Diglycolamides have emerged as an interesting class of extractants for actinide partitioning from high-level waste (HLW). N,N,N´,N´-tetraoctyl diglycolamide (TODGA) has been extensively studied for lanthanide-actinide co-extraction behavior. The present work deals with a branched isomer of TODGA, that is, N,N,N´, N´-tetra(2-ethylhexyl) diglycolamide (TEHDGA). TEHDGA was studied for the extraction of 241 Am and third-phase formation. The effect of using different phase modifiers on the prevention of the formation of a third phase during nitric acid extraction by TEHDGA along with the acid uptake behavior by TEHDGA in the presence of the modifiers was studied. The modifiers used for this purpose were di (n-hexyl)octanamide (DHOA), isodecanol, and n-decanol. The effect of the modifiers on the uptake of 241 Am as a function of acid concentration and as a function of modifier concentration was also examined. DHOA was found to be a suitable modifier, in spite of its high acid uptake. The uptake of lanthanides Ce, La, Eu, Gd, and Nd and elements such as Fe, Ni, Mn, Mo, Ru, Sr, and Cs with DHOA-modified TEHDGA-n-dodecane solvent systems were investigated. The results obtained indicated that, while DHOA-modified TEHDGA/n-dodecane extracted lanthanides and actinides, it did not show any significant uptake of other elements. Thus, the TEHDGA-DHOA/n-dodecane solvent system can be used effectively for the partitioning of lanthanides and actinides from HLW.

N,N,N ,N -tetra(2-ethylhexyl)diglycolamide (TEHDGA) was found to be a promising extractant for actinide partitioning from high-level waste (HLW) (Part I). In order to evaluate the applicability of TEHDGA to the HLW partitioning process, investigations on its radiolytic stability were carried out. The present work deals with the studies on the uptake of americium by γ -irradiated 0.2 M TEHDGA/n-dodecane in the absence and presence of phase modifiers-di(n-hexyl)octanamide (DHOA), isodecanol and n-decanol-against the absorbed dose up to 1 × 10 6 Gy in the presence of nitric acid at varying concentrations. The addition of phase modifiers suppressed the radiolysis of TEHDGA in n-dodecane and DHOA was found to be the most effective radiolysis suppressor. Investigations were also carried out on the degradation of neat TEHDGA by γ -irradiation, and it was attempted to isolate and identify its degradation products by instrumental analysis. The radiolysis study showed that the degradation products were formed by the cleavage of the -C-N bond, to eliminate an ethylhexyl group, and the bond adjacent to the ether bond. The results obtained for TEHDGA radiolysis were compared with that of its straight-chain isomer TODGA, and TEHDGA was observed to be more resistant to radiation than TODGA. The changes in the physico-chemical properties of γ -irradiated TEHDGA against the absorbed dose were also investigated.

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The retention behaviour of uranium, thorium, americium and lanthanides has been investigated, using a reverse phase C 18 column modified with 2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (n-Pr-BTP) with the aim of investigating rapid lanthanide-actinide separations by HPLC technique. Nitric acid and α-hydroxy isobutyric acid (α-HIBA) have been employed as the mobile phase. The influence of mobile phase pH and concentration on the retention of metal ions has been studied. The aim of this study is to investigate the use of BTP coated reverse phase columns as analytical columns for the fast separation of the minor actinides from the lanthanides in the high-level waste (HLW), and to explore whether such columns can be used on a preparative scale for the purification and the recovery of minor actinides from the high-level waste (HLW).It was observed that reverse phase columns modified with BTP showed greater affinity for actinides but exhibited no retention for lanthanides and the lanthanide-actinide separations could be achieved in nitric acid mobile phase, without the need for complexing agents. Americium was separated from the lanthanides with good peak profile and baseline resolution in both nitric acid as well as α-HIBA as the mobile phase. Based on this, the separation of americium from the lanthanides in the HLW was also demonstrated. The retention of a significant amount of thorium by the column in breakthrough studies also indicated that these columns can be used for preparative scale purification of the actinides.