Tuning the Extractive Properties of Purex Solvent using Room Temperature Ionic Liquid

An Aliquat-336 based ionic liquid, namely, tri-n-octylmethylammonium bis(2-ethylhexyl)phosphate ([A3636]⁺[DEHP]^?) was prepared and studied for the extraction of U(VI), Pu(IV), and Am(III) from nitric acid medium. Since the ionic liquid, [A336]⁺[DEHP]^? was miscible in n-dodecane (n-DD), the extraction of these actinides in the PUREX solvent, 1.1 M tri-n-butylphosphate (TBP) in n-dodecane (n-DD), was investigated in the presence of small concentrations of ionic liquid. The distribution ratio of U(VI) and Am(III) in 0.03 M [A336]⁺[DEHP]^?/n-DD decreased with increase in the concentration of nitric acid; whereas the extraction of Pu(IV) initially increased, it reached a maximum at 4 M nitric acid followed by the decrease. The extraction of actinides in ionic liquid medium decreased in the order Pu(IV) > U(VI) >> Am(III), indicating the feasibility of modifying the extractive properties of TBP/n-DD to favor Pu(IV) extraction. Therefore, the extraction of Pu(IV) in a solution of TBP – [A336]⁺[DEHP]^? in n-DD was also studied. The distribution ratio of Pu(IV) increased with increase in the concentration of ionic liquid and decrease in the concentration of TBP in organic phase. The distribution ratio of Pu(IV) determined in the presence of small concentration of ionic liquid in 1.1 M TBP/n-DD was always much higher than that observed in 1.1 M TBP/n-DD. In contrast to this, the distribution ratio of U(VI) decreased by the addition of ionic liquid and Am(III) was inextractable even in the presence of ionic liquid.     

Studies on the Extraction of Actinides by Diamylamyl Phosphonate

Abstract

Diamylamyl phosphonate (DAAP) was synthesised by the Michealis Becker reaction, and was characterized by elemental analysis, IR, and ³¹P NMR. The extraction of U(VI), Th(IV), Pu(IV) and Am(III) by 1.1 M DAAP in n‐dodecane as a function of nitric acid concentration was studied and the results are compared with the extraction behavior of these ions by tributyl phosphate (TBP) and triamyl phosphate (TAP) in n‐dodecane. Some important physical properties of the extractant that have to be met for its use in industrial scale liquid‐liquid extraction such as density, surface tension, viscosity and phase disengagement time with 1.1 M DAAP/n‐dodecane have been measured and compared with those of 1.1 M TBP/n‐dodecane. Studies on the third phase formation behavior of DAAP/n‐dodecane with U(VI) and Th(IV) nitrates in nitric acid medium have been carried out and the results are reported. The breakthrough and elution behavior of U(VI) using a column packed with 50% (w/w) DAAP impregnated on Amberlite XAD‐7 was studied and reported.     

EXTRACTION OF ACTINIDES AND SELECTED FISSION PRODUCTS FROM NITRIC ACID MEDIUM USING LONG CHAIN MONOAMIDES

A series of long chain disubstituted aliphatic amides have been prepared with different substituting groups and the extracting ability for U(VI), Th(IV) and some fission products like Am(III), Zr(IV), Eu(III) and Cs from nitric acid solutions has been studied. All results were compared with those obtained by using TBP under the same conditions. All prepared amides exhibit higher U-Th separation factors than TBP. Distribution ratios of U(VI) as function of nitric acid concentration, extractants concentration and salting-out agent have been measured by using N,N-dihexyloctanamide (DHOA) and N,N-dihexyl(2-ethyl)hexylhexanamide (DHEHA), which were chosen for further studies. The extraction behviour of U(VI), Th(IV) and Zr(IV) with gamma irradiated DHOA, DHEHA and TBP in toluene from 3 M HNO₃ has been studied as a function of absorbed doses. Back extraction of U(VI), Th(IV) and Zr(IV) from organic phases was also studied.     

Plutonium Third Phase Formation in the 30% TBP/Nitric Acid/Hydrogenated Polypropylene Tetramer System

Abstract

A study on plutonium third phase formation in 30% TBP/nitric acid/hydrogenated polypropylene tetramer (HPT) was performed. Characterization studies of HPT indicate its composition to be a mixture of many highly branched alkanes with a volatility close to n‐undecane. This composition results in about a factor of two better resistance to Pu(IV) third phase formation than dodecane. At 7 M nitric acid in the aqueous phase, the presence of Pu(VI) was observed to substantially reduce the organic phase metal concentration necessary to induce phase splitting in both diluents. Spectroscopic investigation of mixed valence systems also suggest a prominent role for Pu(VI) in the formation of the dense organic phase. Accumulation of Pu(VI) in the heavy phase, as well as certain spectral features, suggest that Pu(VI) is forming a different species, possibly a plutonyl trinitrato, with a strong tendency to form third phase.     

EXTRACTION OF ACTINIDES BY BIFUNCTIONAL PHOSPHINIC ACID RESIN

ABSTRACT

The extraction of U(VI), Am( III), Pu( IV), Np( IV) and ThIV) by bifunctional phosphinic acid resin of various cross linkages is reported as function of nitric acid concentration. From the comparison of the distribution coefficient values it is suggested that the recovery of these actinide elements from waste solutions as we II as their mutual separations is possible by using phosphinic acid resin.     

Extraction of Uranium(VI) and Plutonium(IV) with Tetra-Alkylcarbamides

ABSTRACT

The use of tetra-alkylcarbamides as novel extractants for the separation of uranium(VI) and plutonium(IV) by solvent extraction from spent nuclear fuels is investigated in this study. Batch extraction experiments show that tetra-alkylcarbamides strongly extract U(VI) with high distribution ratios. Plutonium(IV) can be co-extracted with U(VI) at high nitric acid concentration, while high U(VI)/Pu(IV) selectivities can be reached at lower acidity. Loading capacity experiments with high uranium concentrations show that alkyl chains longer than butyl are necessary to avoid third phase formation. Nevertheless, the viscosity of uranium-loaded solvents gets too high with alkyl chains longer than pentyl. Overall, this study shows that with TPU extractant (with four pentyl chains), an efficient co-extraction of uranium and plutonium can be reached (D_U,Pu > 1) for a concentration of nitric acid higher than 4 mol?L^?1, while the partition between uranium(VI) and plutonium(IV) could be operated even at 2 mol?L^?1 nitric acid without redox chemistry.     

Extraction Behavior of Some Actinides and Fission Products from Nitric Acid Medium by a New Unsymmetrical Diglycolamide

Abstract

A new unsymmetrical diglycolamide, N,N-di-2-ethylhexyl-N',N'-di-octyl-3-oxapentane-1,5-diamide, trivially known as di-ethylhexyl-di-octyl-diglycolamide (DEHDODGA) has been synthesized, and characterized by ¹H, and ¹³C nmr, mass, and IR spectroscopy. Extraction behavior of ²⁴¹Am(III), ^(152+154)Eu(III), ²³⁹Pu(III), ²³⁹Pu(IV), ²³³U(VI), ¹³⁷Cs(I), and ^(85+89)Sr(II) from nitric acid medium by a solution of DEHDODGA in n-dodecane was studied, at 298–333 K. The effect of concentrations of HNO₃ and DEHDODGA and of temperature on the distribution ratio (D _M) was studied. Extraction of Eu(III), Am(III), Pu(III), and Pu(IV) increased with increase in nitric acid concentration, and the distribution ratio of Cs(I) was insignificant. However, the distribution ratios of U(VI) and Sr(II), though not insignificant, but was quite less compared to trivalents, and Pu(IV). The D _Sr(II) increased with increase in the concentration of nitric acid, reaching a maximum at 4 M followed by decrease. The stoichiometry of Am(III) – DEHDODGA was determined by slope analysis of extraction data, and the enthalpy change accompanied by the extraction of Eu(III), Pu(III), and Am(III) was determined and reported in this article.     

THE EXTRACTION OF Am(III) FROM NITRIC ACID BY OCTYL(PHENYL)-N,N-DIISOBUTYLCARBAMOYLMETHYLPHOSPHINE OXIDE - TRI-n-BUTYL PHOSPHATE MIXTURES

Abstract

The extraction behavior of Am(III) from nitric acid by octy1(phenyl)-N,N-diisobutylcarbamoyl methyphosphine oxides, OØD[IB]CMPO, in the presence of tributylphosphate, TBP, has been studied using diethylbenzene, decalin, and normal aliphatic hydrocarbon diluents. Relative to ØD[IB]CMPO alone, mixtures of TBP and OØD[IB]CMPO show a slight enhancement in the extraction of Am(III) from nitric acid solution above 2 M and a moderate decrease in extraction for lower acid concentrations. The net effect of TBP addition to OØD[IB]CMPO (as well as other selected carbamoyl methylphosphoryl extractants) is a relative insensitivity of the distribution ratio of Am(III) to HNO₃ concentration in the range of 0.5 M to 6 M and facilitated stripping of Am(III) with dilute acid. Since a continuous variation study of Am(III) extraction using mixtures of ØOD[IB]CMPO and TBP at a fixed total concentration revealed no evidence of a mixed complex, the TBP appears to be behaving primarily as a phase modifier

The most significant benefit gained from addition of TBP to ØD[IB]CMPO is the increased metal ion loading capacity and extractant compatibility with alicyclic and aliphatic diluents. The use of TBP to overcome phase compatibility with other bifunctional extractants of the carbamoylmethylphosphoryl type and the use of other phase modifiers with ØD[IB]CMPO have also been investigated.     

STUDIES ON THE EXTRACTION OF PLUTONIUM(IV) FROM AQUEOUS NITRIC ACID - OXALIC ACID BY ALIQUAT-336

ABSTRACT

The extraction of Pu(IV) by Aliquat-336 from aqueous nitric acid containing oxalic acid was studied with a view to exploring the feasibility of recovery of Pu(IV) from Pu(IV) oxalate precipitation effluents. Distribution ratio data were obtained as a function of concentration of nitric acid, oxalic acid and Aliquat-336. The data obtained revealed that Pu(IV) can be extracted almost quantitatively by 20% Aliquate-336 in xylene from aqueous medium containing oxalic acid up to 0.25 M provided the nitric acid concentration is ≥ 4 M. These data suggest that Pu(IV) can be recovered directly from nitric acid - oxalic acid waste generated in Pu-oxalate precipitation by Aliquat-336 extraction.     

Role of Acetohydroxamic Acid in Selective Extraction of Technetium and Uranium Employing N,N-Dihexyloctanamide as Extractant

Straight chain N,N-dihexyloctanamide (DHOA) has been identified as a promising alternate extractant to tributyl phosphate (TBP) for the reprocessing of uranium based spent fuels. The present work compares extraction behavior of technetium using DHOA and TBP solutions in n-dodecane, under varying experimental conditions such as acidity (0.5–6 M HNO₃); extractant concentration (1.1 and 1.5 M), and uranium loading (50 g/L, relevant for Pu rich spent fuel feed solutions). The effect of acetohydroxamic acid concentration on U, Pu, Np, and Tc extraction behavior has also been investigated. Pu(IV)-AHA interaction and its influence on extraction using TBP and DHOA extractants has been studied spectrophotometrically. The experimental data suggest that 1.1 M DHOA is better than 1.1 M TBP with respect to co-extraction of Tc and U, and U decontamination with respect to Np/Pu.     

Note: Effect of Temperature in the Extraction of Uranium and Plutonium by Triisoamyl Phosphate

Abstract

The extraction of uranium(VI) by triisoamyl phosphate (TiAP) has been studied to derive the thermodynamic parameters such as entropy change and the free-energy change. The extraction of U(VI) and Pu(IV) has also been studied with 1.1 M solutions of tri-n-butyl phosphate (TBP), tri-n-amyl phosphate (TAP), and TiAP as a function of temperature. While the enthalpy of U(VI) extraction was found to be exothermic, the enthalpy for the extraction of Pu(IV) was always found to be endothermic. The temperature at which the distribution ratios of U(VI) and Pu(IV) cross each other (the temperature of inversion) has been derived for TBP, TAP, and TiAP, and the results reveal the lowest temperature of inversion occurs for TiAP. The results indicate the advantage of TiAP as an extractant in avoiding plutonium reflux during the PUREX process involving high plutonium feed solutions, in addition to lower aqueous solubility, freedom from the third-phase formation problem, lower degradation, and better economics.     

Recent R&D Studies Related to Coprocessing of Spent Nuclear Fuel Using N,N-Dihexyloctanamide

Abstract

The PUREX process has undergone several modifications to address the issues of high burn up, fewer solvent extraction cycles, and reduced waste arisings. Advanced fuel cycle scenarios have led to a renewed international interest in the development of separation schemes for co-recovering U/Pu from spent fuels. Completely incinerable N,N-dihexyloctanamide (DHOA) has been identified as a promising candidate for the reprocessing of spent fuels. Batch extraction studies were carried out to evaluate DHOA and TBP for the coprocessing (co-extraction and co-stripping) of U and Pu from spent fuel under varying concentrations of nitric acid and of uranium as well as under simulated pressurized heavy water reactor spent fuel feed conditions. At 50 g/L U in 4 M HNO₃, D_Pu values for 1.1 M DHOA and 1.1 M TBP solutions in n-dodecane were 7.9 and 3.8, respectively. In contrast, significantly lower D_Pu value at 0.5 M HNO₃ (4 × 10^?3) for DHOA as compared to TBP (4 × 10^?2) suggested that it was a better choice for coprocessing of spent nuclear fuel. This behavior was attributed to the change in stoichiometry of extracted species at lower acidity vis-a-vis the higher acidity. These studies suggest that plutonium fraction can be enriched with respect to uranium contamination in the product stream. DHOA displays better extraction behavior of plutonium and stripping behavior of uranium under simulated feed conditions. DHOA appears distinctly better than TBP with respect to fission product/structural material decontamination of U/Pu.     

THE EXTRACTION OF Eu(III) FROM ACIDIC MEDIA BY OCTYL(PHENYL)-N,N-DIISOBUTYL CARBAMOYLMETHYLPHOSPHINE OXIDE.

The extraction behavior of Eu(III) from nitric and hydrochloric acid By solutions of CMPO with and without TBP has been studied using mesitylene and dodecane as diluents. Compared to CMPO alone, the CMPO-TBP mixture shows a slight enhancement in the extraction of Eu(III) from nitric acid above 2M and lower DEu’ s from low acidity. The distribution ratios measured for Eu(III) between HN03 and CMPO-TBP in dodecane are higher than the corresponding values in mesitylene.Extractant dependency studies in the presence and absence of TBP show that at low HN03 concentrations, the extractant dependency curve obtained in the presence of TBP lies below the curve obtained in the absence of TBP. At high acidity, the opposite is observed. The extraction of Eu(III) from hydrochloric acid by CMPO-TBP in dodecane is much lower than from nitric acid. A comparison between CMPO and D2EHPA for Eu(III) extraction has been carried out.     

THE EFFECT OF TEMPERATURE ON THE EXTRACTION OF NITRIC ACID AND PLUTONIUM(IV) NITRATE WITH 30 VOL.% TRIBUTYL PHOSPHATE (TBP)

Abstract

Own and published data were evaluated for characterizing the effect of temperature on the distribution of nitric acid and plutonium(IV). The solutes were distributed between 30 vol.% TBP in an aliphatic diluent and aqueous solutions containing nitric acid and zero to macro amounts of plutonium(IV) and uranyl nitrates. The temperature dependence of the distribution ratios is described with empirical model equations and examples of the dependence in the absence and presence of uranium(VI) are given. Taking infinite dilution of all solutes of the system as a standard state, the enthalpy change of the extraction reaction could be estimated as ?17 kJ/mol for nitric acid but no numerical estimate was possible for plutonium(IV).     

DISTRIBUTION BEHAVIOUR OF U(VI), Th(IV) AND Pa(V) FROM NITRIC ACID MEDIUM USING LINEAR AND BRANCHED CHAIN EXTRACTANTS

ABSTRACT

The extraction behaviour of 1M solutions of tri-2-ethylhexyl phosphate (TEHP), di-2-ethyl hexyl isobutyramide (D2EHIBA), tri-n-butyl phosphate (TBP) and di-n-hexyl hexanamide (DHHA) in n-dodecane towards U(VI), Th(IV) and Pa(V) in the presence of 220 g/L of Th from nitric acid medium has been studied. The limiting organic concentrations (LOC) of thorium (g/L) for 1 M TBP and 1 M DHHA are evaluated as 31, 20 ( at 1 M HNO₃) and 25,13 (at 4 M HNO₃) respectively. The distribution ratio (D) values of U(VI), Th(IV) and Pa(V) in the presence of thorium (220 g/L) at. 1 M HNO₃ suggest that branching in the alky group of amides suppresses the extraction considerably. In view of the selective extraction of U over Th by 5 % TBP in THOREX process at 4 M HNO₃, distribution behaviour is also studied employing a lower concenfration (0·18 M) of extractant for comparison purpose, Separation factor (S. F.) values for U(VI) over Th(IV) under different experimental conditions consistently varied in the order: D2EHIBA > DHHA > TEHP > TBP. The quantitative extraction of ²³³U from a synthetic mixture containing ²³³U (10^?5 M). ²³³Pa (10^?11 M) and thorium (220 g/L) at 1 M HNO₃ using 1 M solution of D2EHIBA in n-dodecane is achieved in three stages, Stripping and reusability studies of D2EHIBA have also been carried out.     

Separation and Recovery of Uranium,Neptunium, and Plutonium from High Level Waste Using Tributyl Phosphate: Countercurrent Studies with Simulated Waste Solution

ABSTRACT

The present work deals with countercurrent extraction studies on the partitioning of uranium, neptunium, and plutonium using 30% tributyl phosphate (TBP) from simulated high level waste solution generated during reprocessing of spent uranium fuel from pressurized heavy water reactors. The oxidation states of neptunium and plutonium were adjusted either by 0.01 M potassium dichromate or 0.01 M dioxovanadium ion. Neptunium and plutonium, extracted in the TBP phase, were stripped together using a mixture containing 0.05 M ascorbic acid and 0.25 M hydrogen peroxide in 2.0 M nitric acid solution. Although dioxovanadium ion is more effective for proper adjustment of the oxidation states of plutonium and neptunium, subsequent recovery of these actinides from loaded TBP is better if potassium dichromate is used for the valency adjustment. Results of the stagewise analysis of extraction and stripping of actinides using mixer-settlers are presented.     

Studies Related to the Processing of U–Zr and U–Pu–Zr Metallic Fuels Using Tri-iso-amyl Phosphate (TiAP) as Extractant

Metallic fuel is reprocessed by a compact nonaqueous pyrochemical process. The present study explores the possible uses of an aqueous reprocessing-based method as an alternative to the pyro-processing of metallic fuels. Solvent extraction studies in the batch mode were carried out for both U–Zr- and U–Pu–Zr-based metal alloy systems. Earlier studies carried out in our laboratory have established that Tri-iso-amyl Phosphate (TiAP) is a promising extractant for the reprocessing of spent fuels. In the present study, the distribution data has been generated for the extraction of uranium and zirconium as a function of equilibrium aqueous phase metal ion and nitric acid concentration with TiAP and Tri-n-butyl Phosphate (TBP)-based solvents. These studies indicate the formation of a third phase with zirconium in the presence of uranium with TBP under certain experimental conditions whereas it was not encountered with the TiAP system. Flow sheet for the co-extraction and co-stripping of heavy metal ions by 1.1M TiAP and 1.1M TBP in n-dodecane from U–Zr as well as U–Pu–Zr feed solutions in stage-wise mode has been evaluated. Percentage extraction and stripping of metal ions were calculated stage-wise and the results are discussed.     

Comparison of Extraction Behavior of Neptunium from Nitric Acid Medium Employing Tri-n-Butyl Phosphate and N,N-dihexyl Octanamide as Extractants

Extraction behavior of neptunium has been compared for tri-n-butyl phosphate (TBP) and N,N-dihexyl octanamide (DHOA) extractants as a function of nitric acid concentration (0.5 ? 6 M HNO₃), uranium loading (50 and 300 g/L relevant to Pu rich fast reactor and Pressurized Heavy Water Reactor, PHWR spent fuels, respectively), and in the presence of oxidizing and reducing agents. These studies suggest the possibility of co-recovery of U(VI), Pu(IV) and Np(IV) from spent fuel dissolver solutions (of Pu rich fuels) employing DHOA as extractant.     

EXTRACTION OF URANIUM(IV,VI), PLUTONIUM(III) AND NITRIC ACID BY 30% TRIBUTYL PHOSPHATE (TBP) IN DODECANE

Abstract

Data on the distribution of uranium(IV,VI), plutonium(III) and nitric acid between 30 vol.% TBP in dodecane and aqueous nitrate solutions also containing hydrazine nitrate were mathematically described by empirical equations. This made it possible to present distribution ratios of the extracted components as functions of concentrations and temperature at a single variable being varied and other variables being kept constant. Salting-out and self-salting-out action of the electrolytes present in the system as well as mutual replacement of the extracted components from the organic phase are shown.     

Comparative Evaluation of Tri-n-butyl Phosphate (TBP) and Tris(2-ethylhexyl) Phosphate (TEHP) for the Recovery of Uranium from Monazite Leach Solution

Separation of U(VI) from Th(IV) and rare earth elements (REEs) present in monazite leach solution (nitric acid medium) has been studied using tris(2-ethylhexyl) phosphate (TEHP) and tri-n-butyl phosphate (TBP) dissolved in n-paraffin as solvents under varying experimental conditions such as nitric acid, extractant and metal ion concentrations etc. There is an increase in distribution ratio of U(VI) (D _U ) with increase in aqueous phase acidity up to 5 M HNO₃ beyond which a decrease is observed. Typically for 1 × 10^?3 M U(VI), the D_U values increase from 8 (0.5 M HNO₃) to 80 (5 M HNO₃) for 1.1 M TEHP, and from 2 (0.5 M HNO₃) to 43 (5 M HNO₃) for 1.1 M TBP in n-paraffin. The separation factors of U(VI) (β: D_U/D_M) over metal ions (M) such as Th(IV) and Y(III) (chosen as a representative of heavy REEs) are better for TEHP than TBP at all nitric acid concentrations. Batch solvent extraction data have been used to construct the McCabe-Thiele diagrams for the recovery of U(VI) employing TEHP as the extractant. A process flow sheet has been proposed with 0.2 M TEHP in n-paraffin as solvent for the recovery of U(VI) from simulated monazite leach solution in HNO₃ medium.