The role of chemistry in the oscillating combustion of hydrocarbons: An experimental and theoretical study

A. Stagni (1) , Y. Song (2) , L A Vandewalle (3) , K M van Geem (3) , G B Marin (3) , Olivier Herbinet (2) , Frederique Battin-Leclerc (2) , T. Faravelli (1)

1 Dipartimento di Chimica, Materiali e Ingegneria Chimica"Giulio Natta"
2 LRGP - Laboratoire Réactions et Génie des Procédés
3 UGENT - Universiteit Gent = Ghent University

The stable operation of low-temperature combustion processes is an open challenge, due to the presence of undesired deviations from steady-state conditions: among them, oscillatory behaviors have been raising significant interest. In this work, the establishment of limit cycles during the combustion of hydrocarbons in a well-stirred reactor was analyzed to investigate the role of chemistry in such phenomena. An experimental investigation of methane oxidation in dilute conditions was carried out, thus creating quasi-isothermal conditions and decoupling kinetic effects from thermal ones. The transient evolution of the mole fractions of the major species was obtained for different dilution levels (0.0025≤ ≤ 0.025), inlet temperatures (1080 K≤ ≤1190 K) and equivalence ratios (0.75≤ ≤1). Rate of production analysis and sensitivity analysis on a fundamental kinetic model allowed to identify the role of the dominating recombination reactions, first driving ignition, then causing extinction. A bifurcation analysis provided further insight in the major role of these reactions for the reactor stability. One-parameter continuation allowed to identify a temperature range where a single, unstable solution exists, and where oscillations were actually observed. Multiple unstable states were identified below the upper branch, where the stable (cold) solution is preferred. The role of recombination reactions in determining the width of the unstable region could be captured, and bifurcation analysis showed that, by decreasing their strength, the unstable range was progressively reduced, up to the full disappearance of oscillations. This affected also the oxidation of heavier hydrocarbons, like ethylene. Finally, less dilute conditions were analyzed using propane as fuel: the coupling with heat exchange resulted in multiple Hopf Bifurcations, with the consequent formation of intermediate, stable regions within the instability range in agreement with the experimental observations.

Mots clés: Reactor stability; Methane; Low-temperature combustion; Oscillations; Bifurcation

Domaines: Chimie théorique et/ou physique; Génie des procédés

A. Stagni, Y. Song, L A Vandewalle, K M van Geem, G B Marin, et al.. The role of chemistry in the oscillating combustion of hydrocarbons: An experimental and theoretical study. Chemical Engineering Journal, 2020, 385, pp.123401. ⟨10.1016/j.cej.2019.123401⟩. ⟨hal-02434686⟩