A comprehensive experimental and modeling study of isobutene oxidation

Chong Wen Zhou, Yang Li, Eoin O'Connor, Kieran P. Somers, Sébastien Thion, Charles Keesee, Olivier Mathieu, Eric L. Petersen, Trent A. DeVerter, Matthew A. Oehlschlaeger, Goutham Kukkadapu, Chih Jen Sung, Majed Alrefae, Fathi Khaled, Aamir Farooq, Patricia Dirrenberger, Pierre Alexandre Glaude, Frédérique Battin-Leclerc, Jeffrey Santner, Yiguang JuTimothy Held, Francis M. Haas, Frederick L. Dryer, Henry J. Curran

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Abstract

Isobutene is an important intermediate in the pyrolysis and oxidation of higher-order branched alkanes, and it is also a component of commercial gasolines. To better understand its combustion characteristics, a series of ignition delay time (IDT) and laminar flame speed (LFS) measurements have been performed. In addition, flow reactor speciation data recorded for the pyrolysis and oxidation of isobutene is also reported. Predictions of an updated kinetic model described herein are compared with each of these data sets, as well as with existing jet-stirred reactor (JSR) species measurements. IDTs of isobutene oxidation were measured in four different shock tubes and in two rapid compression machines (RCMs) under conditions of relevance to practical combustors. The combination of shock tube and RCM data greatly expands the range of available validation data for isobutene oxidation models to pressures of 50. atm and temperatures in the range 666-1715. K. Isobutene flame speeds were measured experimentally at 1. atm and at unburned gas temperatures of 298-398. K over a wide range of equivalence ratios. For the flame speed results, there was good agreement between different facilities and the current model in the fuel-rich region. Ab initio chemical kinetics calculations were carried out to calculate rate constants for important reactions such as H-atom abstraction by hydroxyl and hydroperoxyl radicals and the decomposition of 2-methylallyl radicals. A comprehensive chemical kinetic mechanism has been developed to describe the combustion of isobutene and is validated by comparison to the presently considered experimental measurements. Important reactions, highlighted via flux and sensitivity analyses, include: (a) hydrogen atom abstraction from isobutene by hydroxyl and hydroperoxyl radicals, and molecular oxygen; (b) radical-radical recombination reactions, including 2-methylallyl radical self-recombination, the recombination of 2-methylallyl radicals with hydroperoxyl radicals; and the recombination of 2-methylallyl radicals with methyl radicals; (c) addition reactions, including hydrogen atom and hydroxyl radical addition to isobutene and (d) 2-methylallyl radical decomposition reactions. The current mechanism accurately predicts the IDT and LFS measurements presented in this study, as well as the JSR and flow reactor speciation data already available in the literature.The differences in low-temperature chemistry between alkanes and alkenes are also highlighted in this work. In normal alkanes, the fuel radical R˙ adds to molecular oxygen forming alkylperoxyl (RO˙2) radicals followed by isomerization and chain branching reactions which promote low-temperature fuel reactivity. However, in alkenes, because of the relatively shallow well (~20kcalmol-1) for RO˙2 formation compared to ~35kcalmol-1 in alkanes, the R˙+O2 ⇌ RO˙2 equilibrium lies more to the left favoring R˙+O2 rather than RO˙2 radical stabilization. Based on this work, and related studies of allylic systems, it is apparent that reactivity for alkene components at very low temperatures (<800K) emanates from hydroxyl radical addition followed by addition of molecular oxygen to radical. At intermediate temperatures (800-1300K), alkene reactivity is controlled by hydrogen abstraction by molecular oxygen and the reactions between resonantly stabilized radicals and hydroperoxyl radicals which results in chain branching. At higher temperatures (>1300K), the reactivity is mainly governed by the competition between hydrogen abstractions by molecular oxygen and O˙H radicals.

Original languageEnglish (US)
Pages (from-to)353-379
Number of pages27
JournalCombustion and Flame
Volume167
DOIs
StatePublished - May 1 2016

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Fuel Technology
  • Energy Engineering and Power Technology
  • Physics and Astronomy(all)

Keywords

  • Ab initio
  • Chemical kinetics
  • Flame speed
  • Isobutene oxidation
  • Rapid compression machine
  • Shock tube

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