To develop an advanced partitioning process by extraction chromatography using a minimal organic solvent and compact

The solvent extraction of trivalent actinides and lanthanides from aqueous 1M NaNO 3 by the sulfur containing acidic extractant Cyanex 301 was studied. This commercial extractant shows very interesting features for An(III)/Ln(III) separations depending on the purification of its main constituent bis(2,2,4-trimethylpentyl)dithiophosphinic acid. Efficient separations were observed with nonpurified Cyanex 301 for high Ln(III) concentrations, but not for low Ln(III) concentrations. Successful purification of Cyanex 301 was performed by precipitation of the ammonium dithiophosphinate. Very high An(III)/Ln(III) separation factors (higher than 103) were obtained for micro or macro concentrations of Ln(III) at pH 3 4.

New aromatic dithiophosphinic acids (R 2PSSH) with R = C6H 5 -, CIC 6 fi.l-, FC 6H4-and CH3C6H4-were synthesized, characterized and tested as potential separating agents for trivalent actinides over lanthanides. The extraction of Am(III), Eu(III) and other lanthanides was carried out from nitric acid medium with mixtures of R 2PSSHs and neutral organophosphorus compounds. There was no detectable extraction when R 2PSSHs were used alone as extractants for either Am(III) or Eu(III) (DAm,Ell < 10-3 ) under the experimental conditions used in this study. High separation factors (DAm/D Ell > 20) with DAm > I were achieved in the nitric acid range 0.1 -I mol/L by means of a synergistic mixture of bis(chlorophenyl)dithiophosphinic acid + tributylphosphate (TBP), trioctylphosphine oxide (TOPO) or tributylphosphine oxide (TBPO). The high radiation resistance (up to 10 6 Gy absorbed y-doses) of the extractants was also demonstrated.

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