Experimental and modeling study of the thermal decomposition of methyl decanoate

Olivier Herbinet (1) , Pierre Alexandre Glaude (1) , Valérie Warth (1) , Frédérique Battin-Leclerc (1)

1 LRGP - Laboratoire Réactions et Génie des Procédés

The experimental study of the thermal decomposition of methyl decanoate was performed in a jet stirred reactor at temperatures ranging from 773 to 1123 K, at residence times between 1 and 4 s, at a pressure of 800 Torr (106.6 kPa) and at high dilution in helium (fuel inlet mole fraction of 0.0218). Species leaving the reactor were analyzed by gas chromatography. Main reaction products were hydrogen, carbon oxides, small hydrocarbons from C1 to C3, large 1-olefins from 1-butene to 1 nonene, and unsaturated esters with one double bond at the end of the alkyl chain from methyl 2 propenoate to methyl-8-nonenoate. At the highest temperatures, the formation of polyunsaturated species was observed: 1,3-butadiene, 1,3-cyclopentadiene, benzene, toluene, indene, and naphthalene. These results were compared with previous ones about the pyrolysis of n dodecane, an n-alkane of similar size. The reactivity of both molecules was found to be very close. The alkane produces more olefins while the ester yields unsaturated oxygenated compounds. A detailed kinetic model for the thermal decomposition of methyl decanoate has been generated using the version of software EXGAS which was updated to take into account the specific chemistry involved in the oxidation of methyl esters. This model contains 324 species and 3231 reactions. It provided a very good prediction of the experimental data obtained in jet-stirred reactor. The formation of the major products was analyzed. The kinetic analysis showed that the retro-ene reactions of intermediate unsaturated methyl esters are of importance in low reactivity systems.

Mots clés: Methyl decanoate; Biodiesel; Jet-stirred reactor; Thermal decomposition; Pyrolysis; Kinetic modeling

Domaines: Chimie théorique et/ou physique

Olivier Herbinet, Pierre Alexandre Glaude, Valérie Warth, Frédérique Battin-Leclerc. Experimental and modeling study of the thermal decomposition of methyl decanoate. Combustion and Flame, 2011, 158 (7), pp.1288-1300. ⟨10.1016/j.combustflame.2010.11.009⟩. ⟨hal-00724939⟩