STRUCTURE-BASED PREDICTIVE MODEL FOR COAL CHAR COMBUSTION

During the past quarter of this project, significant progress continued was made on both major technical tasks. Progress was made at OSU on advancing the application of computational chemistry to oxidative attack on model polyaromatic hydrocarbons (PAHs) and graphitic structures. This work is directed at the application of quantitative ab initio molecular orbital theory to address the decomposition products and mechanisms of coal char reactivity. Previously, it was shown that the hybrid B3LYP method can be used to provide quantitative information concerning the stability of the corresponding radicals that arise by hydrogen atom abstraction from monocyclic aromatic rings. In the most recent quarter, these approaches have been extended to larger carbocyclic ring systems, such as coronene, in order to compare the properties of a large carbonaceous PAH to that of the smaller, monocyclic aromatic systems. It was concluded that, at least for bond dissociation energy considerations, the properties of the large PAHs can be modeled reasonably well by smaller systems. In addition to the preceding work, investigations were initiated on the interaction of selected radicals in the radical pool with the different types of aromatic structures. In particular, the different pathways for addition vs. abstraction to benzene and furan by H and OH radicals were examined. Thus far, the addition channel appears to be significantly favored over abstraction on both kinetic and thermochemical grounds. Experimental work at Brown University in support of the development of predictive structural models of coal char combustion was focused on elucidating the role of coal mineral matter impurities on reactivity. An inverse approach was used where a carbon material was doped with coal mineral matter. The carbon material was derived from a high carbon content fly ash (Fly Ash 23 from the Salem Basin Power Plant. The ash was obtained from Pittsburgh #8 coal (PSOC 1451). Doped samples were then burned in a high temperature flame reactor fitted with rapid quench extractive sampling. It was found that the specific reaction rate decreased with increasing ash content by about an order of magnitude over the ash content range investigated. In this case, it was concluded that at least one of the primary reasons for the resultant observation was that an increasing amount of carbon becomes inaccessible to oxygen by being covered with a fused, protective, ash layer. Progress continued on equipment modification and testing for the combustion experiments with widely varying flame types at OSU