Molecular Products and Fundamentally Based Reaction Pathways in the Gas-Phase Pyrolysis of the Lignin Model Compound p-Coumaryl Alcohol
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The fractional pyrolysis of lignin model compound para-coumaryl alcohol (p-CMA) containing a propanoid side chain and a phenolic OH group was studied using the System for Thermal Diagnostic Studies at temperatures from 200 to 900 °C, in order to gain mechanistic insight into the role of large substituents in high-lignin feedstocks pyrolysis. Phenol and its simple derivatives p-cresol, ethyl-, propenyl-, and propyl-phenols were found to be the major products predominantly formed at low pyrolysis temperatures (<500 °C). A cryogenic trapping technique was employed combined with EPR spectroscopy to identify the open-shell intermediates registered at pyrolysis temperatures above 500 °C. These were characterized as radical mixtures primarily consisting of oxygen-linked conjugated radicals. A comprehensive potential energy surface analysis of p-CMA and p-CMA + H atom systems was performed using various DFT protocols to examine the possible role of concerted molecular eliminations and free-radical mechanisms in the formation of major products. Other significant unimolecular concerted reactions along with formation and decomposition of primary radicals are also described and evaluated. The calculations suggest that a set of the chemically activated secondary radical channels is relevant to the low temperature product formation under fractional pyrolysis conditions.
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Cresol-type compounds can also be generated from p-hydroxyphenyl units via depolymerization (P3 and P4).
“In addition, cresol-type compounds can also be generated from p-hydroxyphenyl units via depolymerization (P3 and P4) [167].”
From A review on lignin pyrolysis: pyrolytic behavior, mechanism, and relevant upgrading for improving process efficiency (2022) · cites this paper as [167]
The Introduction identifies p-coumaryl alcohol as a lignin model, and the Summary of Mechanisms Relevant to the Major Product Formation reports p-cresol formation during its pyrolysis. The paper studies decomposition of the model compound, not depolymerization of p-hydroxyphenyl units within lignin; it does not establish the specified P3 and P4 routes. Page numbers are unavailable in our copy. (LLM, conf=0.88)
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“In addition, cresol-type compounds can also be generated from p-hydroxyphenyl units via depolymerization (P3 and P4) [167].”
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Self-citation
- Authors
- Asatryan, R., Bennadji, H., Bozzelli, J. W., Ruckenstein, E., & Khachatryan, L.
- Affiliations
- University at Buffalo, State University of New York (US)
- Louisiana State University (US)
- New Jersey Institute of Technology (US)
- Corresponding author
- Asatryan, Rubik
- Venue
- The Journal of Physical Chemistry A
- Publisher
- American Chemical Society (ACS)
- Published
- 2017-04-26
- Volume
- 121
- Issue
- 18
- Pages
- 3352-3371
- ISSN
- 1089-5639 (ISSN-L)
- 1520-5215
- PMC
- PMC7769150
- OpenAlex
- W2606203583
- Cited by
- 46
- References
- 85
- Citations by year
- 2026: 2 · 2025: 5 · 2024: 4 · 2023: 5 · 2022: 3 · 2021: 6 · 2020: 9 · 2019: 6 · 2018: 4 · 2017: 2
- FWCI
- 2.59
- Type
- journal article
- Language
- en
- Open access
- green
- www.ncbi.nlm.nih.gov
- Locations
- The Journal of Physical Chemistry A (publishedVersion)
- PubMed (publishedVersion)
- PubMed Central (acceptedVersion)
- Civil War Book Review (submittedVersion)
- Funders
- National Science Foundation (CBET 1330311)
- Topics
- Physical Sciences › Engineering › Biomedical Engineering › Lignin and Wood Chemistry
- Physical Sciences › Engineering › Biomedical Engineering › Thermochemical Biomass Conversion Processes
- Physical Sciences › Chemical Engineering › Fluid Flow and Transfer Processes › Advanced Combustion Engine Technologies
- Keywords
- p-coumaryl alcohol, lignin model compounds, gas-phase pyrolysis, reaction mechanism, phenol formation, p-cresol, phenyl radical, potential energy surface, concerted elimination, radical mechanism, unimolecular reactions, substituent effects
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