Structure Based Predictive Model for Coal Char Combustion

This unique collaborative project has taken a very fundamental look at the origin of structure, and combustion reactivity of coal chars. It was a combined experimental and theoretical effort involving three universities and collaborators from universities outside the U.S. and from U.S. National Laboratories and contract research companies. The project goal was to improve our understanding of char structure and behavior by examining the fundamental chemistry of its polyaromatic building blocks. The project team investigated the elementary oxidative attack on polyaromatic systems, and coupled with a study of the assembly processes that convert these polyaromatic clusters to mature carbon materials (or chars). We believe that the work done in this project has defined a powerful new science-based approach to the understanding of char behavior. The work on aromatic oxidation pathways made extensive use of computational chemistry, and was led by Professor Christopher Hadad in the Department of Chemistry at Ohio State University. Laboratory experiments on char structure, properties, and combustion reactivity were carried out at both OSU and Brown, led by Principle Investigators Joseph Calo, Robert Essenhigh, and Robert Hurt. Modeling activities were divided into two parts: first unique models of crystal structure development were formulated by the team at Brown (PI'S Hurt and Calo) with input from Boston University and significant collaboration with Dr. Alan Kerstein at Sandia and with Dr. Zhong-Ying chen at SAIC. Secondly, new combustion models were developed and tested, led by Professor Essenhigh at OSU, Dieter Foertsch (a collaborator at the University of Stuttgart), and Professor Hurt at Brown. One product of this work is the CBK8 model of carbon burnout, which has already found practical use in CFD codes and in other numerical models of pulverized fuel combustion processes, such as EPRI's NOxLOI Predictor. The remainder of the report consists of detailed technical discussion organized into chapters whose organization is dictated by the nature of the research performed. Chapter 2 is entitled 'Experimental Work on Char Structure, Properties, and Reactivity', and focuses on fundamental structural studies at Brown using both phenollformaldehyde resin chars as model carbons and real coal chars. This work includes the first known in site high resolution TEM studies of carbonization processes, and some intriguing work on 'memory loss', a form of interaction between annealing and oxidation phenomena in chars. Chapter 3 entitled 'Computational Chemistry of Aromatic Oxidation Pathways' presents in detail the OSU work targeted at understanding the elementary molecular pathways of aromatic oxidation. Chapter 4 describes the 'Mesoscale Structural Models', using a combination of thermodynamic (equilibrium) approaches based on liquid crystal theory and kinetic simulations accounting for the effects of limited layer mobility in many fossil fuel derived carbons containing cross-linking agents. Chapter 5 entitled 'Combustion Modeling' presents work on extinction in the late stages of combustion and the development and features of the CBK8 model