Water Soluble PDCA Derivatives for Selective Ln(III)/An(III) and Am(III)/Cm(III) Separation

The synthesis and solvent extraction behavior of dipicolinic acid (pyridine-2,6-dicarboxylic acid, PDCA) and their derivatives have been studied for possible use in selective back-extraction of actinides, especially americium. The extraction was performed from an organic phase containing a mixture of trivalent actinides and lanthanides pre-extracted with N,N,N’,N’-tetraoctyl diglycolamide (TODGA). The efficiency of the back-extraction was enhanced when the picolinate platform was used in a heterocyclic decadentate ligand called h₄tpaen. Beyond selective An/Ln extraction, the aqueous soluble h₄tpaen ligand seemed a potential reagent for an intra-group Am(III)/Cm(III) separation with a separation factor SF_Cm/Am of about 3.5.     

Novel Diglycolamic Acid Functionalized Iron Oxide Particles for the Mutual Separation of Eu(III) and Am(III)

Iron oxide (Fe₃O₄) particles functionalized with diglycolamic acid (Fe-DGAH) were synthesized and characterized by TG-DTA, X-Ray diffraction,¹H NMR, and scanning electron microscopy (SEM). The extraction behavior of Am(III) and Eu(III) in Fe-DGAH was studied from dilute nitric acid medium to examine the feasibility for the mutual separation of trivalent actinides and lanthanides using Fe-DGAH. For this purpose, the effect of various parameters such as the duration of equilibration and concentrations of europium, nitric acid, and diethylenetriaminepentaacetic acid (DTPA) in the aqueous phase on the distribution ratio (K_d) of Am(III) and Eu(III) was studied. The conditions needed for the efficient separation of Am(III) from Eu(III) were optimized using DTPA. The distribution ratio of ?10⁴ mL/g was obtained for both Am(III) and Eu(III) at pH 3, and it decreased with an increase in the concentration of nitric acid. However, a separation factor of Eu(III) over Am(III) of ?150 was achieved in the presence of DTPA. Rapid sorption of metal ions in the initial stages of equilibration followed by the establishment of equilibrium occurred within 2 h. The sorption data were fitted to the Langmuir adsorption model, and the apparent europium sorption capacity was determined to be ?50 mg/g. The study indicated the feasibility of using Fe-DGAH particles for magnetic separation of Eu(III) from Am(III) with high separation factors.     

Development and Demonstration of Americium (III)-Europium (III) Separation Using Diglycolamic Acid

The extraction behavior of Eu(III) and Am(III) in a solution of bis(2-ethylhexyl)diglycolamic acid (HDEHDGA) in n-dodecane (n-DD) from citric acid (CA) medium was studied as a function of various parameters. The extraction increased with increase of pH, reached a maximum at pH 2 followed by decrease. The stripping behavior of Eu(III) and Am(III) from the loaded organic phase was studied by using a solution of diethylenetriaminepentaacetic acid (DTPA) and CA. The conditions needed for the efficient separation of Am(III) from Eu(III) were optimized. Based on the optimized conditions, the feasibility of separating Am(III) from Eu(III) present in CA feed solution was investigated in a 20- stage mixer-settler. Quantitative extraction of Eu(III) and Am(III) in 0.1 M HDEHDGA/n-DD was achieved in 3–4 stages, whereas the selective back extraction of Am(III) was achieved in ～20 stages upon contacting the loaded organic phase with a stripping formulation composed of DTPA-CA at pH 1.5. The results confirmed the possibility of using diglycolamic acid for the separation of trivalent actinides from the chemically similar lanthanides, which is indeed necessary for transmutation of minor actinides present in high-level liquid waste (HLLW).     

Synergistic Extraction of U(VI), Th(IV), and Lanthanides(III) from Nitric Acid Solutions Using Mixtures of TODGA and Dinonylnaphthalene Sulfonic Acid

The extraction of U(VI), Th(IV), and lanthanides(III) from aqueous nitric acid solutions with mixtures of N,N,N′,N′-tetra(n-octyl)diglycolamide (TODGA) and dinonylnaphtalene sulfonic acid (HDNNS) in n-decane has been investigated. The extraction efficiency of U(VI), Th(IV), and Ln(III) ions is greatly enhanced by addition of HDNNS to an organic phase containing TODGA. The synergistic effect arises from the higher hydrophobicity of U(VI), Th(IV), and Ln(III) extracted species formed by TODGA and DNNS^? anions as compared to those formed by TODGA and NO₃^? ions as counter anions. The synergistic effect for U(VI), Th(IV), and Ln(III) extraction from aqueous nitric acid solutions with mixtures of TODGA and HDNNS becomes weaker when the acidity of the aqueous phase increases. A high synergistic enhancement is accompanied with a high selectivity of Ln(III) extraction from nitric acid solutions.     

Synergistic Extraction of Lanthanides (III) with Mixtures of TODGA and Hydrophobic Ionic Liquid into Molecular Diluent

The extraction of lanthanides(III) from aqueous nitric acid solutions with N,N,N’,N’-tetra(n-octyl)diglycolamide (TODGA) and with mixtures of TODGA and the hydrophobic ionic liquid (IL) [C₄mim][Tf₂N] into 1,2-dichloroethane (DCE) has been investigated. The extraction efficiency of Ln(III) ions was greatly enhanced by the addition of a small amount of IL to an organic phase containing TODGA. The synergistic effect comes from the higher hydrophobicity of Ln(III) extracted species formed by TODGA and the weakly coordinating Tf₂N^? anions compared with those formed by TODGA and NO₃^? ions as the counter-anions. The partition of Tf₂N^? anions between the organic and aqueous phases is the dominant factor governing the extractability of lanthanides(III) with mixtures of TODGA and [C₄mim][Tf₂N]. The extraction of Ln(III) from aqueous nitric acid solutions by TODGA alone and its mixtures with [C₄mim][Tf₂N] into DCE can be described on the basis of the solvation extraction mechanism. However, in the extraction system with added [C₄mim][Tf₂N], the partition of Tf₂N^? between two immiscible phases and the interaction between HTf₂N and TODGA in the organic phase should be taken into account. Possible reasons of the antagonistic effect in the TODGA–[C₄mim][Tf₂N] extraction system are discussed.     

Extraction Behavior of Am(III) and Eu(III) from Nitric Acid Medium in Tetraoctyldiglycolamide-Bis(2-Ethylhexyl)Phosphoric Acid Solution

The extraction behavior of Am(III) and Eu(III) in a solution of tetra-octyldiglycolamide (TODGA), bis(2-ethylhexyl)phosphoric acid (HDEHP), and n-dodecane (n-DD) was studied to understand the role of TODGA and HDEHP in the combined solvent system. The extraction behavior of these metal ions was compared with those observed in TODGA/n-DD and HDEHP/n-DD. The effect of various parameters such as concentrations of HNO₃, TODGA, and HDEHP on the distribution ratio of Am(III) and Eu(III) was studied. Synergistic extraction of both the metal ions observed at lower acidities (<2.0 M) was attributed to the involvement of TODGA and HDEHP for extraction. However, the extraction of Am(III) and Eu(III) in the combined solvent was comparable with that observed in TODGA at higher acidities. The slope analysis of the extraction data confirmed the involvement of both the extractants at all acidities investigated in the present study.     

Selective Extraction of Am(III) from PUREX Raffinate: The AmSel System

The separation of actinides(III) from used nuclear fuel is a key step for the recycling of used nuclear fuel in innovative fuel cycles. However, high neutron dose rates and heat load of short-lived curium isotopes complicate the production and handling of new nuclear fuel containing curium(III) and americium(III). Therefore, new processes have to be developed separating only americium(III) from PUREX (Plutonium-Uranium Recovery by Extraction) raffinate. This is achieved by coextracting An(III) and Ln(III) from PUREX raffinate using N,N,N’,N’-tetraoctyl-diglycolamide (TODGA), followed by the subsequent selective stripping of Am(III) by a water-soluble bis-triazinyl-bipyridin (sodium 3,3’,3’’,3’’’-([2,2’-bipyridine]-6,6’-diylbis(1,2,4-triazine-3,5,6-triyl))tetrabenzenesulfonate, SO₃-Ph-BTBP). The selectivity for Am(III) over Cm(III) is SF_{Cm(III)/Am(III)} ≈ 2.5, due to the inverse selectivity of TODGA and SO₃-Ph-BTBP. Additionally, a separation factor up to 1200 is achieved for the separation of Eu(III) from Am(III). The results demonstrate that the presented system works very well even at acidic conditions using nitric acid as the aqueous phase and does not require additional salting out agents.     

Extraction of Lanthanides(III) from Aqueous Nitrate Media with Tetra‐(p‐tolyl)[(o‐Phenylene)Oxymethylene] Diphosphine Dioxide

A novel tridentate neutral organophosphorus compound, tetra‐(p‐tolyl)[(o‐phenylene)oxymethylene] diphosphine dioxide (I) has been synthesized and its extracting ability for microquantities of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y from HNO₃ and NH₄NO₃ aqueous solutions has been studied. The effect of HNO₃ concentration in the aqueous phase and that of the extractant concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes and conditional extraction constants of Ln(III) have been determined. The extraction behavior of compound I is compared with that of the diglycolamide ligand TODGA. The potentialities of polymeric resin impregnated with compound I for the preconcentration of lanthanides(III) from nitric acid solutions are demonstrated.     

Solvent Extraction and Fluorescence Spectroscopic Investigation of the Selective Am(III) Complexation with TS-BTPhen

An americium(III) selective separation procedure was developed based on the coextraction of trivalent actinides (An(III)) and lanthanides (Ln(III)) by TODGA (N,N,N′,N′-tetraoctyl-diglycolamide), followed by Am(III) selective stripping using the hydrophilic complexing agent TS-BTPhen (3,3′,3?,3?′-[3-(1,10-phenanthroline-2,9-diyl)-1,2,4-triazine-5,5,6,6-tetrayl]tetrabenzenesulfonic acid). Distribution ratios were found at an acidity of 0.65 mol L^?1 nitric acid that allowed for the separation of Am(III) from Cm(III) (D_Cm > 1; D_Am < 1), giving a separation factor between curium and americium of SF_Cm/Am = 3.6 within the stripping step. Furthermore, Am(III) was readily separated from the lanthanides with the lowest selectivity for the Ln(III)/Am(III) separation being lanthanum with a separation factor of SF_La/Am = 20. The influence of the TS-BTPhen concentration on Am(III) distribution ratios was studied, giving a slope (logD vs. log[TS-BTPhen]) of approximately ?1 for the stripping of An(III) with TS-BTPhen from the TODGA-based organic phase. Time-resolved laser fluorescence spectroscopy (TRLFS) measurements of curium(III) were used to analyze the speciation of Cm(III)-TS-BTPhen complexes. Both 1:1 and 1:2 complexes were identified in single-phase experiments. The formation of the 1:1 complex was suppressed in 0.5 mol L^?1 nitric acid but it was significantly present in HClO₄ at pH 3. Conditional stability constants of the complex species were calculated from the TRLFS experiments.     

Thermodynamic and Spectroscopic Studies on Am(III) and Eu(III) in the Extraction System of N,N,N',N'-Tetraoctyl-3-Oxapentane-1,5-Diamide in n-Dodecane/Nitric Acid

Abstract

Thermodynamic parameters (ΔG, ΔH, and ΔS) for the extraction of trivalent f-elements, M(III) (M = Am, Eu), with N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) were determined in nitric acid/n-dodecane extraction system. The extraction of M(III) with TODGA was more exothermic than those with octyl(phenyl)-N,N-diisobutylcarbamoylmethyl phosphine oxide (CMPO) and dihexyl-N,N-diethylcarbamoylmethyl phosphonate (DHDECMP). The difference in ΔH between the extractants was attributed to the difference in the binding mode between them, i.e. tridentate (TODGA) and bidentate (CMPO and DHDECMP). In addition, from the results of luminescence lifetime measurement, it was found that the inner-sphere of extracted Eu(III) was dehydrated completely, and occupied by TODGA and/or NO₃ ^?.     

Modified Diglycolamides for the An(III) + Ln(III) Co-separation: Evaluation by Solvent Extraction and Time-Resolved Laser Fluorescence Spectroscopy

The use of two recently developed diglycolamide-based extractants for the co-separation of trivalent actinides (An(III)) and lanthanides (Ln(III)) is described and compared to the well-known extractant TODGA (N,N,N’,N’-tetraoctyl diglycolamide). The addition of one or two methyl groups to the central methylene carbon atoms of the TODGA molecule leads to a reduction of the extraction efficiency for An(III) and Ln(III). This is attributed to a lower complex formation constant, which was proven by Time-Resolved Laser Fluorescence Spectroscopy (TRLFS). Conditional stability constants were determined by solvent extraction and TRLFS. The reduction in extraction efficiency leads to overall reduced distribution ratios of all tested metal ions, including Sr(II). The reduced Sr(II) extraction is beneficial as a co-extraction in a solvent extraction process could be avoided, while an efficient extraction of the desired An(III) and Ln(III) is still achieved. Furthermore, this might be a benefit, as the stripping behavior might be improved, even at moderate nitric acid concentrations. The slightly higher affinity of the diglycolamides towards Eu(III) over Am(III) is represented by all ligands, although the selectivity is rather low. This results in promising extraction properties of the modified diglycolamides towards the development of continuous solvent extraction processes.     

Synthesis of Pre‐Organized Bisdiglycolamides (BisDGA) and Study of their Extraction Properties for Actinides(III) and Lanthanides(III)

Bisdiglycolamides 1–9 were synthesized and studied as extracting agents for An(III) and Ln(III) from nitric acid solutions. Compounds 1d‐3 with rigid spacers as m‐xylylene and 6b‐9 with more flexible alkyl chain linkers, show higher selectivity for Eu(III) extraction over Am(III) than diglycolamides (TBDGA, DMDODGA, TODGA) in (50:50)_%Vol HPT/1‐octanol mixture. Am(III) and Eu(III) extraction kinetics are very fast and back‐extraction with more than 99% efficiency of both cations is possible after four times of contact of the loaded solvent with fresh 0.01 mol/L nitric acid solutions.     

Extraction of Lanthanides(III) and Am(III) by Mixtures of Malonamide and Dialkylphosphoric Acid

Abstract

N,N′‐dimethyl‐N,N′‐dioctylhexylethoxymalonamide, DMDOHEMA, and di‐n‐hexylphosphoric acid, HDHP, are the extractants of reference for the French DIAMEX–SANEX process for the separation of trivalent actinide ions from the lanthanide ions. In this work, the extraction of Eu³⁺ and Am³⁺ by the two extractants, alone or in mixtures, has been investigated under a variety of experimental conditions. The two cations are extracted by HDHP as the M(DHP · HDHP)₃ complexes with an Eu/Am separation factor of ～10. With DMDOHEMA, Eu³⁺ and Am³⁺ are extracted as the M(NO₃)₃(DMDOHEMA)₂ disolvate species with an Am/Eu separation factor of ～2. The metal distribution ratios measured with a mixture of the two reagents indicated that almost all lanthanides are extracted equally well. The extraction of Eu³⁺ and Am³⁺ by HDHP‐DMDOHEMA mixtures exhibits a change of extraction mechanism and a reversal of selectivity taking place at ～1 M HNO₃ in the aqueous phase. Below this aqueous acidity, HDHP dominates the metal extraction by the mixture, whereas DMDOHEMA is the predominant extractant at higher aqueous acidities. Some measurements indicated apparent modest antagonism between the two extractants in the extraction of Eu³⁺ and synergism in the extraction of Am³⁺. These data were interpreted as resulting from the formation in the organic phase of mixed HDHP‐DMDOHEMA species containing two HDHP and five DMDOHEMA molecules.     

Extraction Behavior of Ln(III) Ions by T2EHDGA/n-Dodecane from Nitric Acid and Sodium Nitrate Solutions

The diglycolamide extractant T2EHDGA has proven to be promising for the separation of lanthanides and minor actinides in high-level nuclear waste reprocessing. This neutral extractant has shown significant extraction capacity for HNO₃ into the nonpolar organic phase, along with hyper-stoichiometric nitrate dependence on extraction of trivalent f-elements. The transport behavior of T2EHDGA/n-dodecane toward trivalent lanthanides is not well understood. This work found a significant increase in distribution ratios for Eu(III) extracted from aqueous HNO₃ media compared with that from NaNO₃. The extraction of Eu(III) from HNO₃ results in a different thermodynamic product than predicted by classic solvent extraction of 3:1 ligand–metal complex as observed with NaNO₃ in FTIR and UV-vis spectroscopy. Experimental distribution measurements in conjunction with mass-action modeling using the solvent extraction modeling program SXLSQI suggest participation of 1 to 2 HNO₃ molecules in the Eu(III)/T2EHDGA complex upon extraction from HNO₃ media, indicative of a mechanism change responsible for the enhanced extraction behavior toward lanthanides in the presence of HNO₃.     

Extraction of Lanthanides(III) with N,N′-Bis(Diphenylphosphinyl-Methylcarbonyl)Diaza-18-Crown-6 in the Presence of Ionic Liquids

The extraction of microquantities of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y from nitric acid solutions into an organic phase containing N,N′-bis(diphenylphosphinyl-methylcarbonyl)diaza-18-crown-6 and ionic liquid (IL) 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (BMImTf₂N) has been studied. The effect of HNO₃ concentration in the aqueous phase and that of the extractant and IL concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes has been determined. A considerable synergistic effect was observed in the presence of IL in the organic phase containing a neutral organophosphorus ligand. This effect is connected with the hydrophobic nature of the IL anion. The partition of IL between the equilibrium organic and aqueous phases is the dominant factor governing the extractability of lanthanide (III) ions in the extraction system. The potentialities of polymeric resin impregnated with compound I and BMImTf₂N for the preconcentration of lanthanides(III) from nitric acid solutions are demonstrated.     

An Additional Insight into the Correlation between the Distribution Ratios and the Aqueous Acidity of the TODGA System

Abstract

Extraction of Eu(III) and Am(III) from HNO₃ into the organic solvents using N,N,N′,N′‐tetraoctyl‐diglycolamide (TODGA) was investigated in order to study the detailed extraction reaction. The chemical species: 1:2 for metal:TODGA complex is present in polar diluents. On the other hand, the metal complexes need three or more TODGA molecules to remain stable in non‐polar diluents. The HNO₃ concentration dependence on the distribution ratio suggests that HNO₃ participates in the metal extraction. Infrared spectra indicate that the carbonyl oxygen coordinates with Eu(III), and luminescence lifetimes suggest that there are no water molecules in the inner coordination sphere of the extracted Eu‐complex.     

Studies on the Use of N,N,N´,N´-Tetra(2-ethylhexyl) Diglycolamide (TEHDGA) for Actinide Partitioning. I: Investigation on Third-Phase Formation and Extraction Behavior

Abstract

Diglycolamides have emerged as an interesting class of extractants for actinide partitioning from high-level waste (HLW). N,N,N´,N´-tetraoctyl diglycolamide (TODGA) has been extensively studied for lanthanide-actinide co-extraction behavior. The present work deals with a branched isomer of TODGA, that is, N,N,N´,N´-tetra(2-ethylhexyl) diglycolamide (TEHDGA). TEHDGA was studied for the extraction of ²⁴¹Am and third-phase formation. The effect of using different phase modifiers on the prevention of the formation of a third phase during nitric acid extraction by TEHDGA along with the acid uptake behavior by TEHDGA in the presence of the modifiers was studied. The modifiers used for this purpose were di(n-hexyl)octanamide (DHOA), isodecanol, and n-decanol. The effect of the modifiers on the uptake of ²⁴¹Am as a function of acid concentration and as a function of modifier concentration was also examined. DHOA was found to be a suitable modifier, in spite of its high acid uptake. The uptake of lanthanides Ce, La, Eu, Gd, and Nd and elements such as Fe, Ni, Mn, Mo, Ru, Sr, and Cs with DHOA-modified TEHDGA–n-dodecane solvent systems were investigated. The results obtained indicated that, while DHOA-modified TEHDGA/n-dodecane extracted lanthanides and actinides, it did not show any significant uptake of other elements. Thus, the TEHDGA-DHOA/n-dodecane solvent system can be used effectively for the partitioning of lanthanides and actinides from HLW.     

Development of a Selective Americium Separation Process Using H4TPAEN as Water-Soluble Stripping Agent

ABSTRACT

Recycling americium from spent nuclear fuel is considered as an important option for a future sustainable nuclear fuel cycle. The PUREX solvent extraction process allows to separate uranium and plutonium from a solution of spent fuel dissolved in nitric acid. In a second step, it would be desirable to separate americium from fission products, and especially lanthanides, but also from curium in order to further transmute americium in future fast neutron reactors. For this purpose, we report the investigation of a new solvent extraction process based on the use of TODGA as an extractant in the organic phase and H₄TPAEN as a selective Am(III) stripping agent in the aqueous phase. With this promising system it is possible to co-extract Am, Cm and lanthanides at high acidity and then selectively strip americium from the loaded organic phase at pH around 1 with H₄TPAEN. Batch extraction data were acquired to evaluate best conditions to develop a liquid-liquid extraction flow sheet. The influence of several parameters like concentration of ligand, cations and temperature on Am(III)/Cm(III) and Am/lanthanides separation was evaluated. Especially, the ability of H₄TPAEN complexing agent to strip macro-concentrations of Am was demonstrated.     

A Novel Solvent System Involving Terpyridine and Cyanex-301 for Am(III) and Eu(III) Separation from Weakly Acidic Feeds

Separation of trivalent actinides and lanthanides is a challenging task and has a great relevance in the nuclear fuel cycle. Bis(2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex-301) show high selectivity for the trivalent actinides over the lanthanides at pH 3 or higher and N-donor ligands were reported to enhance the selectivity. 2,2?:6?,6”-Terpyridine (terpy), on the other hand, has shown to be quite effective at lower pH values and the combination of Cyanex 301 and terpy was evaluated in the present study, for the first time, for the separation of Am(III) from Eu(III), representative actinide and lanthanide elements, respectively at pH 2.0.

Thermodynamic parameters (enthalpy, entropy, and free energy) for the two phase extraction were also determined from the distribution studies at variable temperatures. Extraction of both Am³⁺ and Eu³⁺ was favored by negative enthalpy of extraction. More negative ΔG value indicated that Am³⁺ extraction was more favoured as compared to Eu³⁺ extraction using this solvent system. Effect of diluent composition on the extraction of Am³⁺ and Eu³⁺ was also studied in the present work.     

Direct Selective Extraction of Actinides (III) from PUREX Raffinate using a Mixture of CyMe4BTBP and TODGA as 1-cycle SANEX Solvent

Abstract

Within the framework of our research activities related to the partitioning of spent nuclear-fuel solutions, the direct selective extraction of trivalent actinides from a simulated PUREX raffinate was studied using a mixture of CyMe₄BTBP and TODGA (1-cycle SANEX). The solvent showed a high selectivity for trivalent actinides with a high lanthanide separation factor. However, the coextraction of some fission product elements (Cu, Ni, Zr, Mo, Pd, Ag, and Cd) from a simulated PUREX raffinate was observed, with distribution ratios up to 30 (Cu). The extraction of Zr and Mo could be suppressed using oxalic acid but the use of the well-known Pd complexant N-(2-Hydroxyethyl)-ethylendiamin-N,N′,N′-triacetic acid (HEDTA) was unsuccessful. During screening experiments with different amino acids and derivatives, the sulfur-bearing amino acid L-Cysteine showed good complexation of Pd and prevented its extraction into the organic phase without influencing the extraction of the trivalent actinides Am (III) and Cm (III). The optimization studies included the influence of the L-Cysteine and HNO₃ concentration and the kinetics of the extraction. The development of a process-like extraction series showed very promising results in view of further optimizing the process. A strategy for a single-cycle process is proposed within this article.