(646g) Atr Reforming Of Tetradecane (C14H30): A Mechanistic Explanation For Hydrogen And Carbon Formation

A computational kinetic study was completed to elucidate the mechanism by which tetradecane is converted to hydrogen in an autothermal reforming process. A reaction mechanism was developed to capture the major reactions, which was then validated using experimental data. Heterogeneous reactions for Tetradecane conversion were estimated using a simplified transition state calculation. Subsequent reactions were extracted from published C7 mechanistic work. The mechanism was capable of reproducing the trends for all species measured greater than 0.15 mole%. The concentrations calculated for reactor temperatures from 750^oC to 900^oC were typically less than one order of magnitude of the experimental data over a range of space velocities. A sensitivity study was performed to identify the reaction classes that most influenced product formation. The significance of each major reaction class as the reaction proceeded through the reactor was considered. Our analysis determined the tetradecane reaction sequence starts with oxidation and cracking reactions, with oxidation contributing 30% toward reactant conversion. While the catalyst serves to initiate the reaction mechanism, a mixture of gas phase and surface reactions occur throughout the reactor. Steam reforming was not found to be a significant reaction. Instead, hydrogen production is primarily the result of partial oxidation and water gas shift reactions. The water gas shift reaction was found to be the dominant reaction consuming of water. Finally, a qualitative pathway toward carbon formation was also identified as a result.