Thermal Decomposition of Potential Ester Biofuels. Part I: Methyl Acetate and Methyl Butanoate

Journal Article · Fri Jun 09 04:00:00 EDT 2017 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.7b02639· OSTI ID:1373898

Porterfield, Jessica P.; Bross, David H.; Ruscic, Branko; Thorpe, James H.; Nguyen, Thanh Lam; Baraban, Joshua H.; Stanton, John F.; Daily, John W.; Ellison, G. Barney

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, HCΞCH, 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 β 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 Δ_fH₂₉₈(CH₃COOCH₃) = -98.7 ± 0.2 kcal mol^-1, Δ_fH₂₉₈(CH₃CO₂) = -45.7 ± 0.3 kcal mol^-1, and Δ_fH₂₉₈(COOCH₃) = -38.3 ± 0.4 kcal mol^-1.

• Research Organization: Argonne National Laboratory (ANL)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
• DOE Contract Number: AC02-06CH11357
• OSTI ID: 1373898
• Journal Information: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 24 Vol. 121; ISSN 1089-5639
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

Related Subjects

Active Thermochemical Tables
biofuels
esters
pyrolysis
thermochemistry