In situ electro-oxidation and liquid-liquid extraction of cerium(IV) from nitric acid medium using tributyl phosphate and 2-ethylhexyl hydrogen 2-ethylhexyl phosphonate

The process of in situ electro-oxidation of Ce(III) to Ce(IV) followed by its extraction into the organic phase has been investigated for its applicability in the separation of Ce from nitrate medium. Solvent extraction of cerium from nitric acid after its electro-oxidation to fourth valency state was carried out using tributyl phosphate (TBP) and 2-ethylhexyl hydrogen 2-ethylhexyl phosphonate (KSM-17, equivalent to PC-88A). The efficiency of the extractants at different aqueous phase nitric acid concentrations and different electrode potentials were determined. Various reducing agents such as hydroxylamine hydrochloride, sodium nitrite, ferrous sulphate as well as complexing agents like EDTA, oxalic acid etc. were studied as strippants for the back extraction of cerium from the loaded organic phase. The method developed for the extraction of cerium was further extended to the partitioning of cerium from Ce-Am mixture obtained during the KSM-17 based extraction chromatographic elemental fractionation of PUREX High Activity Waste (HAW) solutions. Recovery of Ce obtained in the extraction experiments by batch as well as by continuous flow organic phase was >95% with good radiochemical purity.