A study of the low temperature autoignition of methyl esters

Abstract The autoignition of a series of C 4 to C 8 fatty acid methyl esters has been studied in a rapid compression machine in the low and intermediate temperature region (650–850 K) and at increasing pressures (4–20 bar). Methyl hexanoate was selected for a full investigation of the autoignition phenomenology, including the identification and determination of the intermediate products of low temperature oxidation. The oxidation scheme and overall reactivity of methyl hexanoate has been examined and compared to the reactivity of C 4 to C 7 n -alkanes in the same experimental conditions to evaluate the impact of the ester function on the reactivity of the n -alkyl chain. The low temperature reactivity leading to the first stage of autoignition is similar to n -heptane. However, the negative temperature coefficient region is located at lower temperature than in the case of the n -alkanes of corresponding reactivity. An evaluation of the distribution of esteralkyl radicals R and esteralkylperoxy radicals ROO gives an insight into the main reaction pathways.

[1]  F. P. Tully,et al.  Hydrogen-atom abstraction from alkanes by OH. 3. Propane , 1986 .

[2]  M. Navarro,et al.  Experimental and modeling study of C5H10O2 ethyl and methyl esters. , 2007, The journal of physical chemistry. A.

[3]  P. Dagaut,et al.  Rapeseed oil methyl ester oxidation over extended ranges of pressure, temperature, and equivalence ratio: Experimental and modeling kinetic study , 2007 .

[4]  Philippe Dagaut,et al.  Chemical kinetic study of the effect of a biofuel additive on jet-A1 combustion. , 2007, The journal of physical chemistry. A.

[5]  J. M. Simoes,et al.  Energetics of organic free radicals , 1996 .

[6]  Anthony J. Marchese,et al.  A wide-ranging kinetic modeling study of methyl butanoate combustion , 2007 .

[7]  P. Dagaut,et al.  The Low Temperature Oxidation of DME and Mutual Sensitization of the Oxidation of DME and Nitric Oxide: Experimental and Detailed Kinetic Modeling , 2001 .

[8]  M. Ribaucour,et al.  Autoignition Delays of a Series of Linear and Branched Chain Alkanes in the Intermediate Range of Temperature , 1996 .

[9]  Guillaume Dayma,et al.  Experimental and Kinetic Modeling Study of the Oxidation of Methyl Hexanoate , 2008 .

[10]  William J. Pitz,et al.  Ignition of Isomers of Pentane: An Experimental and Kinetic Modeling Study , 2000 .

[11]  M. Ribaucour,et al.  On the influence of the position of the double bond on the low-temperature chemistry of hexenes , 2005 .

[12]  Murray J. Thomson,et al.  A comparison of saturated and unsaturated C4 fatty acid methyl esters in an opposed flow diffusion flame and a jet stirred reactor , 2007 .

[13]  C. Bamford,et al.  Comprehensive Chemical Kinetics , 1976 .

[14]  Frederick L. Dryer,et al.  The reaction kinetics of dimethyl ether. II: Low‐temperature oxidation in flow reactors , 2000 .

[15]  Yu-ran Luo Handbook of Bond Dissociation Energies in Organic Compounds , 2002 .

[16]  D. Haworth,et al.  Premixed ignition behavior of alternative diesel fuel-relevant compounds in a motored engine experiment , 2007 .

[17]  William J. Pitz,et al.  DETAILED CHEMICAL KINETIC MECHANISMS FOR COMBUSTION OF OXYGENATED FUELS , 2000 .

[18]  Charles K. Westbrook,et al.  Chemical kinetics of hydrocarbon ignition in practical combustion systems , 2000 .

[19]  M. Ribaucour,et al.  A rapid compression machine investigation of oxidation and auto-ignition of n-Heptane: Measurements and modeling , 1995 .

[20]  M. Navarro,et al.  Enthalpies of formation, bond dissociation energies and reaction paths for the decomposition of model biofuels: ethyl propanoate and methyl butanoate. , 2007, The journal of physical chemistry. A.

[21]  Edward R. Ritter,et al.  THERM: a computer code for estimating thermodynamic properties for species important to combustion and reaction modeling , 1991, J. Chem. Inf. Comput. Sci..

[22]  C. Westbrook,et al.  A Comprehensive Modeling Study of iso-Octane Oxidation , 2002 .

[23]  F. P. Tully,et al.  Hydrogen-atom abstraction from alkanes by OH. IV: Isobutane , 1986 .