The applicability of 2,6-bis[1-(propan-1-ol)-1,2,3-triazol-4-yl)]pyridine (PyTri-Diol) in the innovative Selective ActiNide EXtraction (i-SANEX) process as water-soluble complexing agent was studied. Preliminary batch experiments were aimed at identifying the optimal formulation of the PyTri-Diol solution and at preparing the ground for single-stage centrifugal contactor experiments. A N,N,N′,N′ tetraoctyl diglycolamide (TODGA)-based solvent loaded using a spiked synthetic Plutonium and Uranium Reduction EXtraction raffinate and the optimized PyTri-Diol aqueous phase were contacted in a single-stage annular centrifugal contactor setup with three different flow-rate conditions. No hydrodynamic problems were encountered, and promising minor actinide separation from other cations was achieved with satisfactory kinetics and stage efficiency. The flow sheet of a TODGA–PyTri-Diol-based i-SANEX process was designed exploiting batch and single-stage data, promoting the CHON compliant PyTri-Diol as excellent alternative to the formerly used SO3–Ph–BTP.
The “CHON” compatible water-soluble ligand 3,3′-(pyridine-2,6-diylbis(1H-1,2,3-triazole-4,1-diyl))bis(propan-1-ol) (PTD) has shown promise for selectively stripping actinide ions from an organic phase containing both actinide and lanthanide ions, by preferential complexation of the former. Aiming at improving its complexation properties, PTD-OMe was synthesized, bearing a methoxy group on the central pyridine ring, thus increasing its basicity and hence complexation strength. Unfortunately, solvent extraction experiments in the range of 0.1–1 mol/L nitric acid proved PTD-OMe to be less efficient than PTD. This behavior is explained by its greater pKa value (pKa = 2.54) compared to PTD (pKa = 2.1). This counteracts its improved complexation properties for Cm(III) (log β3(PTD-OMe) = 10.8 ± 0.4 versus log β3(PTD) = 9.9 ± 0.5).
13 October 2018 in Journal of Radioanalytical and Nuclear Chemistry