Combustion of an Illinois No. 6 coal char simulated using an atomistic char representation and the ReaxFF reactive force field

Abstract Coal or biomass chars are complex carbonaceous materials that are important energy sources for electricity production. Reactive molecular dynamics simulations are a useful tool to examine the chemical reactions occurring in complex processes, providing that a realistic structural representation and an applicable reactive force field can be utilized. Combustion of coal (or biomass) char is one such area were additional insight would be helpful for utilization enhancements and pollution control. In this investigation a devolatilized Illinois No. 6 coal char atomistic representation was generated, using Fringe3D and additional Perl scripts, coupled with the ReaxFF reactive force field for hydrocarbon combustion. Fringe3D facilitates the char structure generation process by producing a distribution of aromatic structures based on HRTEM lattice fringe image analyses. Perl scripts were used for incorporating heteroatoms and aliphatic components to aid elimination of investigator bias, and facilitate a more rapid construction process. The char structure was constrained by a combination of elemental and NMR literature data. Chemical and physical parameters were found to be broadly consistent with the experimental data. The ReaxFF force field for hydrocarbon combustion was used to perform simulations to examine the structural transformations and chemical processes associated with char combustion. In this initial work, very high temperatures (3000–4000 K) were selected for ReaxFF simulation under stoichiometric, fuel lean and rich combustion conditions. These elevated temperatures were chosen to observe chemical reactions proceed to completion within a computationally practical simulation time. Analyses indicated that char oxidation process was primarily initialized by either thermal degradation of char structure to form small fragments, that were subsequently oxidized, or by hydrogen abstraction reactions by oxygen molecules and O and OH radicals. A more rapid oxidation and combustion of the polyaromatic structures occurred at fuel lean (oxygen rich) conditions compared with fuel rich combustion. Char transitions included 6-membered ring conversion into 5- and 7-membered rings that further decomposed or reacted with mostly O and OH radicals. This work further demonstrates the utility of ReaxFF force field integration with representative char structural models to investigate physical and chemical transformations of char structure during combustion at high-temperature conditions.