In this thesis, attention was paid to several novel oxygenated fuels—carbonates, polyethers and ketones. Combustion kinetic investigations were performed for typical representative compounds, including dimethyl carbonate, diethyl carbonate, cyclopentanone, 3-pentanone, 1,2-dimethoxyethane and dimethoxymethane. For experiments, suitable diagnostic techniques were used to measure the detailed speciation information of the target fuels under different conditions. For kinetic modeling, rate coefficients for crucial elementary reactions were obtained through high-level theoretical calculations. Based on that, validated kinetic models with good predictive performances were developed. On the basis of experimental measurements and model interpretations, this work highlighted two important combustion characteristics regarding the practical use: the pollutant formation and the ignition performance. Besides, the correlation between oxygen-containing functional groups and the aforementioned combustion characteristics was revealed. To reveal the potential interactions between the reaction networks of oxygenated additives and the hydrocarbon base fuels during combustion. Chemical structures of laminar premixed flames fueled by binary fuels were measured, and by changing the initial fuel compositions, the addition effects of the oxygenates on the fuel consumption and pollutant formation behaviors were explored. It was found that complicated chemical interactions do not exist in the reaction networks under the investigated conditions.

Supercritical carbon dioxide has brought about new questions on the chemical kinetics of several small hydrocarbon fuels and the effects of carbon dioxide as the primary diluent on the different fuels. This report presents work on the ignition delay times and several species time-histories of methane, ethylene and syngas over a range of conditions. All experiments were conducted behind reflected shock waves using two different shock tubes. The ignition delay times were measured using a GaP photodetector to measure the emission of light. The species time-histories were measured using single laser spectroscopy. The effect of CO2 as a diluent on the fluid dynamics of the system were also examined using high-speed camera images. It was determined that the ignition delay times and fuel time-histories were able to be accurately predicted by mechanisms in the literature for pressures up to 30 atm but the literature mechanisms were unable to predict the carbon monoxide time-histories beyond qualitative trends for the various fuels. It was also determined that the carbon monoxide had a string effect on the fluid dynamics of the experiments resulting in a significantly smaller chemical reaction zone. Experiments were also performed to examine the effects of water as a diluent with a ratio up to 66% of the total diluent on the ignition delay times. Using the experimental data, a global kinetic mechanism was created for methane and syngas to predict the ignition delay times and the carbon monoxide time-histories for pressures up to 300 atm.

Work supported by the Office of Standard Reference Data, National Bureau of Standards, Naval Sea Systems Command, Department of the Navy, and Division of Conservation, Research and Technology, Energy Research and Development Administration.

Mathematical Modelling of Gas-Phase Complex Reaction Systems: Pyrolysis and Combustion, Volume 45, gives an overview of the different steps involved in the development and application of detailed kinetic mechanisms, mainly relating to pyrolysis and combustion processes. The book is divided into two parts that cover the chemistry and kinetic models and then the numerical and statistical methods. It offers a comprehensive coverage of the theory and tools needed, along with the steps necessary for practical and industrial applications. Details thermochemical properties and "ab initio" calculations of elementary reaction rates Details kinetic mechanisms of pyrolysis and combustion processes Explains experimental data for improving reaction models and for kinetic mechanisms assessment Describes surrogate fuels and molecular reconstruction of hydrocarbon liquid mixtures Describes pollutant formation in combustion systems Solves and validates the kinetic mechanisms using numerical and statistical methods Outlines optimal design of industrial burners and optimization and dynamic control of pyrolysis furnaces Outlines large eddy simulation of turbulent reacting flows

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One method to access unconventional, heavy-oil and natural bitumen resources as well as waterflood residual oil is to apply in situ combustion (ISC) to oxidize in place a small fraction of the hydrocarbon thereby providing heat to reduce oil viscosity and pressure that enhances recovery. ISC is also attractive because it provides the opportunity to upgrade oil in-situ by increasing the API gravity and decreasing, for instance, sulfur content. Experimental analysis of crude-oil oxidation kinetics provides parameters, such as activation energy, for modeling and optimization of ISC processes. The complex nature of petroleum as a multi-component mixture and multi-step character of oxidation reactions complicates substantially the kinetic analysis of crude-oil. Isoconversional techniques provide model-free methods for estimating activation energy and naturally deconvolve multi-step reactions. In addition, isoconversional methods are also useful as a screening tool to recognize the burning characteristics of different oils. By using experimentally determined combustion kinetics of different oil samples along with combustion tube results, we show that isoconversional analysis of ramped temperature oxidation data is useful to predict combustion-front propagation. It also provides new insight into the nature of the reactions occurring during ISC. Ramped temperature oxidation (RTO) tests with effluent gas analysis are conducted to probe ISC reaction kinetics along with isothermal coke formation experiments. The role of oxygen during coke formation reactions (i.e., fuel formation for ISC) is investigated using X-ray photoelectron spectroscopy (XPS) of intermediate reaction products. The XPS data is analyzed along with companion RTO experiments to obtain a simplified multi-step reaction scheme. Synthetic cases illustrate the connection between a proposed reaction scheme for oil/matrix pairs and one-dimensional combustion front propagation. Analysis of experimental results illustrate that the reaction scheme is capable of reproducing experimental results including the basic trends in oxygen consumption and carbon oxides production for RTO experiments as a function of heating rate for both good and poor ISC candidates. The combination of XPS and RTO studies indicates that the quality (or reactivity) of coke formed during the process is a function of oxygen presence/absence.