Characterization of fractional cuts of co-solvent enhanced lignocellulosic fractionation lignin isolated by sequential precipitation

doi:10.1016/j.biortech.2018.09.130

Title: Characterization of fractional cuts of co-solvent enhanced lignocellulosic fractionation lignin isolated by sequential precipitation

Abstract

Lignin valorization is significantly hindered by the intrinsic heterogeneity of its complex structures and variability of biomass feedstocks. Fractionation of lignin can overcome these challenges by producing functionally distinct lignin cuts that can be further tailored to end products. Herein, lignin was extracted and depolymerized from poplar by the co-solvent enhanced lignocellulosic fractionation method with renewable THF to obtain CELF lignin. Several solvents were screened to separate soluble and insoluble fractions from the parent CELF lignin. The ethanol soluble portion was then fractionated into different molecular weight cuts via sequential precipitation of the lignin by reducing the concentration of THF. The physicochemical structures of different CELF lignin cuts were elucidated by GPC and NMR techniques. These results suggest that CELF lignin cuts with lower molecular weight contain progressively higher phenolic and carboxylic acid OH groups, which can be more suitable as green antioxidants than the parent lignin.

Authors:

Meng, Xianzhi ^[1]; Parikh, Aakash ^[2]; Seemala, Bhogeswararao ^[2]; Kumar, Rajeev ^[2];

^[3]; Wyman, Charles E. ^[2]; Cai, Charles M. ^[2];

^[4]

Univ. of Tennessee, Knoxville, TN (United States)
Univ. of California, Riverside, CA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Publication Date:: 2018-09-27

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of California, Riverside, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office

OSTI Identifier:: 1489560

Alternate Identifier(s):: OSTI ID: 1581904; OSTI ID: 1636689

Grant/Contract Number:: AC05-00OR22725; EE0007006

Resource Type:: Accepted Manuscript

Journal Name:: Bioresource Technology

Additional Journal Information:: Journal Volume: 272; Journal Issue: C; Journal ID: ISSN 0960-8524

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 59 BASIC BIOLOGICAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Lignin valorization; Co-solvent enhanced lignocellulosic fractionation; Sequential precipitation; Molecular weight distribution; 09 BIOMASS FUELS

Citation Formats


                    Meng, Xianzhi, Parikh, Aakash, Seemala, Bhogeswararao, Kumar, Rajeev, Pu, Yunqiao Joseph, Wyman, Charles E., Cai, Charles M., and Ragauskas, Arthur J. Characterization of fractional cuts of co-solvent enhanced lignocellulosic fractionation lignin isolated by sequential precipitation.  United States: N. p., 2018. 
        Web.  doi:10.1016/j.biortech.2018.09.130.

Copy to clipboard


                    Meng, Xianzhi, Parikh, Aakash, Seemala, Bhogeswararao, Kumar, Rajeev, Pu, Yunqiao Joseph, Wyman, Charles E., Cai, Charles M., & Ragauskas, Arthur J. Characterization of fractional cuts of co-solvent enhanced lignocellulosic fractionation lignin isolated by sequential precipitation.  United States.  doi:10.1016/j.biortech.2018.09.130.

Copy to clipboard


                    Meng, Xianzhi, Parikh, Aakash, Seemala, Bhogeswararao, Kumar, Rajeev, Pu, Yunqiao Joseph, Wyman, Charles E., Cai, Charles M., and Ragauskas, Arthur J. Thu .  
        "Characterization of fractional cuts of co-solvent enhanced lignocellulosic fractionation lignin isolated by sequential precipitation".  United States.  doi:10.1016/j.biortech.2018.09.130.  https://www.osti.gov/servlets/purl/1489560.

Copy to clipboard


                    
@article{osti_1489560,

  title        = {Characterization of fractional cuts of co-solvent enhanced lignocellulosic fractionation lignin isolated by sequential precipitation},

  author       = {Meng, Xianzhi and Parikh, Aakash and Seemala, Bhogeswararao and Kumar, Rajeev and Pu, Yunqiao Joseph and Wyman, Charles E. and Cai, Charles M. and Ragauskas, Arthur J.},

  abstractNote = {Lignin valorization is significantly hindered by the intrinsic heterogeneity of its complex structures and variability of biomass feedstocks. Fractionation of lignin can overcome these challenges by producing functionally distinct lignin cuts that can be further tailored to end products. Herein, lignin was extracted and depolymerized from poplar by the co-solvent enhanced lignocellulosic fractionation method with renewable THF to obtain CELF lignin. Several solvents were screened to separate soluble and insoluble fractions from the parent CELF lignin. The ethanol soluble portion was then fractionated into different molecular weight cuts via sequential precipitation of the lignin by reducing the concentration of THF. The physicochemical structures of different CELF lignin cuts were elucidated by GPC and NMR techniques. These results suggest that CELF lignin cuts with lower molecular weight contain progressively higher phenolic and carboxylic acid OH groups, which can be more suitable as green antioxidants than the parent lignin.},

  doi          = {10.1016/j.biortech.2018.09.130},

  journal      = {Bioresource Technology},

  number       = C,

  volume       = 272,

  place        = {United States},

  year         = {2018},

  month        = {9}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (Publisher)

Accepted Manuscript (DOE)

Publisher's Version of Record

DOI: 10.1016/j.biortech.2018.09.130

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 6 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referencing / citing this record:

A simple fractionation method and GPC analysis of organosolv extracts obtained from lignocellulosic materials
journal, January 2020

Andreo-Martínez, Pedro; Ortiz-Martínez, Víctor Manuel; García-Martínez, Nuria
Biomass Conversion and Biorefinery
DOI: 10.1007/s13399-019-00593-0

Determination of hydroxyl groups in biorefinery resources via quantitative 31P NMR spectroscopy
journal, August 2019

Meng, Xianzhi; Crestini, Claudia; Ben, Haoxi
Nature Protocols, Vol. 14, Issue 9
DOI: 10.1038/s41596-019-0191-1

Similar Records in DOE PAGES and OSTI.GOV collections:

Chemical Transformations of Poplar Lignin during Cosolvent Enhanced Lignocellulosic Fractionation Process

Journal Article Meng, Xianzhi ; Parikh, Aakash ; Seemala, Bhogeswararao ; ... - ACS Sustainable Chemistry & Engineering

Converting lignocellulosic biomass to biofuels and bioproducts is significantly hindered by the innate recalcitrance of biomass to chemical and biological breakdown, and it usually requires a pretreatment stage in order to improve conversion yields. A promising novel pretreatment named Cosolvent Enhanced Lignocellulosic Fractionation (CELF) involving dilute acid treatment of biomass in a THF–water mixture was recently developed to overcome biomass recalcitrance. Detailed elucidation of physicochemical structures of the fractionated lignin that is precipitated from CELF pretreatment of hardwood poplar, also called CELF lignin, reveals transformations in its molecular weights, monolignol composition, and hydroxyl group content. Isolated CELF lignin revealed dramaticmore »« less
Cited by 19
DOI: 10.1021/acssuschemeng.8b01028

Full Text Available
Effects of CELF Pretreatment Severity on Lignin Structure and the Lignin-Based Polyurethane Properties

Journal Article Wang, Yunyan ; Sengupta, Priya ; Scheidemantle, Brent ; ... - Frontiers in Energy Research

Conversion of technical lignin into performance biopolymers such as polyurethane offers environmental and economic advantages when combined with production of biofuels from biomass sugars, presenting significant interest toward studying the role of pretreatment on lignin structure and functionality. Co-solvent enhanced lignocellulosic fractionation (CELF) pretreatment, employing acidic aqueous tetrahydrofuran (THF) mixtures, was developed to effectively break down the lignin-carbohydrate matrix and promote extraction of lignin from lignocellulosic biomass with desirable purity and yield. In this study, we report the effects of CELF pretreatment reaction severity on the molecular structure of CELF-extracted lignin and its impact toward the mechanical properties of themore »« less
DOI: 10.3389/fenrg.2020.00149

Full Text Available
Performance of three delignifying pretreatments on hardwoods: hydrolysis yields, comprehensive mass balances, and lignin properties

Journal Article Bhalla, Aditya ; Cai, Charles M. ; Xu, Feng ; ... - Biotechnology for Biofuels

Abstract Background In this work, three pretreatments under investigation at the DOE Bioenergy Research Centers (BRCs) were subjected to a side-by-side comparison to assess their performance on model bioenergy hardwoods (a eucalyptus and a hybrid poplar). These include co-solvent-enhanced lignocellulosic fractionation (CELF), pretreatment with an ionic liquid using potentially biomass-derived components (cholinium lysinate or [Ch][Lys]), and two-stage Cu-catalyzed alkaline hydrogen peroxide pretreatment (Cu-AHP). For each of the feedstocks, the pretreatments were assessed for their impact on lignin and xylan solubilization and enzymatic hydrolysis yields as a function of enzyme loading. Lignins recovered from the pretreatments were characterized for polysaccharide content,more »« less
Cited by 2
DOI: 10.1186/s13068-019-1546-0
THF Co-Solvent Biomass Fractionation to Catalytic Fuel Precursors with High Yields. Final Report

Technical Report Cai, Charles ; Seemala, Bhogeswararao ; Meng, Xianzhi ; ...

The overall goal of this project is to utilize the Co-Solvent Enhanced Lignocellulosic Fractionation (CELF) as a platform technology to realize transformation of real biomass feedstocks to fungible transportation fuels. CELF is a solvolysis method that seeks to break the cost barrier for biomass deconstruction so that high yield liquid intermediates from both sugars and lignin can be recovered for their subsequent catalytic conversion to fungible transportation fuels. It is important for the DOE EERE mission to focus on supporting platform technologies that enable greater end-to-end utilization of biomass whereby the co-development of both process and catalyst is streamlined. CELFmore »« less
DOI: 10.2172/1525374

Full Text Available
Temperature-dependent phase behaviour of tetrahydrofuran–water alters solubilization of xylan to improve co-production of furfurals from lignocellulosic biomass

Journal Article Smith, Micholas Dean ; Cai, Charles M. ; Cheng, Xiaolin ; ... - Green Chemistry

Xylose, Xylan, Hemicellulose, CELF, THF, Co-solvent, Pretreatment, Biomass ABSTRACT: Xylan is an important polysaccharide found in the hemicellulose fraction of lignocellulosic biomass that can be hydrolysed to xylose and further dehydrated to the furfural, an important renewable platform fuel precursor. Here, pairing molecular simulation and experimental evidences, we reveal how the unique temperature-dependent phase behaviour of water-tetrahydrofuran (THF) co-solvent can delay xylan solubilization to synergistically improve catalytic co-processing of biomass to furfural and 5-HMF. Our results indicate, based on polymer correlations between polymer conformational behaviour and solvent quality, that both co-solvent and aqueous environments serve as ‘good’ solvents for xylan.more »« less
Cited by 2
DOI: 10.1039/C7GC03608F

Full Text Available

Similar Records

Title: Characterization of fractional cuts of co-solvent enhanced lignocellulosic fractionation lignin isolated by sequential precipitation

Abstract

Citation Formats

A simple fractionation method and GPC analysis of organosolv extracts obtained from lignocellulosic materials journal, January 2020

Determination of hydroxyl groups in biorefinery resources via quantitative 31P NMR spectroscopy journal, August 2019

A simple fractionation method and GPC analysis of organosolv extracts obtained from lignocellulosic materials
journal, January 2020

Determination of hydroxyl groups in biorefinery resources via quantitative 31P NMR spectroscopy
journal, August 2019