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Determining detailed reaction kinetics for nitrogen- and oxygen-containing fuels

Nicole Jeanne Labbe, University of Massachusetts Amherst


With the emergence of new biorenewable transportation fuels, the role of heteroatoms in combustion has increased tremendously. While petroleum-based fuels are primarily hydrocarbons, many biorenewable fuels contain heteroatoms such as oxygen and nitrogen, introducing new challenges associated with toxic emissions. A fundamental understanding of the chemical kinetics of combustion of these heteroatomic fuels is necessary to elucidate the pathways by which these toxic emissions are formed and may be achieved through the development of combustion models. Reaction sets, the core of these combustion models, may be assembled for individual fuels through a balance of employing vetted rate constants from prior publications, quantum chemistry calculations, and rate constant estimations. For accuracy, reaction sets should be tested against experimental combustion studies such as low-pressure flame experiments using molecular-beam mass spectrometry (MBMS) or chemiluminescence and high-pressure shock-tube experiments. This dissertation presents the development of a new reaction set to describe gas-phase combustion chemistry of fuels containing only hydrogen, carbon, oxygen, and nitrogen. The foundation of this model was a reaction set to describe combustion of ammonia flames. This reaction set contains only H/N/O chemistry for simplicity. The new reaction set was tested against a pyrolysis shock-tube study, as well as 12 MBMS flame experiments under a variety of conditions, including different mixtures of fuels and oxidizers (NH3, N 2O, H2, NO, O2), fuel equivalence ratios (lean to rich), pressures, and concentrations of diluent gas. Additionally, the base H/N/O mechanism was expanded to include carbon chemistry and was tested against flames of dimethylamine, ethylamine, and a methane/ammonia mixture. This reaction set was employed to study heterocyclic biofuels including a fuel-rich flame of tetrahydropyran, the monoether analogue to cyclohexane and the basic ring in cellulose. Additionally, the model was used in a study of morpholine, a 6-membered ring with both ether and amine functionalities, testing the model against fuel-rich flame studies using both MBMS and chemiluminescence techniques and high-pressure shock-tube studies for both oxidation and pyrolysis at elevated temperatures and pressures. Lastly, the model was used to study the combustion of hypergolic rocket fuels, specifically monomethyl hydrazine and tetramethylethyldiamine with red fuming nitric acid.

Subject Area

Chemical engineering

Recommended Citation

Labbe, Nicole Jeanne, "Determining detailed reaction kinetics for nitrogen- and oxygen-containing fuels" (2013). Doctoral Dissertations Available from Proquest. AAI3556262.