Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Effective Biomass Fractionation through Oxygen-Enhanced Alkaline–Oxidative Pretreatment

Journal Article · · ACS Sustainable Chemistry & Engineering
 [1];  [2];  [2];  [3];  [2];  [3];  [3];  [3];  [4];  [5];  [6];  [2];  [3];  [2]
  1. Michigan State Univ., East Lansing, MI (United States); Michigan State University
  2. Michigan State Univ., East Lansing, MI (United States)
  3. Univ. of Wisconsin, Madison, WI (United States)
  4. Montana State Univ., Bozeman, MT (United States)
  5. Michigan Biotechnology Inst., Lansing, MI (United States)
  6. Montana State Univ., Bozeman, MT (United States); LuleÅ Univ. of Technology (Sweden)
The high recalcitrance of plant cell walls is an obstacle for effective chemical or biological conversion into renewable chemicals and transportation fuels. Here, we investigated the utilization of both oxygen (O2) and hydrogen peroxide (H2O2) as co-oxidants during alkaline-oxidative pretreatment to improve biomass fractionation and increase enzymatic digestibility. The oxidative pretreatment of hybrid poplar was studied over a variety of conditions. Employing O2 in addition to H2O2 as a co-oxidant during the two-stage alkaline pre-extraction/copper-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment process resulted in a substantial improvement in delignification relative to using H2O2 alone during the second-stage Cu-AHP pretreatment, leading to high overall sugar yields even at H2O2 loadings as low as 2% (w/w of original biomass). The presence of H2O2, however, was both critical and synergistic. Performing analogous reactions in the absence of H2O2 resulted in approximately 25% less delignification and a 30% decrease in sugar yields. Here, the lignin isolated from this dual oxidant second stage had high aliphatic hydroxyl group content and reactivity to isocyanate, indicating that it is a promising substrate for the production of polyurethanes. To test the suitability of the isolated lignin as a source of aromatic monomers, the lignin was subjected to a sequential Bobbitt’s salt oxidation followed by formic-acid catalyzed depolymerization process. Monomer yields of approximately 17% (w/w) were obtained, and the difference in yields was not significant between lignin isolated from our Cu-AHP process with and without O2 as a co-oxidant. Thus, the addition of O2 did not lead to significant lignin crosslinking, a result consistent with the two-dimensional heteronuclear single-quantum coherence (2D HSQC) NMR spectra of the isolated lignin.
Research Organization:
Michigan State Univ., East Lansing, MI (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Grant/Contract Number:
EE0008148
OSTI ID:
1878349
Alternate ID(s):
OSTI ID: 1848687
Journal Information:
ACS Sustainable Chemistry & Engineering, Journal Name: ACS Sustainable Chemistry & Engineering Journal Issue: 3 Vol. 9; ISSN 2168-0485
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (53)

Recent Progress on Oxygen Delignification of Softwood Kraft Pulp book November 2018
Isolation of Functionalized Phenolic Monomers through Selective Oxidation and CO Bond Cleavage of the β-O-4 Linkages in Lignin journal November 2014
Replacing 100% of phenol in phenolic adhesive formulations with lignin: ARTICLE journal April 2017
The transition to a bio-economy: national perspectives journal May 2012
Catalysis with Cu II (bpy) improves alkaline hydrogen peroxide pretreatment journal December 2012
Liberation of Cellulose from the Lignin Cage: A Catalytic Pretreatment Method for the Production of Cellulosic Ethanol journal September 2010
Chemical aspects of kraft pulping journal January 1980
Characterization of lignins from wheat straw by alkaline peroxide treatment journal January 2000
Technoeconomic analysis of biofuels: A wiki-based platform for lignocellulosic biorefineries journal December 2010
Pretreatments to enhance the digestibility of lignocellulosic biomass journal January 2009
Lignin content versus syringyl to guaiacyl ratio amongst poplars journal February 2009
Ozonolysis: An advantageous pretreatment for lignocellulosic biomass revisited journal January 2016
Structure-antioxidant activity relationship of active oxygen catalytic lignin and lignin-carbohydrate complex journal October 2019
Chemical modification of lignins: Towards biobased polymers journal July 2014
A review on lignin-based polymeric, micro- and nano-structured materials journal December 2014
Depolymerization of lignins and their applications for the preparation of polyols and rigid polyurethane foams: A review journal July 2016
Lignin utilization: A review of lignin depolymerization from various aspects journal June 2019
Potential use of alkaline hydrogen peroxide in lignocellulosic biomass pretreatment and valorization – A review journal September 2019
Integrated Two-Stage Alkaline–Oxidative Pretreatment of Hybrid Poplar. Part 2: Impact of Cu-Catalyzed Alkaline Hydrogen Peroxide Pretreatment Conditions on Process Performance and Economics journal August 2019
Polyurethane Coatings Based on Chemically Unmodified Fractionated Lignin journal April 2015
Alkaline Peroxide Delignification of Corn Stover journal June 2017
High Modulus, Strength, and Toughness Polyurethane Elastomer Based on Unmodified Lignin journal July 2017
Lignin Conversion to Low-Molecular-Weight Aromatics via an Aerobic Oxidation-Hydrolysis Sequence: Comparison of Different Lignin Sources journal January 2018
On the Versatility of Urethane/Urea Bonds: Reversibility, Blocked Isocyanate, and Non-isocyanate Polyurethane journal October 2012
Nitrogen-Centered Activators of Peroxide-Reinforced Oxygen Delignification journal March 2004
Chemoselective Metal-Free Aerobic Alcohol Oxidation in Lignin journal April 2013
A Photochemical Strategy for Lignin Degradation at Room Temperature journal January 2014
Formic-acid-induced depolymerization of oxidized lignin to aromatics journal November 2014
An energy revolution journal December 2011
Alternatives for lignocellulosic pulp delignification using polyoxometalates and oxygen: a review journal January 2007
Development of lignin-based polyurethane thermoplastics journal January 2013
Structural changes in lignins isolated using an acidic ionic liquid water mixture journal January 2015
Cell wall-associated transition metals improve alkaline-oxidative pretreatment in diverse hardwoods journal January 2016
New insights into the structure and composition of technical lignins: a comparative characterisation study journal January 2016
Processing Pine Wood into Vanillin and Glucose by Sequential Catalytic Oxidation and Enzymatic Hydrolysis journal November 2016
Oxygen Delignification Chemistry and Its Impact on Pulp Fibers journal January 2003
Increasing the revenue from lignocellulosic biomass: Maximizing feedstock utilization journal May 2017
CHEMISTRY: Making Fuels from Biomass journal June 2005
The Path Forward for Biofuels and Biomaterials journal January 2006
Biomass Recalcitrance: Engineering Plants and Enzymes for Biofuels Production journal February 2007
Chemicals from Biomass journal November 2007
Cellulosic Biofuels--Got Gasoline? journal August 2009
Feedstocks for Lignocellulosic Biofuels journal August 2010
Lignin Valorization: Improving Lignin Processing in the Biorefinery journal May 2014
Fundamentals of o×ygen delignification. Part II. Functional group formation/elimination in residual kraft lignin journal January 1998
Chemical and structural changes associated with Cu-catalyzed alkaline-oxidative delignification of hybrid poplar journal August 2015
Effective alkaline metal-catalyzed oxidative delignification of hybrid poplar journal February 2016
Integrated experimental and technoeconomic evaluation of two-stage Cu-catalyzed alkaline–oxidative pretreatment of hybrid poplar journal May 2018
Performance of three delignifying pretreatments on hardwoods: hydrolysis yields, comprehensive mass balances, and lignin properties journal September 2019
Pulp delignification with oxygen and copper(II)-polyimine complexes journal May 2014
Structural Changes in Lignin During Kraft Pulping journal January 1984
Statistical comparison of dissolution profiles journal August 2015
Lignin-Based Polyurethanes: Opportunities for Bio-Based Foams, Elastomers, Coatings and Adhesives journal July 2019

Figures / Tables (7)