Chemical separation and inductively coupled plasma–atomic emission spectrometric determination of seventeen trace metals in thorium oxide matrix using a novel extractant – Cyanex-923

Comprehensive studies have been carried out on the extraction behaviour of thorium matrix vis-a-vis 17 trace metallic elements using a novel extractant viz. Cyanex-923. The near total extraction of thorium and quantitative separation of these metals has been established using inductively coupled argon plasma–atomic emission spectrometry (ICP–AES). The recovery of few representative elements has been confirmed by radio-active tracer studies. The studies carried out here have enabled determination of μg/l amounts of all analyte elements with a precision of better than 1% RSD with prior chemical separation from as low as 1 g thorium sample in just five chemical extractions.     

Chemical separation and ICP-AES determination of 22 metallic elements in U and Pu matrices using cyanex-923 extractant and studies on stripping of U and Pu

Comprehensive studies have been carried out on the extraction behavior of uranium and plutonium matrices using cyanex-923 extractant. The near total extraction of U/Pu and quantitative separation of 22 metallic elements at trace levels has been established using inductively coupled plasma-atomic emission spectrometry (ICP-AES). The studies carried out on back extraction of U/Pu from organic phase have established the near total recovery of these matrices into the aqueous phase using 1 M Na(2)CO(3) and saturated oxalic acid, respectively.     

Counter current extraction separation of rare earth traces

The discontinuous counter current extraction separation of radioactive traces of rare earth elements from each other was successfully performed by using a 96 stage automatic microscale counter current apparatus. Choice of the optimum composition of the aqueous phase (var. HNO₃ conc.) and organic phase [di-(2-ethylhexyl) phosphoric acid (HDEHP) in toluene] was made on the basis of the results of liquid-liquid extraction measurements. Providing sufficient content of HDEHP in the organic phase, the presence of macroamounts of uranium(VI) did not interfere with the individual separation of rare earth traces. Consequently, uranium was retained in the organic phase, while separated rare earth traces were redistributed into the aqueous phase. The methods of liquid-liquid extraction and extraction chromatography based on the use of HDEHP were compared. The present results confirm that the liquid-liquid extraction has the advantage to be selective for the separation of rare earth traces from each other and from the macroamount of uranium(VI).     

ICP-AES determination of silver after chemical separation from uranium matrix

The separation of silver from a uranium matrix has been carried out using Cyanex-471X (triisobutylphosphine sulphide) in xylene. The effects of various parameters such as the Cyanex-471X concentration, the nitric acid molarity, the contact time and the nitrate ion concentration on the extraction of silver have been studied. The silver metal ion species extracted into the organic phase was found to be Ag(NO₃)·2S (where S is Cyanex-471X). The stripping of silver into an aqueous medium was carried out with 5% NaHSO₃, followed by its determination using ICP-AES.     

Separation of high purity gadolinium for reactor application by solvent extraction process

A solvent extraction process for the production of nuclear grade Gd₂O₃ for its applications in pressurized heavy water reactor (PHWR) from a crude concentrate of rare earths containing ~70 % Gd₂O₃ has been developed and tested on bench-scale and continuous counter-current operations. The separation of gadolinium from other rare earths with similar chemical properties has been successfully accomplished by adopting a dual cycle solvent extraction employing 2-ethylhexylphosphonic acid, mono-2 ethylhexyl ester (EHEHPA) as an extractant. Taking advantage of the extraction order of rare earths with EHEHPA, in the first cycle, heavy rare earths including Tb, Dy and Y were separated in the product strip solution, while gadolinium was separated in the raffinate solution along with samarium and neodymium. In the second cycle, gadolinium was purified to the extent of >99.5 % with respect to other rare earths. Effects of process variables such as aqueous acidity, phase ratio, metal concentration in the aqueous feed, scrubbing and stripping acidity etc. on separation of terbium and other heavy rare earths in the first cycle and upgrading the purity of Gd₂O₃ in the second cycle have been investigated. The experimental conditions were optimized using computer simulation and validated by bench scale counter-current operations. Under optimized conditions of process parameters, continuous operations of mixer settler yielded kilogram quantity of nuclear pure Gd₂O₃ which was subsequently converted to gadolinium nitrate for PHWR application. The overall recovery was found to be >98 %.     

Extractive separation of Th(IV), U(VI), Ti(IV), La(III) and Fe(III) from Zarigan ore

In this study, the effects of various extraction parameters such as extractant types (Cyanex302, Cyanex272, TBP), acid type (nitric, sulfuric, hydrochloric) and their concentrations were studied on the thorium separation efficiency from uranium(VI), titanium(IV), lanthanum(III), iron(III) using Taguchi^??s method. Results showed that, all these variables had significant effects on the selective thorium separation. The optimum separations of thorium from uranium, titanium and iron were achieved by Cyanex302. The aqueous solutions of 0.01 and 1 M nitric acid were found as the best aqueous conditions for separating of thorium from titanium (or iron) and uranium, respectively. The combination of 0.01 M nitric acid and Cyanex272 were found that to be the optimum conditions for the selective separation of thorium from lanthanum. The results also showed that TBP could selectively extract all studied elements into organic phase leaving thorium behind in the aqueous phase. Detailed experiments showed that 0.5 M HNO₃ is the optimum acid concentration for separating of thorium from other elements with acidic extractants such as Cyanex272 and Cyanex302. The two-stage process containing TBP-Cyanex302 was proposed for separation thorium and uranium from Zarigan ore leachate.     

Estimation of trace impurities in reactor-grade uranium using ICP-AES

Estimation of impurities in reactor grade uranium is important from the point of view of neutron economy. For chemical separation, ion exchange and solvent extraction techniques have been employed although the latter is generally preferred. Amongst various extractants TBP (tri-n-butyl phosphate), TBP-TOPO (tri-n-octyl phosphine oxide), or TOPO only (in CCl(4), xylene, dodecane) is most often used. New reagents like Cyanex-923 (mixture of 4 tri-alkyl phosphine oxides)/TEHP (tri-ethylhexyl phosphoric acid) are also being used. This communication reports chemical separation of uranium by precipitation using 1,2-diaminocyclohexane NNN'N'-tetra acetic acid (CyDTA)/ammonium hydroxide in presence of 1,10-phenanthroline and estimation of impurities in the filtrate by ICP-AES. Quantitative separation of U, a high spectral interferent in plasma and recovery of impurities have been achieved. Recovery of Cd has been improved by using 1,10-phenanthroline. The method is accurate and precise, offering a relative standard deviation ranging from less than 4% (3.8% for Eu at the 10mug g(-1) level) to 12.9% (for Ce at the 2.5 mug g(-1) level) for all the elements studied.     

Liquid–liquid extraction of uranium(VI) using cyanex 272 in toluene from sodium salicylate medium

Liquid–liquid extraction and separation studies of uranium have been carried out from sodium salicylate media using cyanex 272 in toluene. Uranium was quantitatively extracted by 1 × 10⁻³ M sodium salicylate with 5 × 10⁻⁴ M cyanex 272 in toluene. The extracted uranium(VI) was stripped out quantitatively from the organic phase with 1.0 M hydrochloric acid and determined spectrophotometrically with arsenazo(III) at 660 nm. The effect of concentration of sodium salicylate, extractant, diluents, metal ion and strippants has been studied. Separation of uranium(VI) from other elements was achieved from binary as well as from multicomponent mixtures. The method was extended for the separation and determination of uranium(VI) in geological samples. The method is simple, rapid and selective with good reproducibility (approximately ± 2%).     

Separation and Recovery of Uranium and Plutonium from Oxalate Supernatant

The separation of uranium and plutonium from oxalate supernatant, obtained after precipitating plutonium oxalate, containing ~10 g/l uranium and 30–100 mg/l plutonium in 3M HNO₃ and 0.10–0.18M oxalic acid solution has been carried out. In one extraction step with 30% TBP in dodecane: ~92% of uranium and ~7% of Pu is extracted. The raffinate containing the remaining U and Pu is extracted with 0.2M CMPO+1.2 M TBP in dodecane and near complete extraction of both the metal ions is achieved. The metal ions are back extracted from organic phases using suitable stripping agents. The recovery of both the metal ions separately is >99%. The uranium species extracted into the TBP phase from the HNO₃+oxalic acid medium was identified as UO₂(NO₃)₂·2TBP.     

Understanding the extraction mechanism,radiolytic stability and stripping behavior of thorium by ionic liquid based solvent systems: evidence of ‘ion-exchange’ and ‘solvation’ mechanism

The extraction efficiency for thorium followed the trend: Cyanex-923 > Cyanex-272 > DHOA > TBP. In case of TBP and DHOA the extraction proceeded via ‘solvation mechanism’ through Th(NO₃)₄·2L, while for Cyanex-923 and Cyanex-272 it proceeded via ‘ion exchange’ mechanism through (Th(NO₃)₂·2L)²⁺. The extraction process followed slower kinetics while change in Gibb’s energy revealed the spontaneity of the process. These ionic liquid based systems were found to be radiolytically stable, highly efficient and selective for Th. Oxalic acid was found to be suitable for almost quantitative stripping of Th from extracted ionic liquid phase.     

Spectrophotometric determination of zirconium, uranium, thorium and rare earths with arsenazo III after extractions with thenoyltrifluoroacetone and tri-n-octylamine

A method is described for the spectrophotometric determination of microgram amounts of zirconium, uranium(VI), thorium and rare earths with Arsenazo III after systematic separation by extraction. First zirconium is extracted into a xylene solution of thenoyltrifluoroacetone (TTA) from about 4M hydrochloric acid. Uranium(VI) is then extracted into a xylene solution of tri-n-octy lamine from about 4M hydrochloric acid. Thorium is next extracted into TTA solution at pH about 1.5, and finally rare earths are extracted into TTA solution at pH about 4.7. Each metal is back-extracted from the organic phase before determination.     

Dosage par activation neutronique des terres rapes dans des roches uraniferes

The determination of rare earths by activation analysis in uranium containing rocks is disturbed either by fission-produced rare earths, or by neptunium-239 originating from uranium-238. In order to eliminate of these interferences the chemical separation of rare earths from uranium prior to activation should be performed. The purpose of this work was the elaboration of a chemical process to separate rare earths prior to irradiation in a nuclear reactor. The rock sample is fused with sodium borate, then, after addition of hydrochloric acid, the resulting solution is passed through a Dowex 1×8 column. Uranium is retained on the resin and rare earths and scandium are eluted. Aluminium is added as a carrier to the solution and rare earths and scandium are coprecipitated with aluminium hydroxide. This precipitate is irradiated in the nuclear reactor. Gamma spectrometry is used for the determination of each radionuclide. Activities measurements are performed in successive steps during one month. The following elements are determinated: Pr, La, Sm, Nd, Yb, Lu, Ce, Tb, Eu, and Sc. The chemical yield is measured by using scandium as an internal standard.     

Role of ligand softness and diluent on the separation behaviour of Am(III) and Eu(III)

Separation of trivalent actinides (An(III)) and lanthanides (Ln(III)) is a challenging task in the nuclear fuel cycle due to their similar charge and chemical behaviour. Some soft donor ligands show selectivity for An(III) over Ln(III) due to the formation of stronger covalent bonds with the former. The extraction behaviour of Am(III) and Eu(III) is studied in the present work with a mixture of Cyanex-301 (bis(2,4,4-trimethylpentyl)di-thiophosphinic acid) with several various ??N??, ??O?? or ??S?? donor neutral ligands. Comparison of the data was done with that of the oxygen donor analogue of Cyanex-301, i.e. Cyanex-272 (bis(2,4,4-trimethylpentyl)phosphinic acid). Effect of the organic diluent on the extraction behaviour of Am(III) using Cyanex-301 in presence of ??N?? donor synergists was also studied. Ab initio molecular orbital calculations were carried out using GAMESS software and charges on the donor atoms were calculated which helped in understanding the co-ordination chemistry of the ligands and explained the separation behaviour.     

Determination of valuable elements in natural phosphates

Natural phosphates are used on large scale in the fertilizer industry. The usual process of the chemical attack is sulfuric (predominant) and nitric acids. The liquid phosphoric acid phase resulted contains dissolved valuable elements like: uranium and rare earths elements (REEs). Uranium and REEs are recovered in some technologies as valuable products. It is therefore important to know, uranium and REEs content in natural phosphates in view to decide on their recovery. In this paper determinations were carried out to find the uranium and REEs contents. The concentrations involved are low, therefore, it is difficult to find a classical reliable method without incurring important losses, i. e., errors. In this work uranium and REEs were determined by physical methods like: neutron activation analysis (NAA), emission spectroscopy, mass spark spectrometry and X-ray fluorescence. The results obtained were acceptable and intercomparison between various methods was carried out. It was found that most reliable results were given by mass spark spectrometry and activation analysis. The data resulted are in good agreement with uranium and REEs in the green cake (uranium tetrafluoride) and in the REEs concentrate obtained by solvent, extraction from phosphoric acid.     

Extraction studies of the group IB,IIB, and IIIA–VA elements using 1-(2-pyridylazo)-2-naphthol as chelating reagent

The extraction of PAN chelates of the group IB, IIB and IIIA–VA elements from aqueous solutions of pH 1–10 into chloroform has been studied radiochemically. Re-extraction studies have been made to strip the metal ions from the organic phase into aqueous solutions of KCN, HClO₄ and buffer solutions. The effects of certain masking agents on the extraction of these elements have also been studied. The extraction curves indicate the possibilities of devising group chemical separation procedures for use in activation analysis.     

Solvent extraction of uranium from lean grade acidic sulfate leach liquor with alamine 336 reagent

This paper describes the solvent extraction studies carried out on an acidic low assay uranium bearing leach liquor generated during sulfuric acid leaching of a refractory uranium ore using alamine 336?Cisodecenol?Ckerosene reagent combine. The leach liquor has a U₃O₈ content of about 270?mg/L, free acidity 2.4?N H₂SO₄ and total dissolved solids concentration of 260?g/L. Process parameteric variation studies indicated strong influence of free acidity of the leach liquor, alamine 336 concentration and aqueous to organic phase ratio on the extraction efficiency of uranium. An extraction efficiency of about 95% was achieved when the free acidity of leach liquor was 1?N H₂SO₄ or lower, using 2% (v/v) alamine 336 at ambient temperature with an aqueous to organic phase ratio of 1:1. The loading capacity under these conditions was 1.2?g/L of U₃O₈. About 98% of the uranium values could be stripped from the loaded organic using 1?N NaCl in 0.2?N H₂SO₄. The solvent extraction studies aided in developing a suitable process flowsheet for treating refractory uranium ores which need high acidity during leaching and relatively lower acidity for purification by solvent extraction.     

Extraction of uranium, thorium and lanthanides using Cyanex-923: Their separations and recovery from monazite

The extraction behavior of uranium, thorium and lanthanides, represented by cerium and ytterbium, by Cyanex-923 has been investigated. The effect of different variables like the concentration of acids, metal ion and extractant, nature of diluent and temperature has been studied. A composition for the extracted U(VI) and Th(IV) species has been proposed. Based on the partition data some important binary and ternary separations involving the aforesaid metal ions have been achieved. The proposed procedure has been applied for the recovery of uranium, thorium and lanthanide fraction from monazite sand. The stability and regeneration capacity of the extractant have been evaluated.     

Solid phase separation and ICP-OES/ICP-MS determination of rare earth impurities in nuclear grade uranium oxide

A simple, effective and low cost solid phase extraction procedure was standardized for the trace and ultra-trace level determination of rare earth impurities, such as, Ce, Dy, Sm, Gd, Eu, Er etc. which act as neutron poisons, in nuclear grade uranium oxide (U₃O₈?>?99.9% by weight). The method involves selective separation of these elements as their fluorides with the help of activated charcoal from major uranium matrix followed by determination by ICP-MS and high resolution ICP-OES. The residual uranium content of the solution was <10???g/mL. The recovery of REEs ranges from 85 to 105%. The method was validated with nuclear grade uranium oxide standards CRM-I to CRM-V (BARC, Mumbai, India) in addition to some synthetic standards. The RSD of the method was ±12% (n?=?3).     

Insight of solvent extraction process: Reassessment of trace level determinations

Solvent extraction is hoary yet modern technique with great scope of research due to the various intriguing phenomena in the system. Tri-n-butyl phosphate (TBP) is a well known extractant which has been extensively used for separation of uranium matrix prior to elemental profiling. In this paper, one of the impurities namely Fe is being considered as it posed a challenge to the separation due to its co-extraction with TBP along with uranium. In these studies, for the first time, the existence of cation-cation inner sphere complexes between the UO₂²⁺and Fe³⁺ ions in both aqueous and organic phases have been establisted in addition to the selective separation of iron from uranium sample matrix using only TBP. The data from both spectrophotometric and thermophysical studies corroborated one another confirming the presence of cation-cation interactions (CCIs). The developed solvent extraction with only TBP showed almost no interferences on the iron extraction from matrix uranium and other co-ions like aluminum and copper. This has been the first time application of pure TBP for selective removal of iron from uranium samples. The procedure possessed excellent reproducibility and robustness.