Hexavalent Actinide Extraction Using N,N-Dialkyl Amides

McCann, Kevin; Mincher, Bruce J.; Schmitt, Nicholas C.; Braley, Jenifer C.

doi:10.1021/acs.iecr.7b01181

Title: Hexavalent Actinide Extraction Using N,N-Dialkyl Amides

Journal Article · Mon May 15 00:00:00 EDT 2017 · Industrial and Engineering Chemistry Research

DOI:https://doi.org/10.1021/acs.iecr.7b01181· OSTI ID:1471062

McCann, Kevin ^[1];

^[2];

^[1]

Colorado School of Mines, Golden, CO (United States)
Idaho National Lab. (INL), Idaho Falls, ID (United States)

Recently, efforts towards closing the nuclear fuel cycle have considered oxidizing americium to a hexavalent, linear-dioxo cation for co-recovery with hexavalent U, Np, and Pu from molar nitric acid using solvating extraction ligands such as tri-n-butyl phosphate or diamyl amylphosphonate. This work assesses solvent extraction recovery of sodium bismuthate oxidized americium by N,N-di-(2-ethylhexyl)butyramide (DEHBA), N,N-di-(2-ethylhexyl)isobutyramide (DEHiBA), and N,N-dihexyloctanamide (DHOA). Extraction efficiency between the monoamides was found to increase in the order of DEHiBA < DHOA < DEHBA. For all monoamides, oxidized americium extraction was less than 50% from 4 M HNO₃ and below. Extraction efficiency above 50% was obtained using concentrations of 5 M HNO₃ or higher. The DEHBA extractant provided the highest distribution value of 5.4 at 7 M HNO₃. Distribution values were found to be stable for up to 45 seconds aqueous/organic phase mixing times and indicated decreased reduction of hexavalent americium relative to separations completed with organophosphorus extractants. The simultaneous co-extraction of U, Np, Pu, and Am was demonstrated using DEHiBA, and was found to decrease with increasing atomic number (D_U > D_Np > D_Pu > D_Am). Interestingly, a break in recovery was observed where ligher actinides, U and Np, were better recovered relative to the heavier actinides, Pu and Am, in this study. This observation seems to be related to differences in the extracted metal complex for light actinides compared to heavy actinides. In conclusion, the metal:ligand stoichiometry was found to be mixed 1:1 and 1:2 species for U and Np while Pu and Am displayed 1:2 stoichiometry.

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Research Organization:: Idaho National Lab. (INL), Idaho Falls, ID (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE), Fuel Cycle Technologies (NE-5)

Grant/Contract Number:: AC07-05ID14517

OSTI ID:: 1471062

Report Number(s):: INL/JOU-17-41507-Rev000

Journal Information:: Industrial and Engineering Chemistry Research, Vol. 56, Issue 22; ISSN 0888-5885

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 32 works

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References (20)

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Cited By (4)

Relationship Between Structure and Coordination Strength of N and N,O -Hybrid Donor Ligands with Trivalent Lanthanides Nakase, Masahiko; Kobayashi, Tohru; Shiwaku, Hideaki Solvent Extraction and Ion Exchange, Vol. 36, Issue 7 https://doi.org/10.1080/07366299.2018.1532137	journal	November 2018
Development of a Selective Americium Separation Process Using H ₄ TPAEN as Water-Soluble Stripping Agent Marie, Cécile; Kaufholz, Peter; Vanel, Vincent Solvent Extraction and Ion Exchange, Vol. 37, Issue 5 https://doi.org/10.1080/07366299.2019.1643569	journal	July 2019
Extraction of uranium from carbonate solution using synthesized Schiff base and its application for spectrophotometric determination Orabi, Ahmed H. Chemical Papers, Vol. 73, Issue 7 https://doi.org/10.1007/s11696-019-00724-x	journal	February 2019
Inner versus outer sphere metal-monoamide complexation: ramifications for tetravalent & hexavalent actinide selectivity McCann, Kevin; Sinkov, Sergey I.; Lumetta, Gregg J. New Journal of Chemistry, Vol. 42, Issue 7 https://doi.org/10.1039/c7nj04851c	journal	January 2018

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