Neptunium extraction by N,N-dialkylamides

Gogolski, Jarrod M.; Zalupski, Peter R.; Grimes, Travis S.; Jensen, Mark P.

doi:10.1515/ract-2020-0002

Neptunium extraction by N,N-dialkylamides

Journal Article · Sat Apr 18 00:00:00 EDT 2020 · Radiochimica Acta

DOI:https://doi.org/10.1515/ract-2020-0002· OSTI ID:1668706

Gogolski, Jarrod M. ^[1]; Zalupski, Peter R. ^[2]; Grimes, Travis S. ^[2]; Jensen, Mark P. ^[1]

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

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. Furthermore, 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.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Environmental Management (EM); USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: AC07-05ID14517

OSTI ID:: 1668706

Alternate ID(s):: OSTI ID: 22947484

Report Number(s):: INL/JOU--20-58897-Rev000

Journal Information:: Radiochimica Acta, Journal Name: Radiochimica Acta Journal Issue: 9 Vol. 108; ISSN 0033-8230

Publisher:: de GruyterCopyright Statement

Country of Publication:: United States

Language:: English

References (45)

Determination of plutonium oxidation states at trace levels pertinent to nuclear waste disposal Nitsche, H.; Lee, S. C.; Gatti, R. C. Journal of Radioanalytical and Nuclear Chemistry Articles, Vol. 124, Issue 1 https://doi.org/10.1007/BF02035515	journal	September 1988
Redox Behavior of Neptunium(V) in Tributyl Phosphate and N,N-Dihexyl Octanamide Extractants Dissolved in n-Dodecane Pathak, P. N.; Kumari, Neelam; Prabhu, D. R. Journal of Solution Chemistry, Vol. 41, Issue 3 https://doi.org/10.1007/s10953-012-9807-6	journal	March 2012
Solubility of tributyl phosphate and its degradation products in concentrated uranyl nitrate solutions and of uranyl nitrate in tributyl phosphate at elevated temperatures Usachev, V. N.; Markov, G. S. Radiochemistry, Vol. 46, Issue 5 https://doi.org/10.1007/s11137-005-0012-y	journal	September 2004
Studies on mono- and di-n-butylphosphoric acids—III The extraction of zirconium from nitrate solution by di-n-butylphosphoric acid Hardy, C. J.; Scargill, D. Journal of Inorganic and Nuclear Chemistry, Vol. 17, Issue 3-4 https://doi.org/10.1016/0022-1902(61)80160-7	journal	June 1961
Absorption spectra of Np(III), (IV), (V) and (VI) in nitric acid solution Friedman, H. A.; Toth, L. M. Journal of Inorganic and Nuclear Chemistry, Vol. 42, Issue 9 https://doi.org/10.1016/0022-1902(80)80298-3	journal	January 1980
Recent progress in the extraction chemistry of actinide ions Schulz, W. W.; Horwitz, E. P. Journal of the Less Common Metals, Vol. 122 https://doi.org/10.1016/0022-5088(86)90401-7	journal	August 1986
The radiolysis of dodecane-tributylphosphate solutions Holland, J. P.; Merklin, J. F.; Razvi, J. Nuclear Instruments and Methods, Vol. 153, Issue 2-3 https://doi.org/10.1016/0029-554X(78)91011-X	journal	July 1978
The oxidation of neptunium(IV) by nitric acid in 100% TBP and diluted TBP/n-dodecane solutions Taylor, R. J.; Koltunov, V. S.; Savilova, O. A. Journal of Alloys and Compounds, Vol. 271-273 https://doi.org/10.1016/S0925-8388(98)00225-4	journal	June 1998
Emission probabilities of the main γ-rays of 237Np in equilibrium with 233Pa Luca, A.; Etcheverry, M.; Morel, J. Applied Radiation and Isotopes, Vol. 52, Issue 3 https://doi.org/10.1016/S0969-8043(99)00198-0	journal	March 2000
Determination of low level Np-237 by various techniques Benedik, L.; Trdin, M. Applied Radiation and Isotopes, Vol. 126 https://doi.org/10.1016/j.apradiso.2017.02.005	journal	August 2017
Third phase formation studies in the extraction of Th(IV) and U(VI) by N,N-dialkyl aliphatic amides Jha, R. K.; Gupta, K. K.; Kulkarni, P. G. Desalination, Vol. 232, Issue 1-3 https://doi.org/10.1016/j.desal.2007.11.054	journal	November 2008
Reduction of Np(VI) in Irradiated Solutions of Nitric Acid Precek, Martin; Paulenova, Alena; Mincher, Bruce J. Procedia Chemistry, Vol. 7 https://doi.org/10.1016/j.proche.2012.10.010	journal	January 2012
Hexavalent Actinide Extraction Using N , N -Dialkyl Amides McCann, Kevin; Mincher, Bruce J.; Schmitt, Nicholas C. Industrial & Engineering Chemistry Research, Vol. 56, Issue 22 https://doi.org/10.1021/acs.iecr.7b01181	journal	May 2017
Structures of Plutonium(IV) and Uranium(VI) with N , N -Dialkyl Amides from Crystallography, X-ray Absorption Spectra, and Theoretical Calculations Acher, Eléonor; Hacene Cherkaski, Yanis; Dumas, Thomas Inorganic Chemistry, Vol. 55, Issue 11 https://doi.org/10.1021/acs.inorgchem.6b00592	journal	May 2016
Neptunium Recovery and Purification at Hanford Isaacson, R. E.; Judson, B. F. Industrial & Engineering Chemistry Process Design and Development, Vol. 3, Issue 4 https://doi.org/10.1021/i260012a003	journal	October 1964
EFFECTS OF STRUCTURE OF N,N-DISUBSTITUTED AMIDES ON THEIR EXTRACTION OF ACTINIDE AND ZIRCONIUM NITRATES AND OF NITRIC ACID ¹ Siddall, T. H. The Journal of Physical Chemistry, Vol. 64, Issue 12 https://doi.org/10.1021/j100841a014	journal	December 1960
Stabilities of +4 and +5 Oxidation States of the Actinide Elements—the Np(IV)-Np(V) Couple ¹ in Perchloric Acid Solution Magnusson, L. B.; Huizenga, J. R. Journal of the American Chemical Society, Vol. 75, Issue 9 https://doi.org/10.1021/ja01105a064	journal	May 1953
Oxidation-Reduction Reactions of Neptunium(IV) and -(V) ¹ Huizenga, John R.; Magnusson, Lawrence B. Journal of the American Chemical Society, Vol. 73, Issue 7 https://doi.org/10.1021/ja01151a061	journal	July 1951
Kinetics of HNO ₂ Catalyzed Oxidation of Neptunium(V) by Aqueous Solutions of Nitric Acid ¹ Siddall, T. H.; Dukes, E. K. Journal of the American Chemical Society, Vol. 81, Issue 4 https://doi.org/10.1021/ja01513a007	journal	May 1959
Ligands for f-element extraction used in the nuclear fuel cycle Leoncini, Andrea; Huskens, Jurriaan; Verboom, Willem Chemical Society Reviews, Vol. 46, Issue 23 https://doi.org/10.1039/C7CS00574A	journal	January 2017
Inner to outer-sphere coordination of plutonium( iv ) with N,N-dialkyl amide: influence of nitric acid Acher, Eléonor; Dumas, Thomas; Tamain, Christelle Dalton Transactions, Vol. 46, Issue 12 https://doi.org/10.1039/C7DT00031F	journal	January 2017
Radiolytic stability of N , N -dialkyl amide: effect on Pu( iv ) complexes in solution Drader, J. A.; Boubals, N.; Camès, B. Dalton Transactions, Vol. 47, Issue 1 https://doi.org/10.1039/C7DT03447D	journal	January 2018
Comparison of Extraction Behavior of Neptunium from Nitric Acid Medium Employing Tri- n -Butyl Phosphate and N,N -dihexyl Octanamide as Extractants Kumari, Neelam; Pathak, P. N.; Prabhu, D. R. Separation Science and Technology, Vol. 47, Issue 10 https://doi.org/10.1080/01496395.2011.653034	journal	June 2012
Application of N, N-Dialkyl Aliphatic amides in the Separation of Some Actinides Casparini, G. M.; Grossi, G. Separation Science and Technology, Vol. 15, Issue 4 https://doi.org/10.1080/01496398008076273	journal	May 1980
Synthesis and uses of the Amides Extractants Thiollet, G.; Musikas, C. Solvent Extraction and Ion Exchange, Vol. 7, Issue 5 https://doi.org/10.1080/07360298908962339	journal	January 1989
Radiolytic Degradation Studies on N,N‐dihexyloctanamide (DHOA) under PUREX Process Conditions Parikh, K. J.; Pathak, P. N.; Misra, S. K. Solvent Extraction and Ion Exchange, Vol. 27, Issue 2 https://doi.org/10.1080/07366290802672303	journal	March 2009
Review Article long Chain Disubstituted Aliphatic Amides as Extracting Agents in Industrial Applications of Solvent Extraction Gasparini, Giulio Maria; Grossi, Giuseppe Solvent Extraction and Ion Exchange, Vol. 4, Issue 6 https://doi.org/10.1080/07366298608917921	journal	January 1986
Progress towards the Full Recovery of Neptunium in an Advanced PUREX Process Taylor, R. J.; Gregson, C. R.; Carrott, M. J. Solvent Extraction and Ion Exchange, Vol. 31, Issue 4 https://doi.org/10.1080/07366299.2013.800438	journal	July 2013
Distribution Behavior of Neptunium by Extraction with N,N -dialkylamides (DEHDMPA and DEHBA) in Mixer-Settler Extractors Ban, Yasutoshi; Hotoku, Shinobu; Tsutsui, Nao Solvent Extraction and Ion Exchange, Vol. 34, Issue 1 https://doi.org/10.1080/07366299.2015.1130423	journal	December 2015
Simulation of Neptunium Extraction in an Advanced PUREX Process—Model Improvement Chen, Hongyan; Taylor, Robin J.; Jobson, Megan Solvent Extraction and Ion Exchange, Vol. 35, Issue 1 https://doi.org/10.1080/07366299.2016.1273684	journal	January 2017
Radiation chemistry of the branched-chain monoamide di-2-ethylhexyl-isobutyramide Drader, J.; Saint-Louis, G.; Muller, J. M. Solvent Extraction and Ion Exchange, Vol. 35, Issue 7 https://doi.org/10.1080/07366299.2017.1379713	journal	September 2017
The Extraction by N.N-Dialkylamides. ii. Extraction of Actinide Cations Condamines, N.; Musikas, C. Solvent Extraction and Ion Exchange, Vol. 10, Issue 1 https://doi.org/10.1080/07366299208918093	journal	February 1992
Comparing Branched versus Straight-chained Monoamide Extractants for Actinide Recovery McCann, Kevin; Drader, Jessica A.; Braley, Jenifer C. Separation & Purification Reviews, Vol. 47, Issue 1 https://doi.org/10.1080/15422119.2017.1321018	journal	May 2017
Interfacial Tension Studies of N , N ‐Dialkyl Amides Vidyalakshmi, V.; Subramanian, M. S.; Rajeswari, S. Solvent Extraction and Ion Exchange, Vol. 21, Issue 3 https://doi.org/10.1081/SEI-120020218	journal	January 2003
Di(2‐Ethylhexyl) Pivalamide (D2EHPVA): A Promising Extractant for Selective Removal of Uranium from High Level Nuclear Waste Solutions Manchanda, V. K.; Pathak, P. N.; Rao, Ashwin K. Solvent Extraction and Ion Exchange, Vol. 22, Issue 3 https://doi.org/10.1081/SEI-120030396	journal	December 2004
N,N -Dihexyl Hexanamide: A Promising Extractant for Nuclear Fuel Reprocessing Gupta, K. K.; Manchanda, V. K.; Subramanian, M. S. Separation Science and Technology, Vol. 35, Issue 10 https://doi.org/10.1081/SS-100100243	journal	January 2000
Kinetics of neptunium(V) reduction with iron(II) sulfamate in nitric acid solutions Baranov, A. A.; Erin, E. A.; Nagaitseva, L. V. Radiochemistry, Vol. 56, Issue 1 https://doi.org/10.1134/S1066362214010020	journal	January 2014
Distribution of Neptunium between TBP and Some Mineral Acids Ishimori, Tomitaro; Nakamura, Eiko Bulletin of the Chemical Society of Japan, Vol. 32, Issue 7 https://doi.org/10.1246/bcsj.32.713	journal	July 1959
Distribution Behavior of U(VI), Pu(IV), Am(III), and Zr(IV) with N,N-Dihexyl Octanamide under Uranium-Loading Conditions Manchanda, V. K.; Ruikar, P. B.; Sriram, S. Nuclear Technology, Vol. 134, Issue 3 https://doi.org/10.13182/NT01-A3198	journal	June 2001
Separation of neptunium from actinides by monoamides: a solvent extraction study Mahanty, Bholanath; Kanekar, Avinash S.; Ansari, Seraj A. Radiochimica Acta, Vol. 107, Issue 5 https://doi.org/10.1515/ract-2018-3074	journal	May 2019
Extraction of Np(IV), Np(VI), Pu(IV) and U(VI) with Amides, BEHSO and CMPO from Nitric Acid Medium Mathur, J. Ν.; Ruikar, P. Β.; Balarama Krishna, M. V. ract, Vol. 73, Issue 4 https://doi.org/10.1524/ract.1996.73.4.199	journal	August 1996
Thermodynamics of Extraction of Uranium(VI) and Plutonium(IV) with some Long-chain Aliphatic Amides Gupta, K. K.; Manchanda, V. K.; Subramanian, M. S. Radiochimica Acta, Vol. 85, Issue 3-4 https://doi.org/10.1524/ract.1999.85.34.103	journal	January 1999
A spectroscopic study of the hydrolysis, colloid formation and solubility of Np(IV) Neck, Volker; Kim, J. I.; Seidel, B. S. Radiochimica Acta, Vol. 89, Issue 7 https://doi.org/10.1524/ract.2001.89.7.439	journal	July 2001
The redox chemistry of neptunium in γ -irradiated aqueous nitric acid Mincher, Bruce J.; Precek, Martin; Mezyk, Stephen P. Radiochimica Acta, Vol. 101, Issue 4 https://doi.org/10.1524/ract.2013.2013	journal	April 2013
Separation Chemistry for the Nuclear Industry Musikas, Claude; Condamines, Nicole; Cuillerdier, Christine Analytical Sciences, Vol. 7, Issue Supple https://doi.org/10.2116/analsci.7.Supple_11	journal	January 1991

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