Theoretical and experimental study on the autoignition phenomena of homogeneous reactive mixtures

Field: Chemistry (Physical Sciences)

The main objective of this Thesis is the study of the autoignition phenomenon of reactive mixtures from a theoretical and experimental point of view. A wide parametric study has been carried out in a Rapid Compression-Expansion Machine (RCEM) for different initial temperatures, compression ratios, equivalence ratios and molar fractions of oxygen (by using synthetic EGR) for different fuels. The ignition delay referred to cool flames (if it can be identified), as well as the ignition delay referred to the high-temperature stage of the ignition, have been experimentally obtained and their trends have been explained regarding the chemical kinetics of each fuel.\nThe different effects of the species that compose the synthetic EGR on the ignition delay have been studied, decoupling the thermodynamic effects from the chemical ones. Different compositions have been taken into account to generate the synthetic EGR, and validation limits have been obtained for each mixture. The thermodynamic and the chemical effects have shown to be opposed, while the dominant one is different depending on the working temperature.\nSeveral chemical kinetic mechanisms have been validated by comparison to the experimental results. A detailed mechanism for iso-octane and n-heptane blends and a reduced mechanisms for n-dodecane have been analyzed. Moreover, a sub-model for the generation and decay of excited OH* has been validated by comparison to chemiluminescence and spectroscopy results.\nThe different radiation sources have been studied for iso-octane and n-heptane by means of spectroscopy techniques. Besides, chemiluminescence measurements filtered at 310nm (OH* emission wavelength) have been performed in order to analyze the generalization and propagation velocity of the autoignition front. The ignition propagation has shown to depend on the thermodynamic conditions reached in the combustion chamber when the first ignition spot occurs and not on the global reactivity of the mixture. Furthermore, two different radiation sources have been found at 310nm in the spectroscopic analysis depending on the ignition intensity: the decay of the OH* radical from excited to ground state and the oxidation of CO to CO2 (CO continuum). However, these optical techniques have been applied only in the experiments carried out with iso-octane and n-heptane due to technical limitations. \nFinally, a new predictive model has been theoretically developed starting from the Glassman's model for autoignition. This method is based on modeling the accumulation rate of chain carriers up to reach their critical concentration (obtaining the ignition delay referred to cool flames) and, afterwards, modeling the disappearance rate of such chain carriers up to their consumption (when the maximum heat release rate is reached, obtaining the ignition delay referred to the high-temperature stage of the process). The predictive capability of the model has been compared to the ability of other methods that can be found in the literature, such as the Livengood & Wu integral method. The validity of each method has been tested, defining a working methodology to obtain reasonable predictions for the ignition delay.