Theoretical evaluation on selective adsorption characteristics of alkali metal-based sorbents for gaseous oxidized mercury.

Alkali metal-based sorbents are potential for oxidized mercury (Hg(2+)) selective adsorption but show hardly effect to elemental mercury (Hg(0)) in flue gas. Density functional theory (DFT) was employed to investigate the Hg(0) and HgCl2 adsorption mechanism over alkali metal-based sorbents, including calcium oxide (CaO), magnesium oxide (MgO), potassium chloride (KCl) and sodium chloride (NaCl). Hg(0) was found to weakly interact with CaO (001), MgO (001), KCl (001) and NaCl (001) surfaces while HgCl2 was effectively adsorbed on top-O and top-Cl sites. Charge transfer and bond population were calculated to discuss the covalency and ionicity of HgCl2 bonding with the adsorption sites. The partial density of states (PDOS) analysis manifests that HgCl2 strongly interacts with surface sites through the orbital hybridizations between Hg and top O or Cl. Frontier molecular orbital (FMO) energy and Mulliken electronegativity are introduced as the quantitative criteria to evaluate the reactivity of mercury species and alkali metal-based sorbents. HgCl2 is identified as a Lewis acid and more reactive than Hg(0). The Lewis basicity of the four alkali metal-based sorbents is predicted as the increasing order: NaCl < MgO < KCl < CaO, in consistence with the trend of HgCl2 adsorption energies.