Separation of uranium from different uranium oxide matrices employing supercritical carbon dioxide extraction

Uranium from different uranium oxide matrices was extracted with tri-n-butyl phosphate-nitric acid (TBP-HNO3) adduct using supercritical carbon dioxide (SC CO2). While 30 min dissolution time at 323 K was sufficient for U3O8 and UO2 powder, UO2 granule (at 333 K) and crushed green pellet (at 353 K) required 40 min. Crushed sintered pellet required 60 min at 353 K for complete dissolution. Influence of various experimental parameters such as temperature, pressure, volume of TBP-HNO3 adduct, acidity of nitric acid used for preparing TBP-HNO3 adduct and extraction time on uranium extraction efficiency was also investigated. For UO2 powder, temperature of 323 K, pressure of 15.2 MPa, 1 mL TBP-HNO3 adduct, 10 M nitric acid and 30 min extraction time was found to be optimum. similar to 70% uranium extraction efficiency was obtained on extraction with SC CO2 alone which increased to 90% with the addition of 2.5% TBP in SC CO2 stream. Extraction efficiency was found to vary linearly with TBP percentage and nearly complete uranium extraction (similar to 99%) was observed with 20% TBP. Nearly complete extraction was also achieved with addition of 2.5% thenoyltrifluoroacetylacetone (TTA) in methanol. The optimized procedure was extended to remove uranium from simulated tissue paper waste matrix smeared with uranium oxide solids.