Modeling Study of the Low-Temperature Oxidation of Large Methyl Esters

This study focuses on the automatic generation by the software EXGAS of kinetic models for the oxidation of large methyl esters using a single set of kinetic parameters. The obtained models allow to well reproduce the oxidation of n-decane / methyl palmitate mixture in a jet-stirred reactor. This paper also presents the construction and a comparison of models for methyl esters from C7 up to C17 in terms f conversion in a jet-stirred reactor and of ignition delay time in a shock tube. This comparison study showed that methyl esters larger than methyl octanoate behave similarly and have very close reactivities.Comment: European Combustion Meeting 2009, Vienne : Autriche (2009

Experimental and modeling study of the low-temperature oxidation of large alkanes

This paper presents an experimental and modeling study of the oxidation of large linear akanes (from C10) representative from diesel fuel from low to intermediate temperature (550-1100 K) including the negative temperature coefficient (NTC) zone. The experimental study has been performed in a jet-stirred reactor at atmospheric pressure for n-decane and a n-decane/n-hexadecane blend. Detailed kinetic mechanisms have been developed using computer-aided generation (EXGAS) with improved rules for writing reactions of primary products. These mechanisms have allowed a correct simulation of the experimental results obtained. Data from the literature for the oxidation of n-decane, in a jet-stirred reactor at 10 bar and in shock tubes, and of n-dodecane in a pressurized flow reactor have also been correctly modeled. A considerable improvement of the prediction of the formation of products is obtained compared to our previous models. Flow rates and sensitivity analyses have been performed in order to better understand the influence of reactions of primary products. A modeling comparison between linear alkanes for C8 to C16 in terms of ignition delay times and the formation of light products is also discussed

A Lean Methane Prelixed Laminar Flame Doped witg Components of Diesel Fuel. Part I: n)Butylbenzene

To better understand the chemistry involved during the combustion of components of diesel fuel, the structure of a laminar lean premixed methane flame doped with n-butylbenzene has been investigated. The inlet gases contained 7.1% (molar) of methane, 36.8% of oxygen and 0.96% of n-butylbenzene corresponding to an equivalence ratio of 0.74 and a ratio C10H14 / CH4 of 13.5%. The flame has been stabilized on a burner at a pressure of 6.7 kPa using argon as diluent, with a gas velocity at the burner of 49.2 cm/s at 333 K. Quantified species included the usual methane C0-C2 combustion products, but also 16 C3-C5 hydrocarbons, 7 C1-C3 oxygenated compounds, as well as 20 aromatic products, namely benzene, toluene, phenylacetylene, styrene, ethylbenzene, xylenes, allylbenzene, propylbenzene, cumene, methylstyrenes, butenylbenzenes, indene, indane, naphthalene, phenol, benzaldehyde, anisole, benzylalcohol, benzofuran, and isomers of C10H10 (1-methylindene, dihydronaphtalene, butadienylbenzene). A new mechanism for the oxidation of n-butylbenzene is proposed whose predictions are in satisfactory agreement with measured species profiles in flames and flow reactor experiments. The main reaction pathways of consumption of n butylbenzene have been derived from flow rate analyses

The autoignition of cyclopentane and cyclohexane in a shock tube

Ignition delay times of cyclohexane-oxygen-argon and cyclopentane-oxygen-argon mixtures have been measured in a shock tube, the onset of ignition being detected by OH radical emission. Mixtures contained 0.5 or 1 % of hydrocarbon for equivalence ratios ranging from 0.5 to 2. Reflected shock waves allowed temperatures from 1230 to 1800 K and pressures from 7.3 to 9.5 atm to be obtained. These measurements have shown that cyclopentane is much less reactive than cyclohexane, as for a given temperature the observed autoignition delay times were about ten times higher for the C5 compound compared to the C6. Detailed mechanisms for the combustion of cyclohexane and cyclopentane have been proposed to reproduce these results. The elementary steps included in the kinetic models of the oxidation of cyclanes are close to those proposed to describe the oxidation of acyclic alkanes and alkenes. Consequently, it has been possible to obtain these models by using an improved version of software EXGAS, a computer package developed to perform the automatic generation of detailed kinetic models for the gas-phase oxidation and combustion of linear and branched alkanes and alkenes. Nevertheless, the modelling of the oxidation of cyclanes requires to consider new types of generic reactions, and especially to define new correlations for the estimation of the rate constants. Ab initio calculations have been used to better know some of the rate constants used in the case of cyclopentane. The main reaction pathways have been derived from flow rate and sensitivity analyses

Experimental study of the structure of a lean premixed indane/CH4/O2/Ar flame

In order to better understand the chemistry involved during the combustion of components of diesel fuel, the structure of a laminar lean premixed methane flame doped with indane has been investigated. The gases of this flame contains 7.1% (molar) of methane, 36.8% of oxygen and 0.90% of indane corresponding to an equivalence ratio of 0.74 and a ratio C9H10/CH4 of 12.75%. The flame has been stabilized on a burner at a pressure of 6.7 kPa using argon as dilutant, with a gas velocity at the burner of 49.2 cm/s at 333 K. Quantified species included usual methane C0-C2 combustion products, but also 11 C3-C5 hydrocarbons and 3 C1-C3 oxygenated compounds, as well as 17 aromatic products, namely benzene, toluene, phenylacetylene, styrene, ethylbenzene, xylenes, trimethylbenzenes, ethyltoluenes, indene methylindane, methylindene, naphthalene, phenol, benzaldehyde, benzofuran. The temperature was measured thanks to a thermocouple in PtRh (6%)-PtRh (30%) settled inside the enclosure and ranged from 800 K close to the burner up to 2000 K in the burned gases.Comment: 6th International Seminar on Flame Structure, Bruxelles : Belgique (2008