Authors

Abstract

Two methyl esters have been examined as models for the pyrolysis of biofuels. Dilute samples (0.06 - 0.13%) of methyl acetate (CH3COOCH3) and methyl butanoate (CH3CH2CH2COOCH3) were entrained in (He, Ar) carrier gas and decomposed in a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from the methyl esters were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by matrix infrared absorption spectroscopy. Pyrolysis pressures in the pulsed micro-reactor were roughly 20 Torr and residence times through the reactors were approximately 25 - 150 µs. Reactor temperatures of 300 – 1600 K were explored. Decomposition of CH3COOCH3 commences at 1000 K and the initial products are (CH2=C=O and CH3OH). As the micro-reactor is heated to 1300 K, a mixture of (CH2=C=O and CH3OH, CH3, CH2=O, H, CO, CO2) appears. The thermal cracking of CH3CH2CH2COOCH3 begins at 800 K with the formation of (CH3CH2CH=C=O, CH3OH). By 1300 K, the pyrolysis of methyl butanoate yields a complex mixture of (CH3CH2CH=C=O, CH3OH, CH3, CH2=O, CO, CO2, CH3CH=CH2, CH2CHCH2, CH2=C=CH2, HCCCH2, CH2=C=C=O, CH2=CH2, HCCH, CH2=C=O). Based on the results from the thermal cracking of methyl acetate and methyl butanoate, we predict several important decomposition channels for the pyrolysis of fatty acid methyl esters, R CH2-COOCH3. The lowest energy fragmentation will be a 4-center elimination of methanol to form the ketene, RCH=C=O. At higher temperatures, concerted fragmentation to radicals will ensue to produce a mixture of species: (RCH2 + CO2 + CH3) and (RCH2 + CO + CH2=O + H). Thermal cracking of the  C-C bond of the methyl ester will generate the radicals (R and H) as well as CH2=C=O + CH2=O. The thermochemistry of methyl acetate and its fragmentation products have been obtained via the Active Thermochemical Tables (ATcT) approach, resulting in ∆fH298(CH3COOCH3) = -98.7 ± 0.2 kcal mol-1, ∆fH298(CH3CO2) = -45.7 ± 0.3 kcal mol-1, and ∆fH298(COOCH3) = -38.3 ± 0.4 kcal mol-1.