Abstract
Separation of neptunium by solvent extraction has been based on tributylphosphate (TBP) for decades, but TBP is not fully incinerable, which adds to the burden of long-lived radioactive waste. Alternatives to TBP for uranium and plutonium extraction, such as the N,N-diakylamides, previously have been explored in the hopes of transitioning to an extractant that is incinerable. Four N,N-diakylamides, N,N-dihexylhexanamide (DHHA), N,N-dihexyloctanamide (DHOA), N,N-di(2-ethylhexyl)butanamide (DEHBA), and N,N-di(2-ethylhexyl)-iso-butanamide (DEHiBA) were considered in this work for their potential to extract millimolar concentrations of Np(IV), Np(V), and Np(VI) from nitric acid solutions into organic solutions containing 1 M extractant in Exxsol D60. Under these conditions the branching of the alkyl substituents affects the extractability of Np(VI) and Np(IV), causing three of the dialkylamides, DHHA, DHOA and DEHBA, to extract neptunium in the expected order Np(VI) > Np(IV) > > Np(V). In contrast, branched DEHiBA is so poor an extractant for Np(IV) that the extraction order becomes Np(VI) > > Np(V) > Np(IV) between 0.1 and 5.6 M HNO3 due to partial oxidation of the Np(V) in nitric acid.
Acknowledgements
This work is supported by U.S. Department of Energy Offices of Nuclear Energy and Environmental Management under the Radiochemistry Traineeship program at the Colorado School of Mines. The work at the Idaho National Laboratory was performed under contract DE-AC07-05ID14517, in part supported by the Fuel Cycle Research and Development Program, Office of Nuclear Energy, U.S. Department of Energy. We gratefully thank Santa Jansone-Popova for the important insight to dialkylamide synthesis and Laetitia Delmau and David DePaoli for useful discussions on neptunium extraction.
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