Detailed Chemical Kinetic Mechanisms for Combustion of Oxygenated Fuels

Abstract

Thermodynamic properties and detailed chemical kinetic models have been developed for the combustion of two oxygenates: methyl butanoate, a model compound for biodiesel fuels, and methyl formate, a related simpler molecule. Bond additivity methods and rules for estimating kinetic parameters were adopted from hydrocarbon combustion and extended. The resulting mechanisms have been tested against the limited combustion data available in the literature, which was obtained at low temperature, subatmospheric conditions in closed vessels, using pressure measurements as the main diagnostic. Some qualitative agreement was obtained, but the experimental data consistently indicated lower overall reactivities than the model, differing by factors of 10 to 50. This discrepancy, which occurs for species with wellestablished kinetic mechanisms as well as for methyl esters, is tentatively ascribed to the presence of wall reactions in the experiments. The model predicts a region of weak or negative dependence of overall reaction rate on temperature for each methyl ester. Examination of the reaction fluxes provides an explanation of this behavior, involving a temperature-dependent competition between chain-propagating unimolecular decomposition processes and chain-branching processes, similar to that accepted for hydrocarbons. There is an urgent need to obtain more complete experimental data under well-characterized conditions for thorough testing of the model.

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Document Details

Document Type
Technical Report
Publication Date
Aug 04, 2000
Accession Number
ADA452551

Entities

People

  • C. K. Westbrook
  • E. M. Fisher
  • H. J. Curran
  • W. J. Pitz

Organizations

  • Sibley School of Mechanical and Aerospace Engineering

Tags

Communities of Interest

  • Ground and Sea Platforms
  • Materials and Manufacturing Processes
  • Space

DTIC Thesaurus Topics

  • Biodiesels
  • Boiling Point
  • Chemical Reaction Properties
  • Chemical Reactions
  • Chemistry
  • Combustion
  • Cool Flames
  • Decomposition
  • Diesel Fuels
  • Energy
  • Experimental Data
  • Fuels
  • Hydrocarbons
  • Low Temperature
  • Physical Properties
  • Pressure Measurement
  • Thermodynamic Properties

Readers

  • Combustion science or combustion engineering.
  • Computational Modeling and Simulation
  • Organic Chemistry