Formats

Mittal, Ashutosh, Katahira, Rui, Donohoe, Bryon S., Pattathil, Sivakumar, Kandemkavil, Sindhu, Reed, Michelle L., Biddy, Mary J., and Beckham, Gregg T.. Ammonia pretreatment of corn stover enables facile lignin extraction. United States: N. p., 2017. Web. https://doi.org/10.1021/acssuschemeng.6b02892.
Mittal, Ashutosh, Katahira, Rui, Donohoe, Bryon S., Pattathil, Sivakumar, Kandemkavil, Sindhu, Reed, Michelle L., Biddy, Mary J., & Beckham, Gregg T.. Ammonia pretreatment of corn stover enables facile lignin extraction. United States. https://doi.org/10.1021/acssuschemeng.6b02892
Mittal, Ashutosh, Katahira, Rui, Donohoe, Bryon S., Pattathil, Sivakumar, Kandemkavil, Sindhu, Reed, Michelle L., Biddy, Mary J., and Beckham, Gregg T.. Thu . "Ammonia pretreatment of corn stover enables facile lignin extraction". United States. https://doi.org/10.1021/acssuschemeng.6b02892. https://www.osti.gov/servlets/purl/1346537.
@article{osti_1346537,
title = {Ammonia pretreatment of corn stover enables facile lignin extraction},
author = {Mittal, Ashutosh and Katahira, Rui and Donohoe, Bryon S. and Pattathil, Sivakumar and Kandemkavil, Sindhu and Reed, Michelle L. and Biddy, Mary J. and Beckham, Gregg T.},
abstractNote = {Thermochemical pretreatment of lignocellulose is often employed to render polysaccharides more digestible by carbohydrate-active enzymes to maximize sugar yields. The fate of lignin during pretreatment, however, is highly dependent on the chemistry employed and must be considered in cases where lignin valorization is targeted alongside sugar conversion—an important feature of future biorefinery development. Here, a two-step process is demonstrated in which anhydrous ammonia (AA) pretreatment is followed by mild NaOH extraction on corn stover to solubilize and fractionate lignin. As known, AA pretreatment simultaneously alters the structure of cellulose with enhanced digestibility while redistributing lignin. The AA-pretreated residue is then extracted with dilute NaOH at mild conditions to maximize lignin separation, resulting in a digestible carbohydrate-rich solid fraction and a solubilized lignin stream. Lignin removal of more than 65% with over 84% carbohydrate retention is achieved after mild NaOH extraction of AA-pretreated corn stover with 0.1 M NaOH at 25 °C. Two-dimensional nuclear magnetic resonance (2D-NMR) spectroscopy of the AA-pretreated residue shows that ammonolysis of ester bonds occurs to partially liberate hydroxycinnamic acids, and the AA-pretreated/NaOH-extracted residue exhibits a global reduction of all lignin moieties caused by reduced lignin content. A significant reduction (~70%) in the weight-average molecular weight (Mw) of extracted lignin is also achieved. Imaging of AA-pretreated/NaOH extracted residues show extensive delamination and disappearance of coalesced lignin globules from within the secondary cell walls. Glycome profiling analyses demonstrates ultrastructural level cell wall modifications induced by AA pretreatment and NaOH extraction, resulting in enhanced extractability of hemicellulosic glycans, indicating enhanced polysaccharide accessibility. The glucose and xylose yields from enzymatic hydrolysis of AA-pretreated/NaOH-extracted corn stover were higher by ~80% and ~60%, respectively, compared to untreated corn stover at 1% solids loadings. For digestions at 20% solids, a benefit of NaOH extraction is realized in achieving ~150 g/L of total monomeric sugars (glucose, xylose, and arabinose) in the enzymatic hydrolysates from AA-pretreated/NaOH-extracted corn stover. Altogether, this process enables facile lignin extraction in tandem with a leading thermochemical pretreatment approach, demonstrating excellent retention of highly digestible polysaccharides in the solid phase and a highly depolymerized, soluble lignin-rich stream.},
doi = {10.1021/acssuschemeng.6b02892},
journal = {ACS Sustainable Chemistry & Engineering},
number = 3,
volume = 5,
place = {United States},
year = {2017},
month = {2}
}

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