Concentrating Rare Earth Elements from Coal Fly Ash Leachates Using Ligand-Associated Organosilica Media

Rare earth elements (REEs) have many critical uses in advanced technology and the lack of a reliable domestic supply has been identified by the US DOE as a vulnerability to US economic security. Our research focuses on developing an economical process for extracting REEs from coal fly ash and power plant wastewater sludge by coupling a hydrothermal extraction process with the engineering of a ligand-associated media for concentrating REEs from the extraction liquid. Ash samples have been collected from two Detroit-area Power plants that burn 100% low sulfur coal (Trenton Channel) or fuel blends of 75% low sulfur coal and 25% high sulfur coal or 70% low sulfur coal, 15% high sulfur coal, and 15% petcoek (Monroe Power Plant). Ash samples are then subjected to hydrothermal conditions from 100-350 °C for 1-24 h at Los Alamos National Laboratory and leachate concentrations are measured by inductively coupled plasma-mass spectroscopy (ICP-MS) and compared to hydrofluoric acid digestion results. Experiments designed to aid in ligand selection and loading optimization show that di-(2-ethylhexyl)methanediphosphonic acid (H2DEH or DIPEX™) can be successfully loaded to a commercially available swellable organically modified silica (SOMS) media. Preliminary results show that DIPEX-associated SOMS surface loading can exceed 4x on a mass/mass basis and in simplified sorption experiments with Nd solutions (~pH 2), the DIPEX-SOMS media can sorb >90 mg Nd per g of media. Recovery of the sorbed Nd with low pH solutions has had low efficiency with the high (4 g DIPEX/ g dry media); however, near complete recovery was achieved with lower surface loadings (0.05 g DIPEX/ g dry media). Column experiments are being conducted to evaluate the optimal ligand/media ratio for repeated use. Completive sorption with Fe and other major cations are also being evaluated.