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Title: Experimental and modeling study of fuel interactions with an alkyl nitrate cetane enhancer, 2-ethyl-hexyl nitrate

Our study investigates the autoignition behavior of two gasoline surrogates doped with an alkyl nitrate cetane enhancer, 2-ethyl-hexyl nitrate (2EHN) to better understand dopant interactions with the fuels, including influences of accelerating kinetic pathways and enhanced exothermicity. A primary reference fuel (PRF) blend of n-heptane/iso-octane, and a toluene reference fuel (TRF) blend of n-heptane/iso-octane/toluene are used where the aromatic fraction of the latter is set to 20% (liquid volume), while the content of n-heptane is adjusted so that the overall reactivity of the undoped fuels is similar, e.g., Anti-Knock Index (AKI) of similar to 91, Cetane Number (CN) similar to 25. Doping levels of 0.1, 1.0 and 3.0% (liquid volume basis) are used where tests are conducted within a rapid compression machine (RCM) at a compressed pressure of 21 bar, covering temperatures from 675 to 1025 K with stoichiometric fuel-oxygen ratios at O-2 = 11.4%. At the experimental conditions, it is found that the doping effectiveness of 2EHN is fairly similar between the two fuels, though 2EHN is more effective in the aromatic blend at the lowest temperatures, while it is slightly more effective in the non-aromatic blend at intermediate temperatures. Furthermore, kinetic modeling of the experiments indicates that althoughmore » some of the reactivity trends can be captured using a detailed model, the extents of predicted Cetane Number enhancement by 2EHN are too large, while differences in fuel interactions for the two fuels result in excessive stimulation of the non-aromatic blend. Sensitivity analysis using the kinetic model indicates that the CH2O and CH3O2 chemistry are very sensitive to the dopant at all conditions. The rate of 2EHN decomposition is only important at low temperatures where its decomposition rate is slow due to the high activation energy of the reaction. At higher temperatures, dopant-derived 3-heptyl radicals are predicted to play an important role stimulating ignition. Finally, nitrogen chemistry is important through the 'NO - NO2 loop' where this can generate substantial amounts of OH. But, at the highest doping levels the formation of methyl and ethyl nitrite, and nitric acid significantly competes with this so that less OH is generated and this constrains the reactivity enhancement of 2EHN.« less
 [1] ;  [2] ;  [2] ;  [3] ;  [3]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division; Univ. of Illinois, Chicago, IL (United States). Dept. of Mechanical and Industrial Engineering
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division
  3. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Report Number(s):
Journal ID: ISSN 1540-7489; PII: S1540748914002065
Grant/Contract Number:
AC52-07NA27344; AC02-06CH11357
Accepted Manuscript
Journal Name:
Proceedings of the Combustion Institute
Additional Journal Information:
Journal Volume: 35; Journal Issue: 1; Journal ID: ISSN 1540-7489
Research Org:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC)
Country of Publication:
United States
30 DIRECT ENERGY CONVERSION; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; Rapid compression machine; Cetane enhancer; Alkyl nitrates; Fuel interactions
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1251899