Investigation of the Adsorption Behavior of Organic Sulfur in Coal via Density Functional Theory (DFT) Calculation and Molecular Simulation

In this paper, we have investigated the chemical adsorption behavior of O2 on five types of organic sulfur (thiol, sulfoxide, thioether, sulfone, and thiophene) in polycyclic aromatic hydrocarbon (PAH) sheets using density functional theory (DFT) calculations. Here, the adsorption energy of O2-organic sulfur exceeds that of O2-PAH. Sulfone tends to be more favorable for oxidation reactions than other organic sulfur compounds and PAH by energy gap and deformation charge density analyses. A large charge transfer occurs between O2 and organic sulfur compounds by charge analysis. A radical distribution function (RDF) analysis shows that O2/CO2/N2 is preferentially adsorbed on nitrogen/sulfur/oxygen-containing functional groups in coal. To inhibit the reaction of sulfur-containing coal with oxygen, the physical adsorption of pure gas (CO2/O2/N2) and binary mixed gases (CO2 + O2/N2 + O2/CO2 + N2) is conducted at different temperatures and geological depths using molecular dynamics (MD) and grand canonical Monte Carlo (GCMC) simulations. The adsorption capacities of five types of organic sulfur with respect to the pure gases decrease with increasing temperature and increase with increasing depth. For O2/CO2, CO2/N2, and O2/N2 binary gas systems, the order with respect to adsorption amount is CO2 > O2 > N2. The factor of adsorption capacities is also evaluated, and the results show that pore volume plays a key role in adsorption behavior