Role of Activated Carbon Precursor for Mercury Oxidation and Removal: Oxidized Surface and Carbene Site Interaction

Abstract

Activated carbon (AC) is widely accepted for the removal of inorganic contaminants like mercury; however, the raw material used in the production of activated carbon is not always taken into consideration when evaluating its efficacy. Mercury oxidation and adsorption mechanisms governed by carbene sites are more likely to occur when graphitic-like activated carbons (such as those produced from high-ranking coals) are employed versus lignocellulosic-based ACs; this is likely due to the differences in carbon structures where lignocellulosic materials are less aromatic. In this research, the team studied bituminous coal-based ACs in comparison to coconut shell and wood-based (both less aromatic) ACs for elemental mercury removal. Nitric acid of 0.5 M, 1 M, and 5 M concentrations along with 10 M hydrogen peroxide were used to oxidize the surface of the ACs. Boehm titrations and FTIR analysis were used to quantify the addition of functional groups on the activated carbons. A trend was observed herein, resulting in increasing nitric acid molarity and an increased quantity of oxygen-containing functional groups. Gas-phase mercury removal mechanisms including physisorption, oxygen functional groups, and carbene sites were evaluated. The results showed significantly better elemental mercury removal in the gas phase with a bituminous coal-based AC embodying similar physical and chemical characteristics to that of its coconut shell-based counterpart. The ACs treated with various oxidizing agents to populate oxygen functional groups on the surface showed increased mercury removal. It is hypothesized that nitric acid treatment creates oxygen functional groups and carbene sites, with carbene sites being more responsible for mercury removal. Heat treatments post-oxidation with nitric acid showed remarkable results in mercury removal. This process created free carbene sites on the surface and shows that carbene sites are more reactive to mercury adsorption than oxygen. Overall, physisorption and oxygen functional groups were also dismissed as mercury removal mechanisms, leaving carbene-free sites as the most compelling mechanism.