Synergistic Extraction of Dysprosium and Aggregate Formation in Solvent Extraction Systems Combining TBP and HDBP

Anderson, Timothy L.; Braatz, Alex; Ellis, Ross J.; Antonio, Mark R.; Nilsson, Mikael

doi:10.1080/07366299.2013.787023

Synergistic Extraction of Dysprosium and Aggregate Formation in Solvent Extraction Systems Combining TBP and HDBP

Journal Article · Thu Sep 05 04:00:00 EDT 2013 · Solvent Extraction and Ion Exchange

DOI:https://doi.org/10.1080/07366299.2013.787023· OSTI ID:1454603

Anderson, Timothy L. ^[1]; Braatz, Alex ^[2]; Ellis, Ross J. ^[3]; Antonio, Mark R. ^[3]; Nilsson, Mikael ^[2]

Univ. of California, Irvine, CA (United States). Dept. of Chemical Engineering and Materials Science; UC Berkeley
Univ. of California, Irvine, CA (United States). Dept. of Chemical Engineering and Materials Science
Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division

During treatment of nuclear fuel in the Plutonium/URanium EXtraction (PUREX) process, the extractant tri-n-butyl phosphate (TBP) is known to degrade to dibutylphosphoric acid (HDBP), which increases the extraction of metal ions, thereby inhibiting their stripping from the organic phase. To better understand this phenomenon, we investigated how mixtures of TBP and HDBP influenced the extraction of metal, nitric acid, and water, and correlated the results to aggregated structures in the organic phase. The mole ratios of TBP-HDBP mixtures had a non-linear effect on the extraction of Dy³⁺ and water from 0.2 M HNO₃, indicating synergism. In 2 M HNO₃, the TBP:HDBP mole ratio had a more linear relation to Dy³⁺ and water extraction, so the synergistic effect was less pronounced than in the low acid system. The extraction of nitric acid showed no synergistic effect and follows closely what would be expected in a system using TBP only. The small-angle X-ray scattering (SAXS) data of the 0.2 M acid system showed maximum contrast at a TBP:HDBP mole ratio of 0.25, so that the synergistic mixture is also the most aggregated at 0.2 M acid. The 2 M acid system also showed that the mixed system is more aggregated than the end members, although this does not result in peak extraction. Previous studies of synergistic extraction of metal cations explain the enhanced extraction by increased dehydration of the metal ion. Although our data do not rule out the formation of mixed complexes according to the classical mechanism of synergism, our evidence of increased water extraction and aggregate formation in systems combining TBP and HDBP are complementary to the metal-centric dehydration aspects of the process. The findings in this study give insights into the complex chemistry of solvent extraction, thus providing a possible link between formation of aggregates in the organic phase and synergistic extraction.

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of California, Irvine, CA (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE). Nuclear Energy University Program; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

DOE Contract Number:: NE0000156; AC02-06CH11357

OSTI ID:: 1454603

Journal Information:: Solvent Extraction and Ion Exchange, Journal Name: Solvent Extraction and Ion Exchange Journal Issue: 6 Vol. 31; ISSN 0736-6299

Publisher:: Taylor and Francis

Country of Publication:: United States

Language:: English

References (37)

Review Article: The Effects of Radiation Chemistry on Solvent Extraction: 1. Conditions in Acidic Solution and a Review of TBP Radiolysis Mincher, Bruce J.; Modolo, Giuseppe; Mezyk, Stephen P. Solvent Extraction and Ion Exchange, Vol. 27, Issue 1 https://doi.org/10.1080/07366290802544767	journal	January 2009
Solvent Penetration and Sterical Stabilization of Reverse Aggregates based on the DIAMEX Process Extracting Molecules: Consequences for the Third Phase Formation Berthon, L.; Martinet, L.; Testard, F. Solvent Extraction and Ion Exchange, Vol. 25, Issue 5 https://doi.org/10.1080/07366290701512576	journal	August 2007
Aggregation in Solvent Extraction Systems Containing a Malonamide, a Dialkylphosphoric Acid and their Mixtures Antonio, M. R.; Chiarizia, R.; Gannaz, B. Separation Science and Technology, Vol. 43, Issue 9-10 https://doi.org/10.1080/01496390802121537	journal	July 2008
THE NOVEL EXTRACTANTS, DIGLYCOLAMIDES, FOR THE EXTRACTION OF LANTHANIDES AND ACTINIDES IN HNO ₃ – n -DODECANE SYSTEM Sasaki, Yuji; Sugo, Yumi; Suzuki, Shinichi Solvent Extraction and Ion Exchange, Vol. 19, Issue 1 https://doi.org/10.1081/SEI-100001376	journal	January 2001
Supramolecular organisation of tri-n-butyl phosphate in organic diluent on approaching third phase transition Nave, S.; Mandin, C.; Martinet, L. Physical Chemistry Chemical Physics, Vol. 6, Issue 4 https://doi.org/10.1039/b311702b	journal	January 2004
X-ray solution scattering (SAXS) combined with crystallography and computation: defining accurate macromolecular structures, conformations and assemblies in solution Putnam, Christopher D.; Hammel, Michal; Hura, Greg L. Quarterly Reviews of Biophysics, Vol. 40, Issue 3 https://doi.org/10.1017/S0033583507004635	journal	August 2007
Distribution ratios and empirical equations for the extraction of elements in Purex high level waste solution—II: HDEHP Svantesson, I.; Persson, G.; Hagström, I. Journal of Inorganic and Nuclear Chemistry, Vol. 42, Issue 7 https://doi.org/10.1016/0022-1902(80)80397-6	journal	January 1980
Aggregation, reversed micelles, and microemulsions in liquid-liquid extraction: the tri-n-butyl phosphatediluent-water-electrolyte system Osseo-Asare, K. Advances in Colloid and Interface Science, Vol. 37, Issue 1-2 https://doi.org/10.1016/0001-8686(91)80041-H	journal	November 1991
Some aspects of synergism in solvent extraction—II Zangen, M. Journal of Inorganic and Nuclear Chemistry, Vol. 25, Issue 8 https://doi.org/10.1016/0022-1902(63)80041-X	journal	August 1963
Review: Solvent Systems Combining Neutral and Acidic Extractants for Separating Trivalent Lanthanides from the Transuranic Elements Lumetta, Gregg J.; Gelis, Artem V.; Vandegrift, George F. Solvent Extraction and Ion Exchange, Vol. 28, Issue 3 https://doi.org/10.1080/07366291003684253	journal	April 2010
SANS Study of HCl Extraction by Selected Neutral Organophosphorus Compounds in n -Octane Chiarizia, R.; Stepinski, D.; Antonio, M. R. Separation Science and Technology, Vol. 45, Issue 12-13 https://doi.org/10.1080/01496395.2010.493828	journal	July 2010
Extraction of Cerium(IV) Nitrate by Butyl Phosphate Warf, James C. Journal of the American Chemical Society, Vol. 71, Issue 9 https://doi.org/10.1021/ja01177a528	journal	September 1949
Studies on the Partitioning of Actinides from high Level Waste Using a Mixture of Hdehp and cmpo as Extractant Dhami, P. S.; Chitnis, R. R.; Gopalakrishnan, V. Separation Science and Technology, Vol. 36, Issue 2 https://doi.org/10.1081/SS-100001082	journal	December 2001
Complex Formation between Tributyl Phosphate and Nitric Acid and the Hydration of the Complexes in Dodecane Naganawa, Hirochika; Tachimori, Shoichi Bulletin of the Chemical Society of Japan, Vol. 70, Issue 4 https://doi.org/10.1246/bcsj.70.809	journal	April 1997
MODIFICATION OF TODGA- n -DODECANE SOLVENT WITH A MONOAMIDE FOR HIGH LOADING OF LANTHANIDES(III) AND ACTINIDES(III) Tachimori, Shoichi; Sasaki, Yuji; Suzuki, Shin-ichi Solvent Extraction and Ion Exchange, Vol. 20, Issue 6 https://doi.org/10.1081/SEI-120016073	journal	January 2002
Purex Process for Plutonium and Uranium Recovery Lanham, W. B.; Runion, T. C. https://doi.org/10.2172/4165457	report	October 1949
Third Phase Formation Revisited: The U(VI), HNO ₃ –TBP, n ‐Dodecane System Chiarizia, R.; Jensen, M. P.; Borkowski, M. Solvent Extraction and Ion Exchange, Vol. 21, Issue 1 https://doi.org/10.1081/SEI-120017545	journal	January 2003
Complex formation in the dilute uranyl nitrate-nitric acid-dibutyl phosphoric acid-tributyl phosphate-Amsco system Hahn, H. T.; Vander Wall, E. M. Journal of Inorganic and Nuclear Chemistry, Vol. 26, Issue 1 https://doi.org/10.1016/0022-1902(64)80245-1	journal	January 1964
SANS Study of Third Phase Formation in the Extraction of HCl by TBP Isomers in n ‐Octane Chiarizia, R.; Stepinski, D. C.; Thiyagarajan, P. Separation Science and Technology, Vol. 41, Issue 10 https://doi.org/10.1080/01496390600742716	journal	June 2006
Design and performance of a ASAXS instrument at the Advanced Photon Source Seifert, S.; Winans, R. E.; Tiede, D. M. Journal of Applied Crystallography, Vol. 33, Issue 3 https://doi.org/10.1107/S0021889800001333	journal	June 2000
The Extraction of Uranium(VI) with DBP in the Presence of TBP. The "Synergic" Effect: Substitution or Addition?. Dyrssen, David; Kuča, Libor; Hansen, S. E. Acta Chemica Scandinavica, Vol. 14 https://doi.org/10.3891/acta.chem.scand.14-1945	journal	January 1960
Synergic effects in the solvent extraction of the actinides—I uranium(VI) Irving, H.; Edgington, D. N. Journal of Inorganic and Nuclear Chemistry, Vol. 15, Issue 1-2 https://doi.org/10.1016/0022-1902(60)80024-3	journal	September 1960
Extraction of Lanthanides(III) and Am(III) by Mixtures of Malonamide and Dialkylphosphoric Acid Gannaz, Benoît; Chiarizia, Renato; Antonio, Mark R. Solvent Extraction and Ion Exchange, Vol. 25, Issue 3 https://doi.org/10.1080/07366290701285512	journal	April 2007
The Actinide—Lanthanide Analogy as Exemplified by Solvent Extraction Behavior Peppard, D. F.; Gray, P. R.; Markus, M. M. Journal of the American Chemical Society, Vol. 75, Issue 23 https://doi.org/10.1021/ja01119a528	journal	December 1953
Third-Phase Formation in the Extraction of Phosphotungstic Acid by TBP in n -Octane Antonio, Mark R.; Chiarizia, Renato; Jaffrennou, Fanny Separation Science and Technology, Vol. 45, Issue 12-13 https://doi.org/10.1080/01496395.2010.493793	journal	July 2010
Enhanced Solvent Extraction with Water-in-Ok Microemulsions Osseo-asare, K. Separation Science and Technology, Vol. 23, Issue 12-13 https://doi.org/10.1080/01496398808075629	journal	October 1988
Synergistic Solvent Extraction of Trivalent Americium and Europium by 2-Bromodecanoic acid and Neutral Nitrogen-Containing Reagents Hagström, I.; Spjuth, L.; Enarsson, Ȧ. Solvent Extraction and Ion Exchange, Vol. 17, Issue 2 https://doi.org/10.1080/07366299908934610	journal	March 1999
Studies on mono- and di-n-butylphosphoric acids—II The solubility and distribution of mono- and di-n-butylphosphoric acids in aqueous-organic solvent systems Hardy, C. J.; Scargill, D. Journal of Inorganic and Nuclear Chemistry, Vol. 11, Issue 2 https://doi.org/10.1016/0022-1902(59)80057-9	journal	September 1959
Standard and advanced separation: PUREX processes for nuclear fuel reprocessing Herbst, R. S.; Baron, P.; Nilsson, M. Advanced Separation Techniques for Nuclear Fuel Reprocessing and Radioactive Waste Treatment https://doi.org/10.1533/9780857092274.2.141	book	January 2011
Aggregation in Organic Solutions of Malonamides: Consequences for Water Extraction Meridiano, Y.; Berthon, L.; Crozes, X. Solvent Extraction and Ion Exchange, Vol. 27, Issue 5-6 https://doi.org/10.1080/07366290903270148	journal	December 2009
Sulfonic Acids: Catalysts for the Liquid-Liquid Extraction of Metals Osseo-asare, K.; Keeney, M. E. Separation Science and Technology, Vol. 15, Issue 4 https://doi.org/10.1080/01496398008076283	journal	May 1980
Effect of TBP on Extraction of REE and TPE from Nitric Acid Solutions with Dibutylphosphoric Acid and Its Zirconium Salt Shmidt, O. V.; Zilberman, B. Ya.; Fedorov, Yu. S. Radiochemistry, Vol. 45, Issue 6 https://doi.org/10.1023/B:RACH.0000015758.53065.64	journal	November 2003
Third Phase Formation in the Extraction of Inorganic Acids by TBP in n ‐Octane Chiarizia, Renato; Briand, Alexandra Solvent Extraction and Ion Exchange, Vol. 25, Issue 3 https://doi.org/10.1080/07366290701285397	journal	April 2007
Coordination Structures and Supramolecular Architectures in a Cerium(III)–Malonamide Solvent Extraction System Ellis, Ross J.; Antonio, Mark R. Langmuir, Vol. 28, Issue 14 https://doi.org/10.1021/la3002916	journal	March 2012
Purification of di-(2-ethylhexyl)phosphoric acid by precipitation of copper(II) di-(2-ethylhexyl)phosphate Partridge, J. A.; Jensen, R. C. Journal of Inorganic and Nuclear Chemistry, Vol. 31, Issue 8 https://doi.org/10.1016/0022-1902(69)80591-9	journal	August 1969
Small-angle scattering. Information content and error analysis Moore, P. B. Journal of Applied Crystallography, Vol. 13, Issue 2 https://doi.org/10.1107/S002188988001179X	journal	April 1980
The extraction of nitrates by tri-n-butyl phosphate (TBP). Part 1.—The system TBP + Diluent + H ₂ O+HNO ₃ Alcock, K.; Grimley, S. S.; Healy, T. V. Trans. Faraday Soc., Vol. 52, Issue 0 https://doi.org/10.1039/tf9565200039	journal	January 1956

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