Publications

Multi-species time-history measurements during high-temperature acetone and 2-butanone pyrolysis

Multi-species time-history measurements during high-temperature acetone and 2-butanone pyrolysis

K. Y. Lam*, W. Ren, S. H. Pyun, A. Farooq, D. F. Davidson, R. K. Hanson

Proceedings of the Combustion Institute, 34, 607-615, (2013)

K. Y. Lam*, W. Ren, S. H. Pyun, A. Farooq, D. F. Davidson, R. K. Hanson
Shock tube, Acetone, 2-Butanone, Laser absorption
2013
High-temperature acetone and 2-butanone pyrolysis studies were conducted behind reflected shock waves using five species time-history measurements (ketone, CO, CH3, CH4 and C2H4). Experimental conditions covered temperatures of 1100–1600 K at 1.6 atm, for mixtures of 0.25–1.5% ketone in argon. During acetone pyrolysis, the CO concentration time-history was found to be strongly sensitive to the acetone dissociation rate constant k1 (CH3COCH3 → CH3 + CH3CO), and this could be directly determined from the CO time-histories, yielding k1(1.6 atm) = 2.46 × 1014 exp(−69.3 [kcal/mol]/RT) s−1 with an uncertainty of ±25%. This rate constant is in good agreement with previous shock tube studies from Sato and Hidaka (2000) [3] and Saxena et al. (2009) [4] (within 30%) at temperatures above 1450 K, but is at least three times faster than the evaluation from Sato and Hidaka at temperatures below 1250 K. Using this revised k1 value with the recent mechanism of Pichon et al. (2009) [5], the simulated profiles during acetone pyrolysis show excellent agreement with all five species time-history measurements. Similarly, the overall 2-butanone decomposition rate constant ktot was inferred from measured 2-butanone time-histories, yielding ktot(1.5 atm) = 6.08 × 1013 exp(−63.1 [kcal/mol]/RT) s−1 with an uncertainty of ±35%. This rate constant is approximately 30% faster than that proposed by Serinyel et al. (2010) [11] at 1119 K, and approximately 100% faster at 1412 K. Using the measured 2-butanone and CO time-histories and an O-atom balance analysis, a missing removal pathway for methyl ketene was identified. The rate constant for the decomposition of methyl ketene was assumed to be the same as the value for the ketene decomposition reaction. Using the revised ktot value and adding the methyl ketene decomposition reaction to the Serinyel et al. mechanism, the simulated profiles during 2-butanone pyrolysis show good agreement with the measurements for all five species.
DOI: 10.1016/j.proci.2012.06.009