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Direct fired supercritical carbon dioxide cycles are one of the most promising power generation method in terms of their efficiency and environmental friendliness. Two most important challenges in implementing these cycles are the high pressure (300 bar) and high CO2 dilution (>80 %) in the combustor. The design and development of supercritical oxy-combustors for natural gas requires accurate reaction kinetic models to predict the combustion outcomes. The presence of small amount of impurities in natural gas and other feed streams to oxy-combustors makes these predictions even more complex. During oxy-combustion, trace amounts of nitrogen present in the oxidizer is converted to NOx and gets into the combustion chamber along with the recirculated CO2. Similarly, natural gas can contain trace amount of ammonia and sulfurous impurities which gets converted to NOx and SOx and gets back into the combustion chamber with recirculated CO2. In this work, a reaction model is developed for predicting the effect of impurities like NOx and SOx on supercritical methane combustion. The base mechanism used in this work is GRI 3.0. H2S combustion chemistry is obtained from Bongartz et al. while NOx chemistry is from Konnov et al. The reaction model is then optimized for a pressure range of 30–300 bar using high pressure shock tube data from literature. It is then validated with data obtained from literature for methane combustion, H2S oxidation and NOx effects on ignition delay. The effect of impurities on CH4 combustion up to 16 atm is validated using NOx doped methane studies obtained from literature. In order to validate the model for high pressure conditions, experiments are conducted in a high pressure (∼100 bar) shock tube facility at UCF for natural gas identical mixtures with N2O as impurity. Current results show that there is significant change in ignition delay with the presence of impurities. A comparison is made with experimental data using the developed model and predictions are found to be in good agreement. The model developed was used to study the effect of impurities on CO formation from sCO2 combustor. It was found that NOx helps in reducing CO formation while presence of H2S results in formation of more CO. The reaction mechanism developed herein can also be used as a base mechanism to develop reduced mechanism for use in CFD simulations.

The direct-fired supercritical carbon dioxide cycles are one of the most promising power generation methods in terms of their efficiency and environmental friendliness. Two important challenges in implementing these cycles are the high pressure (300 bar) and high CO2 dilution (>80%) in the combustor. The design and development of supercritical oxy-combustors for natural gas require accurate reaction kinetic models to predict the combustion outcomes. The presence of a small amount of impurities in natural gas and other feed streams to oxy-combustors makes these predictions even more complex. During oxy-combustion, trace amounts of nitrogen present in the oxidizer is converted to NOx and gets into the combustion chamber along with the recirculated CO2. Similarly, natural gas can contain a trace amount of ammonia and sulfurous impurities that get converted to NOx and SOx and get back into the combustion chamber with recirculated CO2. In this work, a reaction model is developed for predicting the effect of impurities such as NOx and SOx on supercritical methane combustion. The base mechanism used in this work is GRI Mech 3.0. H2S combustion chemistry is obtained from Bongartz et al. while NOx chemistry is from Konnov. The reaction model is then optimized for a pressure range of 30–300 bar using high-pressure shock tube data from the literature. It is then validated with data obtained from the literature for methane combustion, H2S oxidation, and NOx effects on ignition delay. The effect of impurities on CH4 combustion up to 16 atm is validated using NOx-doped methane studies obtained from the literature. In order to validate the model for high-pressure conditions, experiments are conducted at the UCF shock tube facility using natural gas identical mixtures with N2O as an impurity at ∼100 bar. Current results show that there is a significant change in ignition delay with the presence of impurities. A comparison is made with experimental data using the developed model and predictions are found to be in good agreement. The model developed was used to study the effect of impurities on CO formation from sCO2 combustors. It was found that NOx helps in reducing CO formation while the presence of H2S results in the formation of more CO. The reaction mechanism developed herein can also be used as a base mechanism to develop reduced mechanisms for use in CFD simulations.

The need for more efficient power cycles has attracted interest in super-critical CO2 (sCO2) cycles. However, the effects of high CO2 dilution on auto-ignition at extremely high pressures has not been studied in depth. As part of the effort to understand oxy-fuel combustion with massive CO2 dilution, we have measured shock tube ignition delay times (IDT) for methane/O2/CO2 mixtures and hydrogen/O2/CO2 mixtures using sidewall pressure and OH* emission near 306 nm. Ignition delay time was measured in two different facilities behind reflected shock waves over a range of temperatures, 1045–1578 K, in different pressures and mixture regimes, i.e., CH4/O2/CO2 mixtures at 27–286 atm and H2/O2/CO2 mixtures at 37–311 atm. The measured data were compared with the predictions of two recent kinetics models. Fair agreement was found between model and experiment over most of the operating conditions studied. For those conditions where kinetic models fail, the current ignition delay time measurements provide useful target data for development and validation of the mechanisms.

To reduce the reliance on fossil fuels in the transportation sector and increase combustion efficiency, the Co-Optima initiative from US Department of Energy identified the top 10 biofuels for downsized, boosted, spark-ignition engines. Most of these biofuels have detailed reaction mechanisms available in literature developed based on studies at temperatures lower than 1700 K and an equivalence ratio of less than five. As such, the performance of these detailed mechanisms at high temperature and extremely rich conditions are unknown. It is important to validate kinetic mechanisms at these conditions because they are conducive to soot formation. Prediction of soot by chemical kinetic models relies on the prediction of underlying benchmark species like carbon monoxide and ethylene. In this work, we conduct high temperature (1700–2050 K) and high equivalence ratio(Φ=8.6) oxidation of these biofuels, namely 2,4,4-trimethyl-1-pentene (α-diisobutylene), ethanol, cyclopentanone, methyl acetate, and 2-methylfuran, blended in ethylene behind reflected shock waves at 4–4.7 atm pressure. Carbon monoxide and ethylene time histories are measured simultaneously using a continuous feedback quantum cascade laser near 4.9 µm and a tunable CO2 gas laser at 10.532 nm, respectively. Results show that ethanol blend forms more carbon monoxide than other biofuels and consumes ethylene faster than the biofuel blends in the temperature range considered. The performance of different mechanisms in literature are evaluated against the experimental results. The novel reaction mechanism ‘the Co-Optima model’, which includes the sub mechanisms for all the biofuels in this study, was found to be the best mechanism for the experimental conditions studied.

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 CO2 addition. Using high-speed 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 CO2 mole fraction was varied between a value of X C O 2 = 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, CH4 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 CO2 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 bifurcation effects as different methods in measuring the ignition delay time could result in different interpretations of kinetic mechanisms and impede the development of future mechanisms.

Soot emissions in combustion are unwanted consequences of burning hydrocarbon fuels. The presence of soot during and following combustion processes is an indication of incomplete combustion and has several negative consequences including the emission of harmful particulates and increased operational costs. Efforts have been made to reduce soot production in combustion engines through utilizing oxygenated biofuels in lieu of traditional nonoxygenated feedstocks. The ongoing Co-Optimization of Fuels and Engines (Co-Optima) initiative from the US Department of Energy (DOE) is focused on accelerating the introduction of affordable, scalable, and sustainable biofuels and high-efficiency, low-emission vehicle engines. The Co-Optima program has identified a handful of biofuel compounds from a list of thousands of potential candidates. In this study, a shock tube was used to evaluate the performance of soot reduction of five high-performance biofuels downselected by the Co-Optima program. Current experiments were performed at test conditions between 1,700 and 2,100 K and 4 and 4.7 atm using shock tube and ultrafast, time-resolve laser absorption diagnostic techniques. The combination of shock heating and nonintrusive laser detection provides a state-of-the-art test platform for high-temperature soot formation under engine conditions. Soot reduction was found in ethanol, cyclopentanone, and methyl acetate; conversely, an α-diisobutylene and methyl furan produced more soot compared to the baseline over longer test times. For each biofuel, several reaction pathways that lead towards soot production were identified. The data collected in these experiments are valuable information for the future of renewable biofuel development and their applicability in engines.

In this study, a shock tube is used to investigate combustion tendencies of several fuel mixtures under high carbon dioxide dilution and high fuel loading. Individual mixtures of oxy-syngas and oxy-methane fuels were added to CO2 bath gas environments and ignition delay time data was recorded. Reflected shock pressures maxed around 100 atm, which is above the critical pressure of carbon dioxide in to the supercritical regime. In total, five mixtures were investigated within a temperature range of 1050–1350K. Ignition delay times of all mixtures were compared with predictions of two leading chemical kinetic computer mechanisms for accuracy. The mixtures included four oxy-syngas and one oxy-methane combinations. The experimental data tended to show good agreement with the predictions of literature models for the methane mixture. For all syngas mixtures though the models performed reasonably well at some conditions, predictions were not able to accurately capture the overall behavior. For this reason, there is a need to further investigate the discrepancies in predictions. Additionally, more data must be collected at high pressures to fully understand the chemical kinetic behavior of these mixtures to enable the supercritical CO2 power cycle development.

In this study, syngas combustion was investigated behind reflected shock waves in CO2 bath gas to measure ignition delay times and to probe the effects of CO2 dilution. New syngas data were taken between pressures of 34.58–45.50 atm and temperatures of 1113–1275K. This study provides experimental data for syngas combustion in CO2 diluted environments: ignition studies in a shock tube (59 data points in 10 datasets). In total, these mixtures covered a range of temperatures T, pressures P, equivalence ratios φ, H2/CO ratio θ, and CO2 diluent concentrations. Multiple syngas combustion mechanisms exist in the literature for modelling ignition delay times and their performance can be assessed against data collected here. In total, twelve mechanisms were tested and presented in this work. All mechanisms need improvements at higher pressures for accurately predicting the measured ignition delay times. At lower pressures, some of the models agreed relatively well with the data. Some mechanisms predicted ignition delay times which were 2 orders of magnitudes different from the measurements. This suggests there is behavior that has not been fully understood on the kinetic models and are inaccurate in predicting CO2 diluted environments for syngas combustion. To the best of our knowledge, current data are the first syngas ignition delay times measurements close to 50 atm under highly CO2 diluted (85% per vol.) conditions.

Pyrolysis and oxidation of triethyl phosphate (TEP) were performed in the reflected shock region at temperatures of 1462–1673 K and 1213–1508 K, respectively, and at pressures near 1.3 atm. CO concentration time histories during the experiments were measured using laser absorption spectroscopy at 4580.4 nm. Experimental CO yields were compared with model predictions using the detailed organophosphorus compounds (OPC) incineration mechanism from the Lawrence Livermore National Lab (LLNL). The mechanism significantly underpredicts CO yield in TEP pyrolysis. During TEP oxidation, predicted rate of CO formation was significantly slower than the experimental results. Therefore, a new improved kinetic model for TEP combustion was developed, which was built upon the AramcoMech2.0 mechanism for C0-C2 chemistry and the existing LLNL submechanism for phosphorus chemistry. Thermochemical data of 40 phosphorus (P)-containing species were reevaluated, either using recently published group values for P-containing speci...

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.

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 1 and 31 atm. The experimental mixtures were conducted at an equivalence ratio of 1 with CH4 mole fractions ranging from 3.5%–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 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 the different parameters showing that 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 under these conditions. Current data provides crucial validation data needed for development of future methane/CO2 kinetic mechanisms.

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.