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Cited by 130Lignin and Wood ChemistryThermochemical Biomass Conversion ProcessesThermal and Kinetic Analysis

Kinetics and reaction chemistry for slow pyrolysis of enzymatic hydrolysislignin and organosolv extracted lignin derived from maplewood

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Cho, Joungmo, Chu, Sheng, Dauenhauer, Paul J., Huber, George W.·2012·Green Chem.
DOI 10.1039/c1gc16222e
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Abstract

The kinetics and reaction chemistry for the pyrolysis of Maplewood lignin were investigated using both a pyroprobe reactor and a thermogravimetric analyser mass spectrometry (TGA-MS). Lignin residue after enzymatic hydrolysis and organosolv lignin derived from Maplewood were used to measure the kinetic behaviours of lignin pyrolysis and to analyse pyrolysis product distributions. The enzymatic lignin residue pyrolyzed at lower temperature than that of organosolv lignin. The differential thermogravimetric (DTG) peaks for pyrolysis of the enzymatic residue were more similar to the DTG peaks for pyrolysis of the original Maplewood than DTG of the organosolv lignin. The condensable liquid volatile products were collected from a Pyroprobe reactor with a liquid nitrogen trap. The primary monomeric phenolic compounds were guaiacol, syringol, and vanillic acid. However, only 14–36 carbon% of the sample could be detected by GC-MS. Over 60 carbon% of the condensable products were heavy tar molecules that are not detectable by GC-MS. These heavy tar molecules are the primary products from pyrolysis of lignin. Intermediate solid samples were also collected at various pyrolysis temperatures and characterized by elemental analysis, FT-IR, DP-MAS 13C NMR, and TOC. The methoxy groups and ether linkages decreased and the non-protonated aromatic carbon–carbon bonds increased in the solid residues as the pyrolysis temperature increased. The carbon content of the initial lignin feed (derived from enzymatic hydrolysis) and the solid polyaromatics residue (obtained at 773 K) was 58 wt% and 74 wt% respectively. This polyaromatic residue contained about 69 wt% of the original lignin feed. The solid polyaromatics undergo further slow decomposition accompanied by a constant release of carbon dioxide as the pyrolysis reaction continues. The pyrolysis of the enzymatic lignin residue was modelled by two reactions in series. In the first pyrolysis step the lignin was decomposed with an apparent activation energy of 74 kJ mol−1 and a heat of reaction of −8,780 kJ kg−1. The second pyrolysis step had an apparent activation energy of 110 kJ mol−1 and a heat of reaction of −2,819 kJ kg−1. Lignin pyrolysis has lower activation energies and higher heats of reaction than cellulose pyrolysis.

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  • In the range 0.05 ≤ α ≤ 0.75, PL degradation started easily on aliphatic side chains attached to phenylpropane polymers, generating small molecule gas products such as H2, H2O, CO, CO2, and C2-C4 hydrocarbons.

    “In this range, the degradation started easily on the aliphatic side chains attached to phenylpropane polymers, such as –OH bond, C–C bond of aliphatic groups. Small molecule gas products such as H2, H2O, CO, CO2 and C2-C4 hydrocarbons were correspondingly generated [43].”

    From Evaluation of pyrolysis characteristics and product distribution of black liquor using Py-GC/MS and down tube reactor: Comparison with lignin (2021) · cites this paper as [43]

    The Analysis of lignin pyrolysis products (p. 435) reports water, CO and CO2 as the main gases, with small H2 peaks, and discusses cleavage of lignin ether bonds. It does not establish degradation specifically over 0.05 ≤ α ≤ 0.75 for PL, or report C2–C4 hydrocarbons among the gases. (LLM, conf=0.87)

    Experimental — accuracy not yet measured

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Authors
Cho, J., Chu, S., Dauenhauer, P. J., & Huber, G. W.
Affiliations
University of Massachusetts Amherst (US)
Corresponding author
Huber, George W.
ORCID
Venue
Green Chem.
Publisher
Royal Society of Chemistry (RSC)
Published
2012
Volume
14
Issue
2
Pages
428-439
ISSN
  • 1463-9262 (ISSN-L)
  • 1463-9270
DOI
10.1039/c1gc16222e
OpenAlex
W2065713566
Cited by
130
References
71
Citations by year
2026: 3 · 2025: 9 · 2024: 3 · 2023: 9 · 2022: 10 · 2021: 14 · 2020: 4 · 2019: 8 · 2018: 12 · 2017: 8 · 2016: 14 · 2015: 14 · 2014: 12 · 2013: 6 · 2012: 3
FWCI
4.17
Type
journal article
Language
en
Open access
Locations
  • Green Chemistry (publishedVersion)
  • ScholarWorks@UMassAmherst (University of Massachusetts Amherst) (submittedVersion)
Funders
  • National Science Foundation (0937895)
  • U.S. Department of Defense
  • Royal Society
  • Royal Society of Chemistry
  • Defense Advanced Research Projects Agency (W911NF-09-2-0010)
  • Advanced Research Projects Agency
  • Division of Emerging Frontiers in Research and Innovation (0937895, EFRI-0937895)
Topics
  • Physical Sciences › Engineering › Biomedical Engineering › Lignin and Wood Chemistry
  • Physical Sciences › Engineering › Biomedical Engineering › Thermochemical Biomass Conversion Processes
  • Physical Sciences › Materials Science › Materials Chemistry › Thermal and Kinetic Analysis
Keywords
lignin pyrolysis, enzymatic hydrolysis lignin, organosolv lignin, pyrolysis kinetics, reaction mechanism, tar formation, guaiacol, syringol, vanillic acid, activation energy, two-step reaction model, pyrolysis product distribution, lignin degradation, carbon dioxide release

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