Butyl Acetate Pyrolysis and Combustion Chemistry: Mechanism Generation and Shock Tube Experiments
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butyl_acetate_manuscript_Dspace.pdf
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Author(s)
Dong, Xiaorui
Pio, Gianmaria
Arafin, Farhan
Laich, Andrew
Baker, Jessica
Ninnemann, Erik
Vasu, Subith S.
Green, William H.
Date Issued
March 31, 2023
Journal
The Journal of Physical Chemistry A
Publisher
American Chemical Society (ACS)
Citation
Dong, X.; Pio, G.; Arafin, F.; Laich, A.; Baker, J.; Ninnemann, E.; Vasu, S. S.; Green, W. H. Butyl Acetate Pyrolysis and Combustion Chemistry: Mechanism Generation and Shock Tube Experiments. J. Phys. Chem. A 2023, 127, 3231– 3245.
Version
Author's final manuscript
Abstract
The combustion and pyrolysis behavior of light esters and fatty acid methyl esters have been widely studied due to their relevance as biofuel and fuel additives. However, a knowledge gap exists for mid-size alkyl acetates, especially ones with long alkoxyl groups. Butyl acetate, in particular, is a promising biofuel with its economic and robust production possibilities and ability to enhance blendstock performance and reduce soot formation. However, it is little studied from both experimental and modeling aspects. This work created detailed oxidation mechanisms for the four butyl acetate isomers (normal-, sec-, tert-, and iso-butyl acetate) at temperatures varying from 650 K to 2000 K and pressures up to 100 atm using the Reaction Mechanism Generator. About 60% of species in each model have thermochemical parameters from published data or in-house quantum calculations, including fuel molecules and intermediate combustion products. Kinetics of essential primary reactions, retro-ene and hydrogen atom abstraction by OH or HO2, governing the fuel oxidation pathways, were also calculated quantum-mechanically. Simulation of the developed mechanisms indicates that the majority of the fuel will decompose into acetic acid and relevant butenes at elevated temperatures, making their ignition behaviors similar to butenes. The adaptability of the developed models to high-temperature pyrolysis systems was tested against
newly collected high-pressure shock experiments; the simulated CO mole fraction time histories have a reasonable agreement with the laser measurement in the shock tube. This work reveals the high-temperature oxidation chemistry of butyl acetates and demonstrates the validity of predictive models for biofuel chemistry established on accurate thermochemical and kinetic parameters.
Subjects
Physical and Theoretical Chemistry
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
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Creative Commons Attribution-Noncommercial-Share Alike
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DOI of Published Version
https://doi.org/10.1021/acs.jpca.2c07545
