Diamex process for minor actinide partitioning: Hydrolytic and radiolytic degradations of malonamide extractants

This paper deals with the hydrolysis and radiolysis of malonamides, which a re used as extractants in the DIAMEX process for partitioning minor actinid es from high-level liquid radioactive wastes. The general formula of the ma lonamides included in this study is as follows: (R(R')NCO)(2)CHR" (where R, R', and R" are alkyl or oxyalkyl groups). Qualitative tests were carried o ut to identify malonamide degradation products using gas chromatography (GC ) coupled to Fourier transform infrared spectroscopy (FTIR) or mass spectro metry (MS). The main degradation products were identified in organic phases after radiolysis or hydrolysis in the presence of the nitric acid aqueous phase and quantified using potentiometric titrations and gas chromatography . From the experimental data, a simplified degradation scheme for malonamid e radiolysis and hydrolysis is proposed. The extracting properties of solve nts made of malonamide solutions in an aliphatic diluent vs. actinide(III) and lanthanide(III) nitrates were determined after radiolysis and hydrolysi s. The presence of malonamide degradation products leads to a decrease of t he M(III) distribution ratios. Experiments carried out with synthetic organ ic solutions show that the decrease in solvent extraction properties can be explained by the decrease of the malonamide concentration and by the prese nce of the main malonamide degradation products. The hydrolytic and radioly tic stabilities of several malonamides are compared.