Shock tube studies of methyl butanoate pyrolysis with relevance to biodiesel

Methyl butanoate pyrolysis and decomposition pathways were studied in detail by measuring concentration time-histories of CO, CO2, CH3, and C2H4 using shock tube/laser absorption methods. Experiments were conducted behind reflected shock waves at temperatures of 1200-1800 K and pressures near 1.5 atm using mixtures of 0.1%, 0.5%, and 1% methyl butanoate in Argon. A novel laser diagnostic was developed to measure CO in the v(1) fundamental vibrational band near 4.56 mu m using a new generation of quantum-cascade lasers. Wavelength modulation spectroscopy with second-harmonic detection (WMS-2f) was used to measure CO2 near 2752 nm. Methyl radical was measured using UV laser absorption near 216 nm, and ethylene was monitored using IR gas laser absorption near 10.53 mu m. An accurate methyl butanoate model is critical in the development of mechanisms for larger methyl esters, and the measured time-histories provide kinetic targets and strong constraints for the refinement of the methyl butanoate reaction mechanism. Measured CO mole fractions reach plateau values that are the same as the initial fuel mole fraction at temperatures higher than 1500 K over the maximum measurement time of 2 ms or less. Two recent kinetic mechanisms are compared with the measured data and the possible reasons for this 1:1 ratio between MB and CO are discussed. Based on these discussions, it is expected that similar CO/fuel and CO2/fuel ratios for biodiesel molecules, particularly saturated components of biodiesel, should occur. (c) 2012 The Combustion Institute. Published by Elsevier Inc. All rights reserved.