skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Functionality and molecular weight distribution of red oak lignin before and after pyrolysis and hydrogenation

Abstract

In this paper, three red oak derived lignin samples: 1. lignin extracted from red oak chips using γ-valerolactone (GVL lignin), 2. lignin extracted from the pyrolysis oil of red oak chips by fractionation and water extraction (pyrolytic lignin) and 3. pyrolytic lignin hydrogenated over Ru/C (hydrogenated pyrolytic lignin), were analyzed by FT-ICR MS, NMR, and GPC. More than 1100 distinct molecular weights were observed by FT-ICR MS of the lignin streams while changes in the O/C and H/C ratios suggested the dehydration of hydroxylated sidechains from pyrolysis and partial saturation of the compounds from hydrogenation. The relative average molecular weight of the lignin determined by GPC decreased five-fold after pyrolysis. Quantitative 13C, HSQC, and HMBC NMR revealed a decrease in the C–O aliphatics from pyrolysis potentially forming alkane, alkene, and carbonyl functionalities. Finally, the aldehydes and ketones were highly reactive during hydrogenation and may potentially be responsible for coke formation.

Authors:
 [1];  [2];  [3];  [4];  [5];  [5];  [5]; ORCiD logo [6];  [3];  [2]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering
  2. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering; Wisconsin Energy Inst., Madison, WI (United States). Great Lakes Bioenergy Research Center
  3. Wisconsin Energy Inst., Madison, WI (United States). Great Lakes Bioenergy Research Center; Univ. of Wisconsin, Madison, WI (United States). Dept. of Biochemistry. Dept. of Biological Systems Engineering
  4. Iowa State Univ., Ames, IA (United States). Bioeconomy Inst.
  5. ExxonMobil Research and Engineering, Annandale, NJ (United States)
  6. Iowa State Univ., Ames, IA (United States). Bioeconomy Inst. Dept. of Mechanical Engineering
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States); Wisconsin Energy Inst., Madison, WI (United States); ExxonMobil Research and Engineering, Annandale, NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); National Inst. of Health (NIH) (United States); ExxonMobil (United States)
OSTI Identifier:
1475423
Grant/Contract Number:  
FC02-07ER64494; S10 OD012245
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 19; Journal Issue: 5; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

McClelland, Daniel J., Motagamwala, Ali Hussain, Li, Yanding, Rover, Marjorie R., Wittrig, Ashley M., Wu, Chunping, Buchanan, J. Scott, Brown, Robert C., Ralph, John, Dumesic, James A., and Huber, George W. Functionality and molecular weight distribution of red oak lignin before and after pyrolysis and hydrogenation. United States: N. p., 2017. Web. doi:10.1039/C6GC03515A.
McClelland, Daniel J., Motagamwala, Ali Hussain, Li, Yanding, Rover, Marjorie R., Wittrig, Ashley M., Wu, Chunping, Buchanan, J. Scott, Brown, Robert C., Ralph, John, Dumesic, James A., & Huber, George W. Functionality and molecular weight distribution of red oak lignin before and after pyrolysis and hydrogenation. United States. doi:10.1039/C6GC03515A.
McClelland, Daniel J., Motagamwala, Ali Hussain, Li, Yanding, Rover, Marjorie R., Wittrig, Ashley M., Wu, Chunping, Buchanan, J. Scott, Brown, Robert C., Ralph, John, Dumesic, James A., and Huber, George W. Wed . "Functionality and molecular weight distribution of red oak lignin before and after pyrolysis and hydrogenation". United States. doi:10.1039/C6GC03515A. https://www.osti.gov/servlets/purl/1475423.
@article{osti_1475423,
title = {Functionality and molecular weight distribution of red oak lignin before and after pyrolysis and hydrogenation},
author = {McClelland, Daniel J. and Motagamwala, Ali Hussain and Li, Yanding and Rover, Marjorie R. and Wittrig, Ashley M. and Wu, Chunping and Buchanan, J. Scott and Brown, Robert C. and Ralph, John and Dumesic, James A. and Huber, George W.},
abstractNote = {In this paper, three red oak derived lignin samples: 1. lignin extracted from red oak chips using γ-valerolactone (GVL lignin), 2. lignin extracted from the pyrolysis oil of red oak chips by fractionation and water extraction (pyrolytic lignin) and 3. pyrolytic lignin hydrogenated over Ru/C (hydrogenated pyrolytic lignin), were analyzed by FT-ICR MS, NMR, and GPC. More than 1100 distinct molecular weights were observed by FT-ICR MS of the lignin streams while changes in the O/C and H/C ratios suggested the dehydration of hydroxylated sidechains from pyrolysis and partial saturation of the compounds from hydrogenation. The relative average molecular weight of the lignin determined by GPC decreased five-fold after pyrolysis. Quantitative 13C, HSQC, and HMBC NMR revealed a decrease in the C–O aliphatics from pyrolysis potentially forming alkane, alkene, and carbonyl functionalities. Finally, the aldehydes and ketones were highly reactive during hydrogenation and may potentially be responsible for coke formation.},
doi = {10.1039/C6GC03515A},
journal = {Green Chemistry},
number = 5,
volume = 19,
place = {United States},
year = {Wed Jan 25 00:00:00 EST 2017},
month = {Wed Jan 25 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Catalytic Transformation of Lignin for the Production of Chemicals and Fuels
journal, October 2015


Production of Clean Pyrolytic Sugars for Fermentation
journal, April 2014

  • Rover, Marjorie R.; Johnston, Patrick A.; Jin, Tao
  • ChemSusChem, Vol. 7, Issue 6, p. 1662-1668
  • DOI: 10.1002/cssc.201301259

The Catalytic Valorization of Lignin for the Production of Renewable Chemicals
journal, June 2010

  • Zakzeski, Joseph; Bruijnincx, Pieter C. A.; Jongerius, Anna L.
  • Chemical Reviews, Vol. 110, Issue 6, p. 3552-3599
  • DOI: 10.1021/cr900354u

Solvent Effects on the Hydrogenolysis of Diphenyl Ether with Raney Nickel and their Implications for the Conversion of Lignin
journal, April 2012


Techno-economic comparison of biomass-to-transportation fuels via pyrolysis, gasification, and biochemical pathways
journal, November 2010