Extraction of uranium (VI) from hydrochloric acid solutions by long-chain aliphatic amines

The partition of uranium (vi) between hydrochloric acid solutions and organic solutions of long-chain aliphatic amines has been investigated at different concentrations of hydrochloric acid, solvent and aqueous uranium, and at different temperatures. The effects of amine structure and of organic solvent and the mechanism of uranium extraction are discussed on the basis of the results obtained. From infra-red spectral measurements it is postulated that a chloro complex of uranium (vi) is formed in the extraction of uranium (vi) from hydrochloric acid solution by tri-n-dodecylamine in benzene.     

Extraction of uranium (VI) and thorium from hydrochloric acid solutions by tri-n-butyl phosphate

The partitions of uranium (vi) and thorium between hydrochloric acid solutions and solutions of tri-n-butyl phosphate (TBP) in benzene or kerosene have been investigated at different concentrations of hydrochloric acid and solvent, and at different temperatures. An infra-red spectral study has also been made of the organic solutions obtained in the extraction of uranium. The effect of organic solvent on the extractions has also been examined.     

DILUENT EFFECT ON THE EXTRACTION OF URANIUM(VI) FROM HYDROCHLORIC ACID SOLUTIONS BY TRIOCTYLMETHYLAMMONIUM CHLORIDE

ABSTRACT

The extraction of uranium(VI) from hydrochloric acid solutions by trioctylmethylammonium chloride (TOMAC) has been examined using various diluents such as benzene, chlorobenzene, o-dichlorobenzene, toluene, m-xylene, nitrobenzene, carbon tetrachloride, chloroform and 1,2-dichloroethane. It was found that by assuming a regular solution, the distribution coefficient and the enthalpy change associated with the metal extraction can be expressed in terms of the solubility parameter of TOMAC, diluent and the complex formed in the organic phase and their molar volumes. Additionally an empirical relation holds between distribution coefficient and the viscosity of diluent. Further results for the extraction of divalent manganese, cobalt, copper, zinc and cadmium from hydrochloric acid solutions by TOMAC are investigated in comparison with those of uranium(VI).     

SOLVENT EXTRACTION OF URANIUM( VI) AND THORIUM( IV) FROM NITRATE MEDIA BY CARBOXYLIC ACID AMIDES

ABSTRACT

A series of nineteen N-alkyl carboxylic acid amides (R.CO.NHR') has been prepared, in which the alkyl groups R and R' have been varied in order to introduce different degrees of steric complexity into the compounds. A smaller number of N,N-dialkyl amides (R.CO.NR₂) and non-substituted amides (R.CO.NH₂) has also been prepared for comparison purposes. These amides were characterized by measurement of their boiling points, melting points, refractive indices and densities.|The solvent extraction of uranium(VI) and thorium(IV) from sodium nitrate media by solutions of the amides in toluene was studied. Increasing steric bulk of the alkyl groups R and R' was found to cause a marked decrease in the extraction of thorium, with a much smaller effect on the extraction of uranium, thus considerably enhancing the separation between these metals. Vapour pressure osmometry studies indicate that the N,N-alkyl amides are self-associated in toluene solution, with aggregation numbers up to about 2.5 for 0.6 M solutions at 35°C. In contrast, the N,N-dialkylamides behave as monomers under these conditions. The distribution ratios for the extraction of uranium and thorium show second- and third-order dependences, respectively, on the extractant concentration for both the N-alkyl and N,N-dialkyl amides.     

Comprehensive Studies on Third Phase Formation: Application to U(VI)/Th(IV) Mixtures Extracted by TBP in N-dodecane

ABSTRACT

Phase splitting of tributylphosphate (TBP)/n-dodecane organic phases resulting from the extraction of UO₂(NO₃)₂, Th(NO₃)₄ and mixtures of both actinides from aqueous nitrate solutions has been investigated. Limiting organic concentrations (LOC) and metals distribution beyond third phase formation have been determined, with comparison between the cases of single metal-systems and metals mixtures. Simultaneous quantification of TBP and both metals was achieved through X-ray fluorescence (XRF) analyses. LOC studies reveal that thorium (IV) drives the third phase formation as it is the most destabilizing element in the solvent. After organic phase splitting, studies of the distributions of metals between the heavy organic phase (HOP) and the diluted organic phase (DOP) in the case of U^(VI)/Th^(IV) mixtures revealed that they are similar to those observed when both metals are alone in the solvent: Thorium (IV) has a strong affinity for the HOP, whereas uranium (VI) distributes both in HOP and in DOP. A supersaturation coefficient (N_LOC) is proposed as a new tool to account for the data obtained in the present study. Furthermore, the approach was successfully applied to analyse available data in the literature regarding thorium (IV) distribution studies after phase splitting in various TBP-alkane solvents. Such a study beyond third phase formation paves the way for studying the mechanism involved in third phase formation, as the metal is clearly identified as the key parameter.     

High Molecular Weight Pyridine Amines as Solvents for Uranium(VI) and Its Separation from Thorium

Abstract

Three high-molecular-weight pyridine amines, 5-(4-pyridyl)nonane, 2-hexylpyridine, and diphenyl-2-pyridylmethane, have been studied as components of solvent extraction systems. Results are presented to show the dependence of the uranium extraction coefficient (D _a ^o = [U_org]/[U_aq]) on equilibrium concentrations of hydrochloric, nitric, and sulfuric acid solutions with and without thiocyanate ions. The optimal conditions for the extraction have been carefully selected from an extensive and critical investigation of the various factors involved; e.g., the effects of diluents, concentration of the mineral acids, thiocyanate ions, salting and complexing agents, and the concentration of the solvents. The extraction mechanism and composition of the extracted complexes of uranium have been studied from partition and slope-analysis data. The results obtained give an orderly picture of the mechanism of extraction of uranium thiocyanate complexes (partly in relation to the hydration and solvation of the compounds extracted). Anomalous extraction behavior was observed at solvent concentrations greater than 0.05 M. The results have been interpreted on the basis of the formation of micelles of the salt molecules of the solvents. It has been shown that these pyridines will extract the metal efficiently and reversibly from dilute acid chloride, nitrate, and sulfate solutions containing thiocyanate. Common salts have no depressing effect on extraction. Distribution coefficients and separation factors of several metal ions, with respect to uranium(VI), are reported for the three mineral acid systems, and a method for the separation of thorium-234 from uranium is also described.     

Liquid-Liquid Extraction of Uranium(VI) from Aqueous Solution using 1-Hydroxyalkylidene-1,1-diphosphonic Acids

The extraction of uranium(VI) from aqueous solutions has been investigated using 1-hydroxyhexadecylidene-1,1-diphosphonic acid (HHDPA) and 1-hydroxydodecylidene-1, 1-diphosphonic acid (HDDPA), which were synthesized and characterized by elemental analysis and by FT-IR, ¹H NMR, ³¹P NMR spectroscopy. In this article, we propose a tentative assignment for the shifts of those two ligands and their specific complexes with uranium(VI). We carried out the extraction of uranium(VI) by HHDPA and HDDPA from [carbon tetrachloride?+?2-octanol (v/v: 90%/10%)] solutions. Various factors such as contact time, pH, organic/aqueous phase ratio, and extractant concentration were considered. The optimum conditions obtained were: contact time?=?20 min, organic/aqueous phase ratio?=?1, pH value?=?3.0, and extractant concentration?=?0.3 M. The extraction yields are more significant in the case of the HHDPA which is equipped with a hydrocarbon chain, longer than that of the HDDPA. Logarithmic plots of the uranium(VI) distribution ratio vs. pH_eq and the extractant concentration showed that the ratio of extractant to extracted uranium(VI) (ligand/metal) is 2:1. The formula of the complex of uranium(VI) with the HHDPA and the DHDPA is UO₂(H₃L)₂ (HHDPA and DHDPA are denoted as H₄L). A spectroscopic analysis showed that coordination of uranium(VI) takes place via oxygen atoms.     

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.     

Studies on Third Phase Formation in the Extraction of Th(NO3)4 by Tri-iso-amyl Phosphate in n-alkane Diluents

Third phase formation in the extraction of Th(NO₃)₄ from its solution with near-zero free acidity by 1.1 M solutions of tri-iso-amyl phosphate (TiAP) in n-dodecane, n-tetradecane, n-hexadecane, and n-octadecane has been investigated as a function of equilibrium aqueous phase Th(IV) concentration at 303 K. Distribution of Th(NO₃)₄ between organic and aqueous phases as well as the variation of densities of organic phases in biphasic and triphasic regions for its extraction by the above-mentioned solvents have been investigated with respect to equilibrium aqueous phase Th(IV) concentration under the above experimental conditions. Data on the ratio of volume of the diluent-rich phase to that of third phase for various TiAP/n-alkane-Th(NO₃)₄-303 K systems have also been generated in the present study. The results obtained are compared with literature data available for tri-n-butyl phosphate (TBP) and tri-n-amyl phosphate (TAP) systems which were experimented under identical conditions.     

The extraction of divalent cobalt,copper, zinc and cadmium from hydrochloric acid solutions by tri-n-butyl phosphate

The partition of divalent cobalt, copper, zinc and cadmium between hydrochloric acid solutions and solutions of tri-n-butyl phosphate (TBP) in benzene or kerosene has been investigated under different conditions. Further the absorption spectra of both the aqueous and organic phases have been studied, and the infrared spectra of the organic phases have been examined. It was found that the order of the extraction efficiency of TBP for divalent metalsis Zu > Cd > Cu > Co for [HCl]_aq < 8M and Zn > Cd > Co > Cu for [HCl]_aq > 8M.     

Extraction of U(VI), Th(IV), and Lanthanides(III) from Nitric Acid Solutions with CMPO-Functionalized Ionic Liquid in Molecular Diluents

The extraction of microquantities of U(VI), Th(IV), and lanthanides(III) from nitric acid solutions with CMPO-functionalized ionic liquid 1-[3[[(diphenylphosphinyl)acetyl]amino]propyl]-3-tetradecyl-1H-imidazol-3-ium hexafluorophosphate, CMPO-FIL(I) in molecular organic diluents has been studied. The effect of HNO₃ concentration in the aqueous phase and that of extractant concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes was determined. CMPO-FIL(I) demonstrates greater extraction ability towards Ln(III) than its neutral CMPO analog, diphenylphosphorylacetic acid N-nonylamide. This inner synergistic effect increases with a decreasing organic diluent polarity. The partition of CMPO-FIL(I) between the equilibrium organic and aqueous phases is the dominant factor governing the extractability of Ln(III) ions in the extraction system.     

Synergistic Effects in the Extraction of Uranium(VI) by Di-4-octylphenyl Phosphoric Acid

Abstract

The extraction of uranium(VI) from sulfuric acid solutions by di-4-octylphenyl phosphoric acid (DOPPA) is enhanced by the addition of neutral organophosphorus compounds due to synergistic action. The effect of tri-n-butyl phosphate (TBP), dibutylbutyl phosphonate (DBBP), and tri-n-octyl phosphine oxide (TOPO) was studied. The synergistic effect increased in this order. In the case of TBP and DBBP the extraction coefficient for U(VI) decreased with increasing concentration of synergistic agent after reaching a maximum. With TOPO, on the other hand, there was an increase even after this limit. This was because of the extraction of uranium by TOPO itself. The effect of uranium loading in the organic phase on the synergistic behavior was studied and the results were compared with those obtained with di-2-ethylhexyl phosphoric acid (DEHPA) in the presence of the same synergistic agents. The results with these two extractants indicate that with TOPO the synergism is mainly due to the formation of substitution products of the type UO₂A₂B₂ and with TBP addition products of the type UO₂(HA₂)₂B.     

Compositional Characterization of Organic Phases after the Phase Splitting in the Extraction of Th(NO3)4 by 1.1 M Tri-n-butyl phosphate/n-Alkane

Third phase formation in the extraction of Th(IV) by 1.1 M solutions of tri-n-butyl phosphate (TBP) in n-decane and n-hexadecane from Th(NO₃)₄ solution in 1 M HNO₃ has been investigated as a function of equilibrium aqueous phase Th(IV) concentration ([Th(IV)]_aq,eq) to estimate the concentrations of Th(NO₃)₄, HNO₃, and TBP in the third phase (TP) and the diluent-rich phase (DP). In this connection, new methods for the estimation of TBP in the organic phases after the phase splitting have been developed by exploiting the linear relationships of the density and refractive index of the solvent, the limiting organic concentration (LOC) for the third phase formation in the extraction of Th(IV) from solution with near-zero free acidity with TBP concentration in the solvent. TBP concentrations estimated by the above-mentioned methods have been validated by nitric acid (8 M) equilibration method. Experimental values for the concentration of TBP in the TP and DP for 1.1 M TBP/n-alkane–Th(NO₃)₄/1 M HNO₃ systems have been compared with the values computed based on a model proposed earlier. In addition, the density of organic phases and the ratio of the volume of the DP to that of the TP have been measured for the above-mentioned systems as a function of [Th(IV)]_aq,eq at 303 K.     

Rhodamine-B modified silica for uranium(VI) extraction from aqueous waste samples

Silica modified with rhodamine-B has been synthesized, characterized and used for solid phase extraction (SPE) of uranium(VI) (U(VI)) from aqueous waste solutions. Adsorption efficiency was influenced by various parameters, which have been investigated such as solution pH, shaking time, initial concentration, adsorbent dose and possible competing ions. The study showed that uranium adsorption was found to be quantitative at pH 5. The adsorption percentage of U(VI) was found to be 94% at the optimum conditions. Desorption conditions were also examined. About 99% of uranium loaded on modified silica was desorbed by 6% of HCl. The method was applicable for removal of uranium from natural samples.     

THE EQUILIBRIUM REACTION OF THE EXTRACTION OF URANIUM(VI) WITH DI-(2-ETHYLHEXYL) PHOSPHORIC ACID FROM NITRIC ACID SOLUTIONS

The equilibrium reactions for the extraction of uranium(VI) with di(2-ethylhexyl)phosphoric acid from nitric acid solutions is investigated. In this work, proton NMR technique was used to verify that the nitrate ligand in the resulting complexes originated from the complexing of nitric acid. Organic solutions of 0.05 M (dimeric HDEHP, the upper bar denotes the species in the organic phase) in kerosene were used to extract aqueous solutions containing various concentrations of uranyl nitrate and nitric acid. The concentrations of nitric acid and uranium(VI) in the organic phase were measured, and used to determine the composition of the resulting complex. Which were found to be varied with the uranium(VI) loading and the nitric acid loading of HDEHP. Parallel reactions of forming UO were proposed to describe this extraction system. The proposed reactions elucidate the equilibrium behavior consistently, for the loadings of uranium(VI) and nitric acid ranging from very low value to the vicinity of saturation.     

Evaluation of two-phase separation in N,N-di(2-ethylhexyl)butanamide-nitric acid systems using turbidity measurements

Quantitative evaluation of the two-phase separation between N,N-di(2-ethylhexyl)butanamide (DEHBA) and tri-n-butyl phosphate (TBP) diluted with n-dodecane and uranyl nitrate solution in nitric acid medium was achieved using turbidity measurements. The turbidities of DEHBA were relatively high, particularly at high DEHBA concentrations, while that of TBP rapidly decreased irrespective of nitric acid concentration. A high concentration of DEHBA, nitric acid, and uranium increased the turbidities in the organic phase, which could be ascribed to the increase in viscosity. Distribution ratios of uranium were also measured, and it was indicated that turbidity did not have a critical effect on the distribution ratio when the turbidity was below a certain value.     

Separation and concentration processes of solutions of Co(II), Ni(II), Cr(III), Fe(III) and Mn(II) by extraction with toluene-dissolved rosin

The extraction and stripping of Co(II), Ni(II), Cr(III) and Fe(III) from aqueous solutions by rosin dissolved in toluene has been investigated. Results obtained show that rosin is better extractant than abietic or n-lauric acids under comparable conditions. From these results, and the data of Mn(II) solvent extraction studied previously under the same conditions, a separation and concentration process for these five cations in aqueous solutions has been designed. Saturated solutions of Fe(III), Cr(III), Mn(II) and finally Co(II) and Ni(II) have been obtained successively by extraction and stripping, by addition of ammonium hydroxide to obtain the appropriate pH value, and by modifying adequately the organic phase/aqueous phase volume ratio.     

The Use of Tri-n-octylamine for the Separation of Vanadium(V) from Acidic Sulfate Uranium Leach Liquors

Abstract

Extraction of vanadium(V) from acidic sulfate solutions by a mixture of tri-n-octylamine and tributylphosphate (used as modifier) dissolved in kerosene has been studied. The distribution coefficient of vanadium(V) increases with an increase in pH and vanadium(V) concentration. The presence of iron(III) in aqueous solution does not have any appreciable effect, while large amounts of sulfate ion depress the distribution coefficient. Uranium(VI) has a distribution different from vanadium(V). Based upon these results, a scheme for the separation of vanadium(V) from uranium leach liquors has been made and checked experimentally.     

Extraction of cobalt (II) from hydrochloric acid solutions by long-chain aliphatic amines

The partition of cobalt (II) between hydrochloric acid solutions and organic solutions of long-chain aliphatic amines has been investigated under different conditions. The extracted species has been examined spectro-photometrically, and an infra-red study has also been made of the organic phases. The mechanism of extraction is discussed on the basis of the results obtained, and in addition a structure is proposed for the complex formed in this extraction system.     

Adsorption of Uranium(VI) and Zirconium(IV) from Acid Solutions on Silica Gel

Abstract

Adsorption of uranium(VI) and zirconium(IV) from aqueous solutions on silica gel was investigated by the batch equilibration method. The influence of shaking time and concentrations of nitric acid (i.e., pH of solution) and metal ions in solution were studied. Adsorption of uranium(VI) and zirconium(IV) increases with an increase of pH (decrease of nitric acid concentration) and ion concentrations. The adsorption mechanism of uranium(VI) and zirconium(IV) from aqueous solutions on silica gel is proposed. It is shown that zirconium(IV) and uranium(VI) can be separated if the concentration of nitric acid in solution is higher than 0.01 mol/dm³.