A jet-stirred reactor and kinetic modeling study of ethyl propanoate oxidation

• Published in: Combustion and flame 2009-01, Vol.156 (1), p.250-260
• Main Authors: Metcalfe, W.K., Togbé, C., Dagaut, P., Curran, H.J., Simmie, J.M.
• Format: Article
• Language: English
• Subjects: ACTIVATION ENERGY; ADVANCED PROPULSION SYSTEMS; Applied sciences; BIOFUELS; CARBON DIOXIDE; CARBON MONOXIDE; CHEMICAL REACTION KINETICS; Chemical Sciences; Combustion; Delay; DIESEL FUELS; Energy; Energy. Thermal use of fuels; Engineering Sciences; Engines and turbines; Equipments for energy generation and conversion: thermal, electrical, mechanical energy, etc; Equivalence ratio; Ethyl propanoate; ETHYLENE; Exact sciences and technology; FORMALDEHYDE; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; JETS; JSR; METHANE; Modeling; or physical chemistry; OXIDATION; PRESSURE RANGE KILO PA; Propanoic acid; PROPIONIC ACID; Reaction kinetics; Reactive fluid environment; Reactors; SENSITIVITY ANALYSIS; SIMULATION; TEMPERATURE RANGE 0400-1000 K; TEMPERATURE RANGE 1000-4000 K; Theoretical and; WATER
• ISSN: 0010-2180; 1556-2921
• DOI: 10.1016/j.combustflame.2008.09.007

A jet-stirred reactor study of ethyl propanoate, a model biodiesel molecule, has been carried out at 10 atm pressure, using 0.1% fuel at equivalence ratios of 0.3, 0.6, 1.0 and 2.0 and at temperatures in the range 750 – 1100 K with a constant residence time of 0.7 seconds. Concentration profiles of ethyl propanoate were measured together with those of major intermediates, ethylene, propanoic acid, methane and formaldehyde, and major products, water, carbon dioxide and carbon monoxide. This data was used to further validate a previously published detailed chemical kinetic mechanism, containing 139 species and 790 reversible reactions. It was found that this mechanism required a significant increase in the rate constant of the six-centered unimolecular elimination reaction which produces ethylene and propanoic acid in order to correctly reproduce the measured concentrations of propanoic acid. The revised mechanism was then used to re-simulate shock tube ignition delay data with good agreement observed. Rate of production and sensitivity analyses were carried out under the experimental conditions, highlighting the importance that ethylene chemistry has on the overall reactivity of the system.