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Title: Reductive catalytic fractionation of agricultural residue and energy crop lignin and application of lignin oil as antimicrobials

Abstract

Cheap and abundant waste from bioethanol and agricultural processing industries are an alluring alternative feedstock for biorefineries. In this work, we employ reductive catalytic fractionation (RCF) to depolymerize, over Ru/C powder and Ru/Al2O3 pellets, five herbaceous biomass feedstocks, namely corn stover, miscanthus, switchgrass, sugarcane bagasse, and wheat straw into phenolic monomers with high yields (~40 wt.% based on total (Klason + acid soluble) lignin and > 50 wt.% when stabilized using aldehydes), leaving behind a carbohydrate pulp residue. Interestingly, a polar solvent is sufficient to solubilize and fragment the lignin polymer into monomers without any catalyst. Here, contrary to woody biomass, where the monomer yields are positively correlated with the S-content of lignin, principal component analysis indicates that the monomer yields from herbaceous biomass depend on the content of lignin crosslinker – ferulate. Using NMR, we further identify α – 6 C-C linked oligomers formed from condensation reactions, explaining the unexpected low monomer yields of high β-O-4 herbaceous biomass. Recyclability experiments indicate that catalyst deactivation occurs through sintering, leaching, and fouling. Lignin oil from herbaceous biomass exhibits bacteriostatic effects against Staphylococcus aureus, highlighting a potential application in functional food development and as food or feed preservative.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1]
  1. University of Delaware, Newark, DE (United States)
Publication Date:
Research Org.:
Univ. of Delaware, Newark, DE (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Contributing Org.:
Delaware Environmental Institute Fellows Program from the University of Delaware. Advanced Material Characterization Laboratory (AMCL), and the W.M. Keck Microscopy Facility at the University of Delaware. Great Lakes Bioenergy Research Center, Michigan State University. Idaho National laboratory and Forest concepts.
OSTI Identifier:
1669112
Alternate Identifier(s):
OSTI ID: 1671352
Grant/Contract Number:  
SC0001004
Resource Type:
Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 2020; Journal Issue: 22; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; 09 BIOMASS FUELS; 99 GENERAL AND MISCELLANEOUS; Lignin; Valorization; Biomass; Antimicrobial activity; Machine learning; Biorefinery

Citation Formats

Ebikade, Osamudiamhen Elvis, Samulewicz, Nicholas, Xuan, Shuangqing, Sheehan, James D., Wu, Changqing, and Vlachos, Dionisios G.. Reductive catalytic fractionation of agricultural residue and energy crop lignin and application of lignin oil as antimicrobials. United States: N. p., 2020. Web. doi:10.1039/D0GC02781B.
Ebikade, Osamudiamhen Elvis, Samulewicz, Nicholas, Xuan, Shuangqing, Sheehan, James D., Wu, Changqing, & Vlachos, Dionisios G.. Reductive catalytic fractionation of agricultural residue and energy crop lignin and application of lignin oil as antimicrobials. United States. https://doi.org/10.1039/D0GC02781B
Ebikade, Osamudiamhen Elvis, Samulewicz, Nicholas, Xuan, Shuangqing, Sheehan, James D., Wu, Changqing, and Vlachos, Dionisios G.. Wed . "Reductive catalytic fractionation of agricultural residue and energy crop lignin and application of lignin oil as antimicrobials". United States. https://doi.org/10.1039/D0GC02781B. https://www.osti.gov/servlets/purl/1669112.
@article{osti_1669112,
title = {Reductive catalytic fractionation of agricultural residue and energy crop lignin and application of lignin oil as antimicrobials},
author = {Ebikade, Osamudiamhen Elvis and Samulewicz, Nicholas and Xuan, Shuangqing and Sheehan, James D. and Wu, Changqing and Vlachos, Dionisios G.},
abstractNote = {Cheap and abundant waste from bioethanol and agricultural processing industries are an alluring alternative feedstock for biorefineries. In this work, we employ reductive catalytic fractionation (RCF) to depolymerize, over Ru/C powder and Ru/Al2O3 pellets, five herbaceous biomass feedstocks, namely corn stover, miscanthus, switchgrass, sugarcane bagasse, and wheat straw into phenolic monomers with high yields (~40 wt.% based on total (Klason + acid soluble) lignin and > 50 wt.% when stabilized using aldehydes), leaving behind a carbohydrate pulp residue. Interestingly, a polar solvent is sufficient to solubilize and fragment the lignin polymer into monomers without any catalyst. Here, contrary to woody biomass, where the monomer yields are positively correlated with the S-content of lignin, principal component analysis indicates that the monomer yields from herbaceous biomass depend on the content of lignin crosslinker – ferulate. Using NMR, we further identify α – 6 C-C linked oligomers formed from condensation reactions, explaining the unexpected low monomer yields of high β-O-4 herbaceous biomass. Recyclability experiments indicate that catalyst deactivation occurs through sintering, leaching, and fouling. Lignin oil from herbaceous biomass exhibits bacteriostatic effects against Staphylococcus aureus, highlighting a potential application in functional food development and as food or feed preservative.},
doi = {10.1039/D0GC02781B},
journal = {Green Chemistry},
number = 22,
volume = 2020,
place = {United States},
year = {Wed Jan 01 00:00:00 EST 2020},
month = {Wed Jan 01 00:00:00 EST 2020}
}

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