A Study Of Syngas Oxidation At High Pressures And Low Temperatures

Ignition and oxidation characteristics of CO/H2, H2/O2 and CO/H2/CH4/CO2/Ar fuel blends in air were studied using both experimental and computer simulation methods. Shock-tube experiments were conducted behind reflected shock waves at intermediate temperatures (825 \u3c T \u3c 1400 K) for a wide range of pressures (1 \u3c P \u3c 45 atm). Results of this study provide the first undiluted fuel-air ignition delay time experiments to cover such a wide range of syngas mixture compositions over the stated temperature range. Emission in the form of chemiluminescence from the hydroxyl radical (OH*) transition near 307 nm and the pressure behind the reflected shock wave were used to monitor reaction progress from which ignition delay times were determined. In addition to the experimental analysis, chemical kinetics calculations were completed to compare several chemical kinetics mechanisms to the new experimental results. Overall, the models were in good agreement with the shock-tube data, especially at higher temperatures and lower pressures, yet there were some differences between the models at higher pressures and the lowest temperatures, in some cases by as much as a factor of five. In order to discern additional information from the chemical kinetics mechanisms regarding their response to a wide range of experimental conditions, ignition delay time and reaction rate sensitivity analyses were completed at higher and lower temperatures and higher and lower pressures. These two sensitivity analyses allow for the identification of the key reactions responsible for ignition. The results of the sensitivity analysis indicate that the ignition-enhancing reaction H + O2 = O + OH and hydrogen oxidation kinetics in general were most important regardless of mixture composition, temperature or pressure. However, lower-temperature, higher-pressure ignition delay time results indicate additional influence from HO2- and CO- containing reactions, particularly the well-known H + O + M = HO2 + M reaction and also the CO + O + M = CO2 + M and CO + HO2 = CO2 + OH reactions. Differences in the rates of the CO-related reactions are shown to be the cause of some of the discrepancies amongst the various models at elevated pressures. However, the deviation between the models and the experimental data at the lowest temperatures could not be entirely explained by discrepancies in the current rates of the reactions contained within the mechanisms. Additional calculations were therefore performed to gain further understanding regarding the opposing ignition behavior for calculated and measured ignition delay time results. Impurities, friction induced ionization, static charge accumulation, boundary layer effects, wall reaction effects, and revised chemical kinetics were all considered to be possible mechanisms for the model and measured data disparity. For the case of wall-reaction effects, additional shock-tube experiments were conducted. For the remaining effects listed above, only detailed calculations were conducted. Results from this preliminary anomaly study are at this time inconclusive, but likely avenues for future study were identified. Additional kinetics calculations showed that the large difference between the experimental data and the chemical kinetics models predictions at low temperatures can be explained by at least one missing reaction relevant to low-temperature and high-pressure experimental conditions involving the formation of H2O2, although further study beyond the scope of this thesis is required to prove this hypothesis both theoretically and experimentally