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Title: Thermodynamic Studies to Support Actinide/Lanthanide Separations

Abstract

Thermodynamic data on the complexation of Np(V) with HEDTA in a wide pH region were re-modeled by including a dimeric complex species, (NpO 2) 2(OH) 2L 2 6- where L 3- stands for the fully deprotonated HEDTA ligand and better fits were achieved for the spectrophotometric data. The presence of the dimeric complex species in high pH region was verified for the first time by the EXAFS experiments at Stanford Synchrotron Radiation Laboratory (SSRL).

Authors:
 [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1306332
Report Number(s):
LBNL-1006035
ir:1006035; TRN: US1601813
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; HEDTA; NEPTUNIUM OXIDES; DIMERS; LIGANDS; THERMODYNAMIC PROPERTIES; NEPTUNIUM COMPLEXES

Citation Formats

Rao, Linfeng. Thermodynamic Studies to Support Actinide/Lanthanide Separations. United States: N. p., 2016. Web. doi:10.2172/1306332.
Rao, Linfeng. Thermodynamic Studies to Support Actinide/Lanthanide Separations. United States. doi:10.2172/1306332.
Rao, Linfeng. Sun . "Thermodynamic Studies to Support Actinide/Lanthanide Separations". United States. doi:10.2172/1306332. https://www.osti.gov/servlets/purl/1306332.
@article{osti_1306332,
title = {Thermodynamic Studies to Support Actinide/Lanthanide Separations},
author = {Rao, Linfeng},
abstractNote = {Thermodynamic data on the complexation of Np(V) with HEDTA in a wide pH region were re-modeled by including a dimeric complex species, (NpO2)2(OH)2L26- where L3- stands for the fully deprotonated HEDTA ligand and better fits were achieved for the spectrophotometric data. The presence of the dimeric complex species in high pH region was verified for the first time by the EXAFS experiments at Stanford Synchrotron Radiation Laboratory (SSRL).},
doi = {10.2172/1306332},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Sun Sep 04 00:00:00 EDT 2016},
month = {Sun Sep 04 00:00:00 EDT 2016}
}

Technical Report:

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  • This milestone report summarizes the data obtained in FY15 on the complexation of HEDTA with Np(V) and U(VI) in a temperature range from 25 to 70°C. The results show the effect of temperature on the chemical speciation of Np(V) and U(VI) in the modified TALSPEAK Process, and help to evaluate the effectiveness of the process when the operation envelope (e.g., temperature) varies. Eventually, the results from this study will help to achieve a better control of the separation process based on the HEDTA/HEH[EHP] combination.
  • The separation of An(III) ions from chemically similar Ln(III) ions is perhaps one of the most difficult problems encountered during the processing of nuclear waste. In the 3+ oxidation states, the metal ions have an identical charge and roughly the same ionic radius. They differ strictly in the relative energies of their f- and d-orbitals, and to separate these metal ions, ligands will need to be developed that take advantage of this small but important distinction. The extraction of uranium and plutonium from nitric acid solution can be performed quantitatively by the extraction with the TBP (tributyl phosphate). Commercially, thismore » process has found wide use in the PUREX (plutonium uranium extraction) reprocessing method. The TRUEX (transuranium extraction) process is further used to coextract the trivalent lanthanides and actinides ions from HLLW generated during PUREX extraction. This method uses CMPO [(N, N-diisobutylcarbamoylmethyl) octylphenylphosphineoxide] intermixed with TBP as a synergistic agent. However, the final separation of trivalent actinides from trivalent lanthanides still remains a challenging task. In TRUEX nitric acid solution, the Am(III) ion is coordinated by three CMPO molecules and three nitrate anions. Taking inspiration from this data and previous work with calix[4]arene systems, researchers on this project have developed a C3-symmetric tris-CMPO ligand system using a triphenoxymethane platform as a base. The triphenoxymethane ligand systems have many advantages for the preparation of complex ligand systems. The compounds are very easy to prepare. The steric and solubility properties can be tuned through an extreme range by the inclusion of different alkoxy and alkyl groups such as methyoxy, ethoxy, t-butoxy, methyl, octyl, t-pentyl, or even t-pentyl at the ortho- and para-positions of the aryl rings. The triphenoxymethane ligand system shows promise as an improved extractant for both tetravalent and trivalent actinide recoveries form high level liquid wastes and a general actinide clean-up procedure. The selectivity of the standard extractant for tetravalent actinides, (N,N-diisobutylcarbamoylmethyl) octylphenylphosphineoxide (CMPO), was markedly improved by the attachment of three CMPO-like functions onto a triphenoxymethane platform, and a ligand that is both highly selective and effective for An(IV) ions was isolated. A 10 fold excess of ligand will remove virtually all of the 4+ actinides from the acidic layer without extracting appreciable quantities of An(III) and Ln(III) unlike simple CMPO ligands. Inspired by the success of the DIAMEX industrial process for extractions, three new tripodal chelates bearing three diglycolamide and thiodiglycolamide units precisely arranged on a triphenoxymethane platform have been synthesized for an highly efficient extraction of trivalent f-element cations from nitric acid media. A single equivalent of ligand will remove 80% of the Ln(III) ion from the acidic layer since the ligand is perfectly suited to accommodate the tricapped trigonal prismatic geometry preferred by the metal center. The ligand is perhaps the most efficient binder available for the heavier lanthanides and due to this unique attribute, the extraction event can be easily followed by 1H NMR spectroscopy confirming the formation of a TPP complex. The most lipophilic di-n-butyl tris-diglycolamide was found to be a significantly weaker extractant in comparison to the di-isopropyl analogs. The tris-thiodiglycolamide derivative proved to be an ineffective chelate for f-elements and demonstrated the importance of the etheric oxygens in the metal binding. The results presented herein clearly demonstrate a cooperative action of these three ligating groups within a single molecule, confirmed by composition and structure of the extracted complexes, and since actinides prefer to have high coordination numbers, the ligands should be particularly adept at binding with three arms. The use of such an extractant permits the extraction of metal ions form highly acidic environment through the ability of the compound to buffer the effect of high acid concentration. Stability toward hydrolysis and ease of synthesis and purification are additional favorable properties. The ligands describe above based on the triphenoxymethane platform are not only easily available in large quantities but also amenable to nearly unlimited chemical modifications. Finally, with this platform, two highly effective ligands incorporating CMPO and glycoldiamide moieties have been prepared and fully characterized, and both examples are perhaps the most efficient and selective examples of these important classes of ligands. Continued refinements of these systems have the potentially further improve the selectivity and affinity for An(III) ions.« less
  • This project seeks to determine if inorganic or hybrid inorganic ion-exchange materials can be exploited to provide effective americium and curium separations. Specifically, we seek to understand the fundamental structural and chemical factors responsible for the selectivity of the tested ion-exchange materials for actinide and lanthanide ions. During FY13, experimental work focused in the following areas: (1) investigating methods to oxidize americium in dilute nitric acid with subsequent ion-exchange performance measurements of ion exchangers with the oxidized americium and (2) synthesis, characterization and testing of ion-exchange materials. Ion-exchange materials tested included alkali titanates, alkali titanosilicates, carbon nanotubes and group(IV) metalmore » phosphonates. Americium oxidation testing sought to determine the influence that other redox active components may have on the oxidation of Am(III). Experimental findings indicated that Pu(IV) is oxidized to Pu(VI) by peroxydisulfate, but there are no indications that the presence of plutonium affects the rate or extent of americium oxidation at the concentrations of peroxydisulfate being used. Tests also explored the influence of nitrite on the oxidation of Am(III). Given the formation of Am(V) and Am(VI) in the presence of nitrite, it appears that nitrite is not a strong deterrent to the oxidation of Am(III), but may be limiting Am(VI) by quickly reducing Am(VI) to Am(V). Interestingly, additional absorbance peaks were observed in the UV-Vis spectra at 524 and 544 nm in both nitric acid and perchloric acid solutions when the peroxydisulfate was added as a solution. These peaks have not been previously observed and do not correspond to the expected peak locations for oxidized americium in solution. Additional studies are in progress to identify these unknown peaks. Three titanosilicate ion exchangers were synthesized using a microwave-accelerated reaction system (MARS) and determined to have high affinities for lanthanide ions in dilute nitric acid. The K-TSP ion exchanger exhibited the highest affinity for lanthanides in dilute nitric acid solutions. The Ge-TSP ion exchanger shows promise as a material with high affinity, but additional tests are needed to confirm the preliminary results. On the other hand, carbon nanotubes and nitrogen-doped carbon nanotubes exhibited low, but measureable affinities for lanthanide ions in dilute nitric acid solutions (pH 3 and 6). The MWCNT exhibited much lower affinities than the K-TSP in dilute nitric acid solutions. However, the MWCNT are much more chemically stable in concentrated nitric acid solutions and, therefore, may be candidates for ion exchange in more concentrated nitric acid solutions.« less