Abstracts Chemistry

A Detailed Chemical Kinetic Modeling of Nitrogen Containing Fuel Oxidation

by Mohammad Ashraful Alam

Nitrogen-containing organic fuels i.e., Methylamine (CH3NH2), Dimethylamine (CH3NHCH3), Ethylamine (CH3CH2NH2), and/or solvent i.e., 2-aminoethanol (NH2CH2CH2OH) are the most common aliphatic amines extensively used in the chemical, petrochemical, energy industries, or carbon capture technology in natural gas or coal power plant. In the oxidation or combustion process, these organic fuels or solvents are released into the atmosphere as a form of hazardous compounds e.g., NH3, CO2, NOx, or volatile organic compounds (VOCs) which leads to the formation of nitramine and nitrosamines in the atmospheric oxidation process. In recent decades, the number of kinetic models of nitrogen base amine fuel combustion has been elucidated in a wide range of gas phases and supercritical water conditions. Although extensive experiment or computational research evaluated the number of intermediates and products including identified the relation to environmental degradation products, a detailed understanding of major nitrogen containing intermediates contributing to NH3, CO2, NOx, and N2 formation are still lacking, as well as has not been well demonstrated the efficiency of hydroperoxy radical reaction chemistry. A detailed analysis and understanding in-sight into the combustion or oxidation process of these nitrogen containing organic fuels or solvent are important to elucidate the mechanism by which these hazardous or polluant compounds are formed and may be achieved through a refined or developed reaction kinetic model. In this dissertation, peroxy radical chemistry and its role in nitrogen-based organic fuel combustion or solvent degradation in supercritical water or gas phase conditions have been thoroughly investigated. This work also investigated the formation of an imine and decomposition reaction followed by hydrolysis reaction chemistry. This dissertation proposed new reaction sets which have been computationally tested and validated against several experiments under a variety of conditions, for instance, fuel equivalence ratios, temperature, and concentrations of diluent gas, which have simultaneously described the importance of new reactions set in the combustion model of nitrogen containing fuels oxidation and degradation in the gas phase and supercritical water condition.