Fission product interactions with nitrogen donor ligands used for spent nuclear fuel treatment

The so called BTBP (bis-triazine bi-pyridine)-type molecules have been developed for liquid-liquid extraction in the advanced reprocessing of used nuclear fuel. One solvent composition that has proven to be promising for such an application is the combination of CyMe4-BTBP and tri-butyl phosphate (TBP) in cyclohexanone. This solvent can extract the actinides successfully but unfortunately some fission products are also co-extracted. One of the most problematic fission products is palladium, but silver and cadmium are also extracted by the proposed solvent, which has been investigated here. In this study it was found that CyMe4-BTBP in cyclohexanone, when extracting palladium from nitric acid, forms complexes that are soluble both in the organic and aqueous phase. The predominant complex observed in both phases established with mass spectrometry and confirmed by NMR is a 1:1 complex, contrary to silver that forms 2:2 complexes and cadmium that forms 1:2 complexes. The nitrate dependency of the palladium extraction from nitric acid into a BTBP containing organic phase was found to be two. However, with higher ionic strengths, such as under process conditions, the palladium was found to be salted out into the organic phase. (C) 2012 Elsevier Ltd. All rights reserved.