Highly efficient solid phase extraction of uranium with TOPO-menthol based eutectic solvent as stationary phase from acidic feed relevant to front-end applications

Abstract

Novel methods of separation and purification are envisaged for natural uranium, containing 0.7% of fissile 235U, a precious resource that fuels nuclear power plants. The present study demonstrates Solid phase extraction (SPE) of uranium as a sustainable alternative to conventional liquid-liquid extraction, leading to minimisation of organic inventory and enhancement of ease of operation concerning usage of viscous eutectic solvent. Overcoming the issue of the low solubility of organophosphorus extractant tri-octyl phosphine oxide (TOPO) in a hydrocarbon diluent, the aqueous insoluble, non-ionic eutectic solvent could be prepared with biodegradable menthol having TOPO: menthol mole ratio of 1:2 (MT2), 1:3 (MT3) and 1:4 (MT4). Eutectic solvents were sorbed on radio chemically stable Chromosorb W resin as solid support (MTC2, MTC3, MTC4), with loading of 45% for MTC2 and 40% for both MTC3 and MTC4, confirmed by weight difference and thermogravimetry. Batch sorption studies of U(VI) from nitric acid medium revealed attainment of equilibrium at 60 min., following a pseudo-second-order rate equation, Langmuir adsorption isotherm and a static capacity of 19 mg g−1. The U(VI) uptake was found to increase with the increase in acid molarity indicating solvating mechanism of extraction (KD = 1240 ± 4, 4 M HNO3). Recyclability was established and stripping was effective with 0.5 M HNO3. Column operation was also successfully demonstrated (breakthrough capacity = 18.9 mg g−1). The U(VI) uptake of >98% was indicated for nitric acid-digested crude yellow cake matrices viz. sodium diuranate (SDU), magnesium diuranate (MDU) and heat-treated uranium peroxide (HTUP). For higher matrix content, near complete uranium uptake and suppression of extraction of representative impurities (Fe, Mn, Ni, Ce) was revealed indicating facile uranium separation and purification from matrices relevant to the front end of the nuclear fuel cycle.