DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Fractionation and characterization of lignin streams from unique high-lignin content endocarp feedstocks

Abstract

In this paper, lignin is a promising source of building blocks for upgrading to valuable aromatic chemicals and materials. Endocarp biomass represents a non-edible crop residue in an existing agricultural setting which cannot be used as animal feed nor soil amendment. With significantly higher lignin content and bulk energy density, endocarps have significant advantages to be converted into both biofuel and bioproducts as compared to other biomass resources. Deep eutectic solvent (DES) is highly effective in fractionating lignin from a variety of biomass feedstocks with high yield and purity while at lower cost comparing to certain ionic liquids. In the present study, the structural and compositional features of peach and walnut endocarp cells were characterized. Compared to typical woody and herbaceous biomass, endocarp biomass exhibits significantly higher bulk density and hardness due to its high cellular density. The sugar yields of DES (1:2 choline chloride: lactic acid) pretreated peach pit (Prunus persica) and walnut shell (Juglans nigra) were determined and the impacts of DES pretreatment on the physical and chemical properties of extracted lignin were characterized. Enzymatic saccharification of DES pretreated walnut and peach endocarps gave high glucose yields (over 90%); meanwhile, compared with dilute acid and alkaline pretreatment, DESmore » pretreatment led to significantly higher lignin removal (64.3% and 70.2% for walnut and peach endocarps, respectively). The molecular weights of the extracted lignin from DES pretreated endocarp biomass were significantly reduced. 1H–13C HSQC NMR results demonstrate that the native endocarp lignins were SGH type lignins with dominant G-unit (86.7% and 80.5% for walnut and peach endocarps lignins, respectively). DES pretreatment decreased the S and H-unit while led to an increase in condensed G-units, which may contribute to a higher thermal stability of the isolated lignin. Nearly all β-O-4' and a large portion of β-5' linkages were removed during DES pretreatment. In conclusion, the high lignin content endocarps have unique cell wall characteristics when compared to the other lignocellulosic biomass feedstocks. DES pretreatment was highly effective in fractionating high lignin content endocarps to produce both sugar and lignin streams while the DES extracted lignins underwent significant changes in SGH ratio, interunit linkages, and molecular sizes.« less

Authors:
; ; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1618740
Alternate Identifier(s):
OSTI ID: 1492154
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Published Article
Journal Name:
Biotechnology for Biofuels
Additional Journal Information:
Journal Name: Biotechnology for Biofuels Journal Volume: 11 Journal Issue: 1; Journal ID: ISSN 1754-6834
Publisher:
Springer Science + Business Media
Country of Publication:
Netherlands
Language:
English
Subject:
09 BIOMASS FUELS; Endocarp; Deep eutectic solvent; Pretreatment; Lignin; Biofuel; Biorefinery

Citation Formats

Li, Wenqi, Amos, Kirtley, Li, Mi, Pu, Yunqiao, Debolt, Seth, Ragauskas, Arthur J., and Shi, Jian. Fractionation and characterization of lignin streams from unique high-lignin content endocarp feedstocks. Netherlands: N. p., 2018. Web. doi:10.1186/s13068-018-1305-7.
Li, Wenqi, Amos, Kirtley, Li, Mi, Pu, Yunqiao, Debolt, Seth, Ragauskas, Arthur J., & Shi, Jian. Fractionation and characterization of lignin streams from unique high-lignin content endocarp feedstocks. Netherlands. https://doi.org/10.1186/s13068-018-1305-7
Li, Wenqi, Amos, Kirtley, Li, Mi, Pu, Yunqiao, Debolt, Seth, Ragauskas, Arthur J., and Shi, Jian. Thu . "Fractionation and characterization of lignin streams from unique high-lignin content endocarp feedstocks". Netherlands. https://doi.org/10.1186/s13068-018-1305-7.
@article{osti_1618740,
title = {Fractionation and characterization of lignin streams from unique high-lignin content endocarp feedstocks},
author = {Li, Wenqi and Amos, Kirtley and Li, Mi and Pu, Yunqiao and Debolt, Seth and Ragauskas, Arthur J. and Shi, Jian},
abstractNote = {In this paper, lignin is a promising source of building blocks for upgrading to valuable aromatic chemicals and materials. Endocarp biomass represents a non-edible crop residue in an existing agricultural setting which cannot be used as animal feed nor soil amendment. With significantly higher lignin content and bulk energy density, endocarps have significant advantages to be converted into both biofuel and bioproducts as compared to other biomass resources. Deep eutectic solvent (DES) is highly effective in fractionating lignin from a variety of biomass feedstocks with high yield and purity while at lower cost comparing to certain ionic liquids. In the present study, the structural and compositional features of peach and walnut endocarp cells were characterized. Compared to typical woody and herbaceous biomass, endocarp biomass exhibits significantly higher bulk density and hardness due to its high cellular density. The sugar yields of DES (1:2 choline chloride: lactic acid) pretreated peach pit (Prunus persica) and walnut shell (Juglans nigra) were determined and the impacts of DES pretreatment on the physical and chemical properties of extracted lignin were characterized. Enzymatic saccharification of DES pretreated walnut and peach endocarps gave high glucose yields (over 90%); meanwhile, compared with dilute acid and alkaline pretreatment, DES pretreatment led to significantly higher lignin removal (64.3% and 70.2% for walnut and peach endocarps, respectively). The molecular weights of the extracted lignin from DES pretreated endocarp biomass were significantly reduced. 1H–13C HSQC NMR results demonstrate that the native endocarp lignins were SGH type lignins with dominant G-unit (86.7% and 80.5% for walnut and peach endocarps lignins, respectively). DES pretreatment decreased the S and H-unit while led to an increase in condensed G-units, which may contribute to a higher thermal stability of the isolated lignin. Nearly all β-O-4' and a large portion of β-5' linkages were removed during DES pretreatment. In conclusion, the high lignin content endocarps have unique cell wall characteristics when compared to the other lignocellulosic biomass feedstocks. DES pretreatment was highly effective in fractionating high lignin content endocarps to produce both sugar and lignin streams while the DES extracted lignins underwent significant changes in SGH ratio, interunit linkages, and molecular sizes.},
doi = {10.1186/s13068-018-1305-7},
journal = {Biotechnology for Biofuels},
number = 1,
volume = 11,
place = {Netherlands},
year = {Thu Nov 08 00:00:00 EST 2018},
month = {Thu Nov 08 00:00:00 EST 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1186/s13068-018-1305-7

Citation Metrics:
Cited by: 43 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: a Bulk density of endocarp biomass in four form in comparison with switchgrass and lodge pole pine in four and pellet forms [7]; b confocal microscopographs of Calcofour White stained raw biomass comparing (1) switchgrass stem (1st internode), (2) pine stem (heartwood), (3) walnut endocarp, and (4) peachmore » endocarp« less

Save / Share:

Works referenced in this record:

Thermal degradation behaviour of isotactic polypropylene blended with lignin
journal, March 2006


Characteristics of hemicellulose, cellulose and lignin pyrolysis
journal, August 2007


The effect of liquid hot water pretreatment on the chemical–structural alteration and the reduced recalcitrance in poplar
journal, November 2017


‘Cradle-to-grave’ assessment of existing lignocellulose pretreatment technologies
journal, June 2009

  • da Costa Sousa, Leonardo; Chundawat, Shishir PS; Balan, Venkatesh
  • Current Opinion in Biotechnology, Vol. 20, Issue 3
  • DOI: 10.1016/j.copbio.2009.05.003

Unique low-molecular-weight lignin with high purity extracted from wood by deep eutectic solvents (DES): a source of lignin for valorization
journal, January 2016

  • Alvarez-Vasco, Carlos; Ma, Ruoshui; Quintero, Melissa
  • Green Chemistry, Vol. 18, Issue 19
  • DOI: 10.1039/C6GC01007E

Natural deep eutectic solvents as new potential media for green technology
journal, March 2013


Elucidation of the structure of cellulolytic enzyme lignin
journal, July 2006

  • Hu, Zhoujian; Yeh, Ting-Feng; Chang, Hou-min
  • Holzforschung, Vol. 60, Issue 4
  • DOI: 10.1515/HF.2006.061

Natural deep eutectic solvent mediated pretreatment of rice straw: bioanalytical characterization of lignin extract and enzymatic hydrolysis of pretreated biomass residue
journal, June 2015

  • Kumar, Adepu K.; Parikh, Bhumika S.; Pravakar, Mohanty
  • Environmental Science and Pollution Research, Vol. 23, Issue 10
  • DOI: 10.1007/s11356-015-4780-4

A comparison of chemical pretreatment methods for improving saccharification of cotton stalks
journal, November 2007


Differential Staining for Cellulosic and Modified Plant Cell Walls
journal, January 1996


The effect of the biomass components lignin, cellulose and hemicellulose on TGA and fixed bed pyrolysis
journal, May 2013

  • Burhenne, Luisa; Messmer, Jonas; Aicher, Thomas
  • Journal of Analytical and Applied Pyrolysis, Vol. 101
  • DOI: 10.1016/j.jaap.2013.01.012

Variability in Lignin Composition and Structure in Cell Walls of Different Parts of Macaúba ( Acrocomia aculeata ) Palm Fruit
journal, December 2017

  • Rencoret, Jorge; Kim, Hoon; Evaristo, Anderson B.
  • Journal of Agricultural and Food Chemistry, Vol. 66, Issue 1
  • DOI: 10.1021/acs.jafc.7b04638

Structural Elucidation of Sorghum Lignins from an Integrated Biorefinery Process Based on Hydrothermal and Alkaline Treatments
journal, July 2014

  • Sun, Shao-Long; Wen, Jia-Long; Ma, Ming-Guo
  • Journal of Agricultural and Food Chemistry, Vol. 62, Issue 32
  • DOI: 10.1021/jf501669r

Physico-chemical characterization of lignins from different sources for use in phenol–formaldehyde resin synthesis
journal, May 2007


Comparative data on effects of leading pretreatments and enzyme loadings and formulations on sugar yields from different switchgrass sources
journal, December 2011


Opportunities and challenges for a sustainable energy future
journal, August 2012

  • Chu, Steven; Majumdar, Arun
  • Nature, Vol. 488, Issue 7411, p. 294-303
  • DOI: 10.1038/nature11475

Lignin chemistry?past, present and future
journal, January 1977


Pretreatment technologies for an efficient bioethanol production process based on enzymatic hydrolysis: A review
journal, July 2010


Hydroxystilbenes Are Monomers in Palm Fruit Endocarp Lignins
journal, June 2017

  • Carlos del Río, José; Rencoret, Jorge; Gutiérrez, Ana
  • Plant Physiology, Vol. 174, Issue 4
  • DOI: 10.1104/pp.17.00362

Sodium Hydroxide Pretreatment of Switchgrass for Ethanol Production
journal, March 2010

  • Xu, Jiele; Cheng, Jay J.; Sharma-Shivappa, Ratna R.
  • Energy & Fuels, Vol. 24, Issue 3
  • DOI: 10.1021/ef9014718

Identification and thermochemical analysis of high-lignin feedstocks for biofuel and biochemical production
journal, January 2011

  • Mendu, Venugopal; Harman-Ware, Anne E.; Crocker, Mark
  • Biotechnology for Biofuels, Vol. 4, Issue 1
  • DOI: 10.1186/1754-6834-4-43

Impact of mixed feedstocks and feedstock densification on ionic liquid pretreatment efficiency
journal, January 2013

  • Shi, Jian; Thompson, Vicki S.; Yancey, Neal A.
  • Biofuels, Vol. 4, Issue 1
  • DOI: 10.4155/bfs.12.82

Deep eutectic solvents: syntheses, properties and applications
journal, January 2012

  • Zhang, Qinghua; De Oliveira Vigier, Karine; Royer, Sébastien
  • Chemical Society Reviews, Vol. 41, Issue 21
  • DOI: 10.1039/c2cs35178a

Effect of ultrasound treatment on the physicochemical properties of alkaline lignin
journal, December 2012

  • García, Araceli; Erdocia, Xabier; González Alriols, María
  • Chemical Engineering and Processing: Process Intensification, Vol. 62
  • DOI: 10.1016/j.cep.2012.07.011

Comparison of alkaline- and fungi-assisted wet-storage of corn stover
journal, April 2012


Recirculating calcium hydroxide solution: A practical choice for on-farm high solids lignocellulose pretreatment
journal, March 2017


Deep Eutectic Solvents (DESs) for the Isolation of Willow Lignin (Salix matsudana cv. Zhuliu)
journal, October 2017

  • Li, Tengfei; Lyu, Gaojin; Liu, Yu
  • International Journal of Molecular Sciences, Vol. 18, Issue 11
  • DOI: 10.3390/ijms18112266

Lignin Valorization: Improving Lignin Processing in the Biorefinery
journal, May 2014

  • Ragauskas, A. J.; Beckham, G. T.; Biddy, M. J.
  • Science, Vol. 344, Issue 6185, p. 1246843-1246843
  • DOI: 10.1126/science.1246843

Sugar yields from dilute sulfuric acid and sulfur dioxide pretreatments and subsequent enzymatic hydrolysis of switchgrass
journal, October 2011


Phloroglucinol Stain for Lignin
journal, January 2010


Characterization and Catalytic Transfer Hydrogenolysis of Deep Eutectic Solvent Extracted Sorghum Lignin to Phenolic Compounds
journal, June 2018


The irreversible momentum of clean energy
journal, January 2017


Insights into the Synthesis and Properties of Deep Eutectic Solvents Based on Cholinium Chloride and Carboxylic Acids
journal, September 2014

  • Florindo, C.; Oliveira, F. S.; Rebelo, L. P. N.
  • ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 10
  • DOI: 10.1021/sc500439w

Carbon–ionic liquid double-layer capacitors
journal, March 2004

  • Lewandowski, A.; Galiński, M.
  • Journal of Physics and Chemistry of Solids, Vol. 65, Issue 2-3, p. 281-286
  • DOI: 10.1016/j.jpcs.2003.09.009

Comparison of the pyrolysis behavior of lignins from different tree species
journal, September 2009


Features of promising technologies for pretreatment of lignocellulosic biomass
journal, April 2005


Opportunities and challenges in biological lignin valorization
journal, December 2016


Biomass Ethanol: Technical Progress, Opportunities, and Commercial Challenges
journal, November 1999


Process and technoeconomic analysis of leading pretreatment technologies for lignocellulosic ethanol production using switchgrass
journal, December 2011


Quantitative Structures and Thermal Properties of Birch Lignins after Ionic Liquid Pretreatment
journal, January 2013

  • Wen, Jia-Long; Sun, Shao-Long; Xue, Bai-Liang
  • Journal of Agricultural and Food Chemistry, Vol. 61, Issue 3
  • DOI: 10.1021/jf3051939

Modeling and optimization of the dilute-sulfuric-acid pretreatment of corn stover, poplar and switchgrass
journal, February 1997

  • Esteghlalian, Alireza; Hashimoto, Andrew G.; Fenske, John J.
  • Bioresource Technology, Vol. 59, Issue 2-3, p. 129-136
  • DOI: 10.1016/S0960-8524(97)81606-9

Deep eutectic solvent pretreatment and subsequent saccharification of corncob
journal, September 2015


Biomass pretreatment using deep eutectic solvents from lignin derived phenols
journal, January 2018

  • Kim, Kwang Ho; Dutta, Tanmoy; Sun, Jian
  • Green Chemistry, Vol. 20, Issue 4
  • DOI: 10.1039/C7GC03029K

Pretreatment: the key to unlocking low-cost cellulosic ethanol
journal, January 2008

  • Yang, Bin; Wyman, Charles E.
  • Biofuels, Bioproducts and Biorefining, Vol. 2, Issue 1
  • DOI: 10.1002/bbb.49

Deep Eutectic Solvents Formed between Choline Chloride and Carboxylic Acids:  Versatile Alternatives to Ionic Liquids
journal, July 2004

  • Abbott, Andrew P.; Boothby, David; Capper, Glen
  • Journal of the American Chemical Society, Vol. 126, Issue 29
  • DOI: 10.1021/ja048266j

Impact of Pretreatment Technologies on Saccharification and Isopentenol Fermentation of Mixed Lignocellulosic Feedstocks
journal, February 2015


The effect of ionic liquid cation and anion combinations on the macromolecular structure of lignins
journal, January 2011

  • George, Anthe; Tran, Kim; Morgan, Trevor J.
  • Green Chemistry, Vol. 13, Issue 12
  • DOI: 10.1039/c1gc15543a

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.