The combustion of methane in air results in large amounts of CO 2 and NO X emissions. In order to reduce the NO X emissions, one possible solution is the oxy-methane combustion with large CO 2 dilution so that the combustion products can be reduced mainly to CO 2 and H 2 O. However, there are very few studies on the chemical kinetics of oxy-methane combustion in a CO 2 diluted environment. In this study, methane time-histories, CH* emission profiles, and pressure time-histories measurements were conducted behind reflected shock waves to gain insight into the effects of CO 2 dilution of the gas mixtures on the ignition of methane. The measurements were carried out for mixtures of CH 4 , CO 2 and O 2 in argon bath gas at temperatures of 1577-2144 K, pressures of 0.53-4.4 atm, equivalence ratios (Φ) of 0.5, 1, and 2, and CO 2 mole fractions (X CO2) of 0, 30%, and 60%. The laser absorption measurements were conducted using a continuous wave distributed feedback interband cascade laser (DFB ICL) centered at 3403.4 nm. The results showed the decrease of activation energy and the increase of ignition delay time as the amount of CO 2 dilution was increased. However, the changes were minor and within the experimental uncertainties of the measurements. Also, the results were compared to the predictions of two different natural gas mechanisms: GRI 3.0 and AramcoMech 1.3 mechanisms. In general the predictions were reasonable when compared to the experimental data; however, there were discrepancies at some conditions. Three different influences of CO 2 addition to the argon bath gas in regards to chemistry, collision efficiencies, and heat capacities were examined. In addition, the present study included experimentally obtained correlations for absorption cross sections of methane for its P(8) line in the v 3 band in argon bath gas with and without carbon-dioxide dilutions at temperatures between 1200 < T < 2000 K and pressures between 0.7 < P <1.2 atm. 1. INTRODUCTION Energy consumption has increased dramatically as the world advances and becomes more industrialized. Over the next twenty five years, the U.S. Department of Energy expects the energy demand to increase by 29% with almost all of the new energy from natural gas [1]. A problem is that current methods for the combustion of natural gas (e.g., gas turbines) result in large amounts of CO 2 and NO X emissions. In order to reduce the greenhouse gases, one possible solution is the oxy-methane

Common definitions for ignition delay time are often hard to determine due to the issue of bifurcation and other non-idealities that result from high levels of CO 2 addition. Using highspeed camera imagery in comparison with more standard methods (e.g., pressure, emission, and laser absorption spectroscopy) to measure the ignition delay time, the effect of bifurcation has been examined in this study. Experiments were performed at pressures between 0.6 and 1.2 atm for temperatures between 1650 and 2040 K. The equivalence ratio for all experiments was kept at a constant value of 1 with methane as the fuel. The CO 2 mole fraction was varied between a value of X CO2 = 0.00 to 0.895. The ignition delay time was determined from three different measurements at the sidewall: broadband chemiluminescent emission captured via a photodetector, CH 4 concentrations determined using a distributed feedback interband cascade laser centered at 3403.4 nm, and pressure recorded via a dynamic Kistler type transducer. All methods for the ignition delay time were compared to high-speed camera images taken of the axial cross-section during combustion. Methane time-histories and the methane decay times were also measured using the laser. It was determined that the flame could be correlated to the ignition delay time measured at the side wall but that the flame as captured by the camera was not homogeneous as assumed in typical shock tube experiments. The bifurcation of the shock wave resulted in smaller flames with large boundary layers and that the flame could be as small as 30% of the cross-sectional area of the shock tube at the highest levels of CO 2 dilution. Comparisons between the camera images and the different ignition delay time methods show that care must be taken in interpreting traditional ignition delay data for experiments with large

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Ignition delay times and methane species time-histories were measured for methane/O2 mixtures in a high CO2 diluted environment using shock tube and laser absorption spectroscopy. The experiments were performed between 1300 K and 2000 K at pressures between 6 and 31 atm. The test mixtures were at an equivalence ratio of 1 with CH4 mole fractions ranging from 3.5% to 5% and up to 85% CO2 with a bath of argon gas as necessary. The ignition delay times and methane time histories were measured using pressure, emission, and laser diagnostics. Predictive ability of two literature kinetic mechanisms (gri 3.0 and aramco mech 1.3) was tested against current data. In general, both mechanisms performed reasonably well against measured ignition delay time data. The methane time-histories showed good agreement with the mechanisms for most of the conditions measured. A correlation for ignition delay time was created taking into account the different parameters showing the ignition activation energy for the fuel to be 49.64 kcal/mol. Through a sensitivity analysis, CO2 is shown to slow the overall reaction rate and increase the ignition delay time. To the best of our knowledge, we present the first shock tube data during ignition of methane/CO2/O2 under these conditions. Current data provides crucial validation data needed for the development of future kinetic mechanisms.

In this study, syngas combustion was investigated behind reflected shock waves in order to gain insight into the behavior of ignition delay times and effects of the CO2 dilution. Pressure and light emissions time-histories measurements were taken at a 2 cm axial location away from the end wall. High-speed visualization of the experiments from the end wall was also conducted. Oxy-syngas mixtures that were tested in the shock tube were diluted with CO2 fractions ranging from 60% to 85% by volume. A 10% fuel concentration was consistently used throughout the experiments. This study looked at the effects of changing the equivalence ratios (ϕ), between 0.33, 0.5, and 1.0 as well as changing the fuel ratio (θ), hydrogen to carbon monoxide, from 0.25, 1.0, and 4.0. The study was performed at 1.61–1.77 atm and a temperature range of 1006–1162 K. The high-speed imaging was performed through a quartz end wall with a Phantom V710 camera operated at 67,065 frames per second. From the experiments, when increasing the equivalence ratio, it resulted in a longer ignition delay time. In addition, when increasing the fuel ratio, a lower ignition delay time was observed. These trends are generally expected with this combustion reaction system. The high-speed imaging showed nonhomogeneous combustion in the system; however, most of the light emissions were outside the visible light range where the camera is designed for. The results were compared to predictions of two combustion chemical kinetic mechanisms: GRI v3.0 and AramcoMech v2.0 mechanisms. In general, both mechanisms did not accurately predict the experimental data. The results showed that current models are inaccurate in predicting CO2 diluted environments for syngas combustion.

Incorporating high energy nanoparticulate additives is considered as a means to enhance the performance of hypergolic ionic liquid (IL) propellants. In this manuscript, we demonstrate the energy content of borane–aluminum nanoparticles produced by ball milling and examine the ignition and combustion behavior of hypergolic ILs loaded with up to 30 weight percent (wt %) of the particles, as measured by two different methods. The goal is to better understand the effects of particle loading on hypergolic ignition and combustion mechanism. Bomb calorimetry and differential scanning calorimetry/thermal gravimetric analysis (DSC/TGA) combined with X-ray diffraction (XRD) were used to determine the combustible energy content of particles with different capping layers and to examine the nature of the combustion products. Particles were found to have up to 97% of combustible metal content. Rapid scan-Fourier transform infrared spectroscopy (RS-FTIR) and photographic methods were used to examine ignition delay and the nature of the flames produced. The addition of borane–aluminum nanoparticles was found to have only small effects on ignition delay, but even small particle loadings were found to significantly change the flame structure and increase the duration of the combustion event. The effects of particle addition on specific impulse and density impulse were estimated.

Diisopropyl ketone (DIPK) is a promising biofuel candidate, which is produced using endophytic fungal conversion. In this work, a high temperature detailed combustion kinetic model for DIPK was developed using the reaction class approach. DIPK ignition and pyrolysis experiments were performed using UCF shock tube. The shock tube oxidation experiments were conducted between 1093 K and 1630 K for different reactant compositions, equivalence ratios (φ =0.5-2.0), and pressures (1-6 atm). In addition, methane concentration time-histories were measured during 2% DIPK pyrolysis in argon using cw laser absorption near 3400 nm at temperatures between 1300 and 1400 K near 1atm. To the best of our knowledge, current ignition delay times (above 1050 K) and methane time histories are the first such experiments performed in DIPK at high temperatures. Present data were used as validation targets for the new kinetic model and simulation results showed fair agreement compared to the experiments. The reaction rates corresponding to the main consumption pathways of DIPK were found to have high sensitivity in controlling the reactivity, so these were adjusted to attain better agreement between the simulation and experimental data. A correlation was developed based on the experimental data to predict the ignition delay times using the temperature, pressure, fuel concentration and oxygen concentration.

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