The development of accurate chemical kinetic models capable of predicting the combustion of methane and dimethyl ether in common combustion environments such as compression ignition engines and gas turbines is important as it provides valuable data and understanding of these fuels under conditions that are difficult and expensive to study in the real combustors. In this work, both experimental and chemical kinetic model-predicted ignition delay time data are provided covering a range of conditions relevant to gas turbine environments (T = 600 − 1600 K, p = 7 − 41 atm, φ = 0.3, 0.5, 1.0, and 2.0 in 'air' mixtures). The detailed chemical kinetic model (Mech 56.54) is capable of accurately predicting this wide range of data, and it is the first mechanism to incorporate high-level rate constant measurements and calculations where available for the reactions of DME. This mechanism is also the first to apply a pressure-dependent treatment to the low-temperature reactions of DME. It has been validated using available literature data including flow reactor, jet-stirred reactor, shock-tube ignition delay times, shock-tube speciation, flame speed, and flame speciation data. New ignition delay time measurements are presented for methane, dimethyl ether, and their mixtures; these data were obtained using three different shock tubes and a rapid compression machine. In addition to the DME/CH 4 blends, high-pressure data for pure DME and pure methane were also obtained. Where possible, the new * address:

The low-temperature oxidation of n-heptane, one of the reference species for the octane rating of gasoline, was investigated using a jet-stirred reactor and two methods of analysis: gas chromatography and synchrotron vacuum ultra-violet photo-ionization mass spectrometry (SVUV-PIMS) with direct sampling through a molecular jet. The second method allowed the identification of products, such as molecules with hydroperoxy functions, which are not stable enough to be detected using gas chromatography. Mole fractions of the reactants and reaction products were measured as a function of temperature (500-1100K), at a residence time of 2s, at a pressure of 800 torr (1.06 bar) and at stoichiometric conditions. The fuel was diluted in an inert gas (fuel inlet mole fraction of 0.005). Attention was paid to the formation of reaction products involved in the low temperature oxidation of n-heptane, such as olefins, cyclic ethers, aldehydes, ketones, species with two carbonyl groups (diones) and ketohydroperoxides. Diones and ketohydroperoxides are important intermediates in the low temperature oxidation of n-alkanes but their formation have rarely been reported. Significant amounts of organic acids (acetic and propanoic acids) were also observed at low temperature. The comparison of experimental data and profiles computed using an automatically generated detailed kinetic model is overall satisfactory. A route for the formation of acetic and propanoic acids was proposed. Quantum calculations were performed to refine the consumption routes of ketohydroperoxides towards diones.

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An understanding of the ignition and oxidation characteristics of propanol, as well as other alcohols, is important toward the development and design of combustion engines that can effectively utilize bioderived and bioblended fuels. Building upon a database for “first-generation” alcohols including methanol and ethanol, the ignition characteristics of the two isomers of propanol (n-propanol and iso-propanol) have been studied in a shock tube. Ignition delay times for propanol/oxygen/argon mixtures have been measured behind reflected shock waves at temperatures ranging from approximately 1350 to 2000 K and a pressure of 1 atm. Equivalence ratios of 0.5, 1.0, and 2.0 have been used. Pressure measurements and CH* emissions were used to determine ignition delay times. The influences of equivalence ratio, temperature, and mixture strength on ignition delay have been characterized and compared to the behavior seen with a newly developed detailed kinetic mechanism. The overall trends are captured fairly well by the mechanism, which include a greater level of reactivity for the n-propanol mixtures relative to iso-propanol at the conditions used in this study.

The experimental study of the oxidation of cyclohexane has been performed in a jet-stirred reactor at temperatures ranging from 500 to 1100 K (low-and intermediate temperature zones including the negative temperature-coefficient area), at a residence time of 2 s and for dilute mixtures with equivalence ratios of 0.5, 1, and 2. Experiments were carried out at quasi-atmospheric pressure (1.07 bar). The fuel and reaction product mole fractions were measured using online gas chromatography. A total of 34 reaction products have been detected and quantified in this study. Typical reaction products formed in the low-temperature oxidation of cyclohexane include cyclic ethers (1,2-epoxycyclohexane and 1,4-epoxycyclohexane), 5-hexenal (formed from the rapid decomposition of 1,3-epoxycyclohexane), cyclohexanone, and cyclohexene, as well as benzene and phenol. Cyclohexane displays high low-temperature reactivity with well-marked negative temperature-coefficient (NTC) behavior at equivalence ratios 0.5 and 1. The fuel-rich system (ϕ = 2) is much less reactive in the same region and exhibits no NTC. To the best of our knowledge, this is the first jet-stirred reactor study to report NTC in cyclohexane oxidation. Laminar burning velocities were also measured by the heated burner method at initial gas temperatures of 298, 358, and 398 K and at 1 atm. The laminar burning velocity values peak at ϕ = 1.1 and are measured as 40 and 63.1 cm/s for T i = 298 and 398 K, respectively. An updated detailed chemical kinetic model including low-temperature pathways was used to simulate the present (jet-stirred reactor and laminar burning velocity) and literature experimental (laminar burning velocity, rapid compression machine, and shock tube ignition delay times) data. Reasonable agreement is observed with most of the products observed in our reactor, as well as the literature experimental data considered in this paper.

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Alkanes such as methane, ethane, and propane make up a large portion of most natural gas fuels. Natural gas is the primary fuel used in industrial gas turbines for power generation. Because of this, a fundamental understanding of the physical characteristics such as the laminar flame speed is necessary. Most importantly, this information is needed at elevated pressures to have the most relevance to the gas turbine industry for engine design. This study includes experiments performed at elevated pressures, up to 10 atm initial pressure, and investigates the fuels in a pure form as well as in binary blends. Flame speed modeling was done using an improved version of the kinetics model that the authors have been developing over the past few years. Modeling was performed for a wide range of conditions, including elevated pressures. Experimental conditions include pure methane, pure ethane, 80/20 mixtures of methane/ethane, and 60/40 mixtures of methane/ethane at initial pressures of 1 atm, 5 atm, and 10 atm. Also included in this study are pure propane and 80/20 methane/propane mixtures at 1 atm and 5 atm. The laminar flame speed and Markstein length measurements were obtained from a high-pressure flame speed facility using a constant-volume vessel. The facility includes optical access, a high-speed camera, a schlieren optical setup, a mixing manifold, and an isolated control room. The experiments were performed at room temperature, and the resulting images were analyzed using linear regression. The experimental and modeling results are presented and compared with previously published data. The data herein agree well with the published data. In addition, a hybrid correlation was created to perform a rigorous uncertainty analysis. This correlation gives the total uncertainty of the experiment with respect to the true value rather than reporting the standard deviation of a repeated experiment. Included in the data set are high-pressure results at conditions where in many cases for the single-component fuels few data existed and for the binary blends no data existed prior to this study. Overall, the agreement between the model and data is excellent.

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