Investigation of structural effects of aromatic compounds on sooting tendency with mechanistic insight into ethylphenol isomers
Abstract
Small aromatic molecules with oxygen-containing functional groups are a promising class of fuel additives, as they can be readily sourced from depolymerized lignin. These oxygenated aromatic compounds (OACs) show a lower sooting tendency than aromatic hydrocarbons, but OACs having alkyl groups such as ethylphenol show a higher sooting tendency than other OACs such as phenol and anisole, despite the oxygen moiety. In this study, we investigate the relationship between chemical structure and soot precursor formation to explain observed differences in the sooting tendency of OACs and to gain insight into how alkyl or oxygenated substituents on the aromatic ring affect soot precursor formation. The weakest bond for 15 aromatic compounds was identified and cleavage of these bonds was shown to generate either benzyl or phenoxy radicals. A linear relationship between standard enthalpy of formation (ΔHfo) of these radicals and the yield sooting index (YSI) was found, and thus ΔHf° can be applied as a metric to estimate YSIs of various aromatic compounds; higher ΔHfo of a radical indicates an increase in the radical reactivity and leads to more soot precursor formation. Flow reactor experiments were performed for 2-ethylphenol and 3-ethylphenol to elucidate how ortho and meta substitution effects the sootingmore »
- Authors:
-
[1];
[2];
[1];
[1];
[1];
[4];
[4];
[1];
[1]
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
- Colorado School of Mines, Golden, CO (United States)
- Yale Univ., New Haven, CT (United States)
- Publication Date:
- Research Org.:
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office; National Science Foundation (NSF)
- OSTI Identifier:
- 1726042
- Alternate Identifier(s):
- OSTI ID: 1777038
- Report Number(s):
- NREL/JA-2800-78383
Journal ID: ISSN 1540-7489; MainId:32300;UUID:d0abfc33-7752-458f-a8ad-a498c6400b72;MainAdminID:18855
- Grant/Contract Number:
- AC36-08GO28308; EE0007983; CBET 1604983; MCB-090159
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Proceedings of the Combustion Institute
- Additional Journal Information:
- Journal Volume: 38; Journal Issue: 1; Journal ID: ISSN 1540-7489
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; DFT; flow reactor; soot; yield sooting index (YSI)
Citation Formats
Kim, Yeonjoon, Etz, Brian D., Fioroni, Gina M., Hays, Cameron K., St. John, Peter, Messerly, Richard, Vyas, Shubham, Beekley, Brian P., Guo, Facheng, McEnally, Charles S., Pfefferle, Lisa D., McCormick, Robert L., and Kim, Seonah. Investigation of structural effects of aromatic compounds on sooting tendency with mechanistic insight into ethylphenol isomers. United States: N. p., 2020.
Web. doi:10.1016/j.proci.2020.06.321.
Kim, Yeonjoon, Etz, Brian D., Fioroni, Gina M., Hays, Cameron K., St. John, Peter, Messerly, Richard, Vyas, Shubham, Beekley, Brian P., Guo, Facheng, McEnally, Charles S., Pfefferle, Lisa D., McCormick, Robert L., & Kim, Seonah. Investigation of structural effects of aromatic compounds on sooting tendency with mechanistic insight into ethylphenol isomers. United States. https://doi.org/10.1016/j.proci.2020.06.321
Kim, Yeonjoon, Etz, Brian D., Fioroni, Gina M., Hays, Cameron K., St. John, Peter, Messerly, Richard, Vyas, Shubham, Beekley, Brian P., Guo, Facheng, McEnally, Charles S., Pfefferle, Lisa D., McCormick, Robert L., and Kim, Seonah. Tue .
"Investigation of structural effects of aromatic compounds on sooting tendency with mechanistic insight into ethylphenol isomers". United States. https://doi.org/10.1016/j.proci.2020.06.321. https://www.osti.gov/servlets/purl/1726042.
@article{osti_1726042,
title = {Investigation of structural effects of aromatic compounds on sooting tendency with mechanistic insight into ethylphenol isomers},
author = {Kim, Yeonjoon and Etz, Brian D. and Fioroni, Gina M. and Hays, Cameron K. and St. John, Peter and Messerly, Richard and Vyas, Shubham and Beekley, Brian P. and Guo, Facheng and McEnally, Charles S. and Pfefferle, Lisa D. and McCormick, Robert L. and Kim, Seonah},
abstractNote = {Small aromatic molecules with oxygen-containing functional groups are a promising class of fuel additives, as they can be readily sourced from depolymerized lignin. These oxygenated aromatic compounds (OACs) show a lower sooting tendency than aromatic hydrocarbons, but OACs having alkyl groups such as ethylphenol show a higher sooting tendency than other OACs such as phenol and anisole, despite the oxygen moiety. In this study, we investigate the relationship between chemical structure and soot precursor formation to explain observed differences in the sooting tendency of OACs and to gain insight into how alkyl or oxygenated substituents on the aromatic ring affect soot precursor formation. The weakest bond for 15 aromatic compounds was identified and cleavage of these bonds was shown to generate either benzyl or phenoxy radicals. A linear relationship between standard enthalpy of formation (ΔHfo) of these radicals and the yield sooting index (YSI) was found, and thus ΔHf° can be applied as a metric to estimate YSIs of various aromatic compounds; higher ΔHfo of a radical indicates an increase in the radical reactivity and leads to more soot precursor formation. Flow reactor experiments were performed for 2-ethylphenol and 3-ethylphenol to elucidate how ortho and meta substitution effects the sooting tendency. Soot precursors were identified from the experiment and their formation pathways were investigated computationally. 2-ethylphenol produces more oxygenated products than 3-ethylphenol since the ortho position has increased resonance stabilization of radical intermediates, which leads to lower YSI. Overall, these results further inform the selection of potential biomass-derived fuel blendstocks that have favorable sooting tendencies.},
doi = {10.1016/j.proci.2020.06.321},
journal = {Proceedings of the Combustion Institute},
number = 1,
volume = 38,
place = {United States},
year = {Tue Sep 08 00:00:00 EDT 2020},
month = {Tue Sep 08 00:00:00 EDT 2020}
}
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