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Title: Experimental and theoretical study of oxidative stability of alkylated furans used as gasoline blend components

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 » 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.« less
Authors:
 [1] ;  [1] ; ORCiD logo [1] ;  [1] ;  [1] ;  [2] ; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Univ. of Oxford, Oxford (United Kingdom)
Publication Date:
Report Number(s):
NREL/JA-5400-70052
Journal ID: ISSN 0016-2361
Grant/Contract Number:
AC36-08GO28308
Type:
Accepted Manuscript
Journal Name:
Fuel
Additional Journal Information:
Journal Volume: 212; Journal Issue: C; Journal ID: ISSN 0016-2361
Publisher:
Elsevier
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), Bioenergy Technologies Office (EE-3B)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; alkyl furan; methylfuran; dimethylfuran; gasoline; oxidation stability
OSTI Identifier:
1408693

Christensen, Earl, Fioroni, Gina M., Kim, Seonah, Fouts, Lisa A., Gjersing, Erica L., Paton, Robert S., and McCormick, Robert L.. Experimental and theoretical study of oxidative stability of alkylated furans used as gasoline blend components. United States: N. p., Web. doi:10.1016/j.fuel.2017.10.066.
Christensen, Earl, Fioroni, Gina M., Kim, Seonah, Fouts, Lisa A., Gjersing, Erica L., Paton, Robert S., & McCormick, Robert L.. Experimental and theoretical study of oxidative stability of alkylated furans used as gasoline blend components. United States. doi:10.1016/j.fuel.2017.10.066.
Christensen, Earl, Fioroni, Gina M., Kim, Seonah, Fouts, Lisa A., Gjersing, Erica L., Paton, Robert S., and McCormick, Robert L.. 2017. "Experimental and theoretical study of oxidative stability of alkylated furans used as gasoline blend components". United States. doi:10.1016/j.fuel.2017.10.066. https://www.osti.gov/servlets/purl/1408693.
@article{osti_1408693,
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 A. and Gjersing, Erica L. 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 States},
year = {2017},
month = {11}
}