Experimental and theoretical study of oxidative stability of alkylated furans used as gasoline blend components
Abstract
Alkylated furans such as 2,5-dimethylfuran and 2-methylfuran can be produced from biomass and have very attractive properties for use as spark-ignition fuel blendstocks. Their high octane numbers, relatively high energy density, low water solubility, and minimal effect on gasoline blend volatility are potentially significant advantages over alcohol-based fuels. However, prior studies have reported poor oxidative stability for furanic compound-gasoline blends, as well as the potential for the formation of dangerous organic peroxides. We show that alkylated furans have very low oxidative stability compared to conventional gasoline. Upon oxidation they form highly polar ring-opening products that can react with the starting furanic compound to form dimers, trimers, and higher polymers with intact furan rings. Dimers of the starting furan compounds were also observed. These gasoline-insoluble gums can be problematic for fuel storage or in vehicle fuel systems. Evaporation to dryness under ambient conditions also produced gum with similar composition. Gums produced via evaporation were found to contain peroxides; however, whether these pose a threat of shock initiated explosion has not been determined. We also propose a density functional theory-based analysis of possible reaction pathways, showing that OH radicals can form by reaction of the alkyl group and that addition of OHmore »
- Authors:
- Publication Date:
- Research Org.:
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office
- OSTI Identifier:
- 1631354
- Alternate Identifier(s):
- OSTI ID: 1408693
- Report Number(s):
- NREL/JA-5400-70052
Journal ID: ISSN 0016-2361; S0016236117313145; PII: S0016236117313145
- Grant/Contract Number:
- DE347AC36-99GO10337; AC36-08GO28308
- Resource Type:
- Published Article
- Journal Name:
- Fuel
- Additional Journal Information:
- Journal Name: Fuel Journal Volume: 212 Journal Issue: C; Journal ID: ISSN 0016-2361
- Publisher:
- Elsevier
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 09 BIOMASS FUELS; alkyl furan; methylfuran; dimethylfuran; gasoline; oxidation stability
Citation Formats
Christensen, Earl, Fioroni, Gina M., Kim, Seonah, Fouts, Lisa, Gjersing, Erica, Paton, Robert S., and McCormick, Robert L. Experimental and theoretical study of oxidative stability of alkylated furans used as gasoline blend components. United Kingdom: N. p., 2018.
Web. doi:10.1016/j.fuel.2017.10.066.
Christensen, Earl, Fioroni, Gina M., Kim, Seonah, Fouts, Lisa, Gjersing, Erica, Paton, Robert S., & McCormick, Robert L. Experimental and theoretical study of oxidative stability of alkylated furans used as gasoline blend components. United Kingdom. https://doi.org/10.1016/j.fuel.2017.10.066
Christensen, Earl, Fioroni, Gina M., Kim, Seonah, Fouts, Lisa, Gjersing, Erica, Paton, Robert S., and McCormick, Robert L. Mon .
"Experimental and theoretical study of oxidative stability of alkylated furans used as gasoline blend components". United Kingdom. https://doi.org/10.1016/j.fuel.2017.10.066.
@article{osti_1631354,
title = {Experimental and theoretical study of oxidative stability of alkylated furans used as gasoline blend components},
author = {Christensen, Earl and Fioroni, Gina M. and Kim, Seonah and Fouts, Lisa and Gjersing, Erica and Paton, Robert S. and McCormick, Robert L.},
abstractNote = {Alkylated furans such as 2,5-dimethylfuran and 2-methylfuran can be produced from biomass and have very attractive properties for use as spark-ignition fuel blendstocks. Their high octane numbers, relatively high energy density, low water solubility, and minimal effect on gasoline blend volatility are potentially significant advantages over alcohol-based fuels. However, prior studies have reported poor oxidative stability for furanic compound-gasoline blends, as well as the potential for the formation of dangerous organic peroxides. We show that alkylated furans have very low oxidative stability compared to conventional gasoline. Upon oxidation they form highly polar ring-opening products that can react with the starting furanic compound to form dimers, trimers, and higher polymers with intact furan rings. Dimers of the starting furan compounds were also observed. These gasoline-insoluble gums can be problematic for fuel storage or in vehicle fuel systems. Evaporation to dryness under ambient conditions also produced gum with similar composition. Gums produced via evaporation were found to contain peroxides; however, whether these pose a threat of shock initiated explosion has not been determined. We also propose a density functional theory-based analysis of possible reaction pathways, showing that OH radicals can form by reaction of the alkyl group and that addition of OH radicals to the furan ring is energetically favored and leads to ring opening products. As a result, antioxidant additives can be effective at limiting the oxidation reaction in gasoline, but require much higher concentrations than are commonly used in commercial gasolines.},
doi = {10.1016/j.fuel.2017.10.066},
journal = {Fuel},
number = C,
volume = 212,
place = {United Kingdom},
year = {Mon Jan 01 00:00:00 EST 2018},
month = {Mon Jan 01 00:00:00 EST 2018}
}
https://doi.org/10.1016/j.fuel.2017.10.066
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Works referencing / citing this record:
Synthesis and Properties of Photodegradable Poly(furan-amine)s by a Catalyst-free Multicomponent Cyclopolymerization
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- Fu, Wei-Qiang; Zhu, Gui-Nan; Shi, Jian-Bing
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