Separation and determination of zirconium and hafnium in uranium matrix

Hafnium and zirconium are separated from uranium using an anion exchange resin column. The two elements are then separated from each other using extraction chromatography and determined separately by precipitation as tetramandelate. The determination method was verfied by isotopic cilution technique. The method proved to be selective, quantitative (>99%) and gives an error of <±2%.     

Separation of uranium and thorium using tris(2-ethylhexyl) phosphate as extractant

The distribution behavior of uranium and thorium has been investigated in a biphasic system of different aqueous nitric acid concentrations and a solution of tris(2-ethylhexyl) phosphate (TEHP) inn-dodecane at 25°C. The effect of different uranium and thorium concentrations in the aqueous phase on the extraction of these metal ions is evaluated. These results indicate that TEHP is a better choice than tri-n-butyl phosphate (TBP) for the separation of²³³U from the irradiated thorium matrix.     

Separation of strontium and yttrium in nitric acid solutions using zirconium titanium phosphate and Dowex exchangers

Sulfonated ion irradiated (H⁺ and He²⁺) PEEK films were synthesized with a range of cross-linking density and a variety of sulfonation degrees. Batch adsorption experiments were carried out at an initial pH of 6.0 ± 0.2, initial concentrations of Pb²⁺ and ¹³⁷Cs ions of 10.0 mg L⁻¹ and 5500 Bq L⁻¹, respectively. The maximum adsorption capacity was 60 mg g⁻¹ for Pb²⁺, and the distribution coefficient reached 6200 cm³ g⁻¹ for ¹³⁷Cs. The results indicated that sulfonation could be used to recycle low cross-linked PEEK and prepare efficient adsorbents to remove toxic Pb²⁺ and ¹³⁷Cs from polluted aqueous solutions.

     

Neutron activation determination of uranium by coprecipitation of neptunium-239 on zirconium phosphate

A method is proposed for neutron activation determination of U via²³⁹Np. This is separated by coprecipitation of ZrO(H₂PO₄)₂ and its 106 keV γ-peak measured. The sensitivity of the determination is 10⁻⁹ g. The method is based on the well-known ability of Np(IV) to coprecipitate with zirconium phosphate, while Np(VI) does not form insoluble phosphates or fluorides. This permits elimination of elements interfering, with the determination of²³⁹Np via the 106 keV γ-peak: Sm, Nd, Yb, Lu, Pa (from Th) and Ta. The rare earths are eliminated by coprecipitation on LaF₃, and Pa and Ta as insoluble phosphates in an oxidizing medium. The method is suitable for phosphorus-containing samples: phosphorites, apatites and their industrial treatment products. The results obtained for the uranium content with the proposed method are in good agreement with the results of other methods and authors.     

Extraction-chromatographic separation of uranium from long-lived fission products using tributyl phosphate

Extraction-chromatographic separation of uranium from fission products was performed using undiluted tributyl phosphate sorbed on Chromosorb W as a stationary phase, and nitric acid (1: 3) as a mobile phase. Most of the fission products that contributed greatly to the radiation level of the sample passed through the column; this effected considerable decontamination. Uranium retained on the column was quantitatively recovered by elution with water.     

Separation of thorium from uranium ore

Thorium-230 has many research applications, but there is not a commercial source of this isotope. However, since ²³⁰Th is part of the ²³⁸U decay chain, it can be separated from naturally occurring uranium. In this work, a novel procedure was developed to separate thorium from uranium ore, consisting of leaching, liquid–liquid extraction, precipitations and ion exchange chromatography. The final product was 91.32?±?0.77 mg of thorium with a purity of 99.5?±?1.2 wt%. Of that, 7.65?±?0.10 mg was ²³⁰Th and the remainder ²³²Th. The total yield of ²³⁰Th was 71.1?±?5.4%. Ways to improve the yield by further processing the back-extraction solution are suggested.

     

Extraction behaviour of uranium,zirconium and ruthenium with gamma-irradiated sulfoxides and tri-n-butyl phosphate

The extraction, scrubbing and stripping behaviour of uranium, zirconium and ruthenium with di-n-hexyl and di-n-octyl sulfoxides in Solvesso-100 and tri-n-butyl phosphate (TBP) in shell Sol-T irradiated by various gamma doses (0–169 Mrads) have been investigated. 2M HNO₃ was used for extraction and scrubbing and 0.01M HNO₃ for stripping purposes. Results indicate that the extraction of uranium with TBP increases and that with sulfoxide decreases with dose. This is reflected in their corresponding scrubbing percentages too. The stripping percentage of uranium with TBP decreases with dose while the reverse is the case with sulfoxide. The extraction of zirconium with TBP increases sharply with dose as compared to sulfoxides. The extraction scrubbing and stripping of ruthenium remain almost unaffected by dose both in the case of TBP and sulfoxides. These results lead to much higher overall decontamination factors for uranium with respect to zirconium as well as ruthenium with irradiated sulfoxides as compared to those with irradiated TBP.     

Anodic electrodeposition of highly oriented zirconium phosphate and polyaniline-intercalated zirconium phosphate films

Films of highly oriented alpha-zirconium phosphate and polyaniline-intercalated zirconium phosphate with controllable thickness in the micrometer range were grown anodically on Pt electrodes. To optimize the electrodeposition conditions, the exfoliation of alpha-zirconium phosphate by tetrabutylammonium (TBA) salts was investigated in several nonaqueous solvents. Acetonitrile was found to be the best solvent for making crack-free, oriented films because of its high vapor pressure, low viscosity, and relatively high permittivity. With TBA salts of neutral or weakly acidic anions (TBACl, TBABr, TBAI, TBA(HSO4), or TBA(H2PO4)), full exfoliation did not occur and alpha-zirconium phosphate and/or polyaniline were deposited as rough films. With basic anions (TBAF or TBAOH), dense, adherent films were obtained. X-ray diffraction patterns of the films showed that they were highly oriented along the stacking axis. The thickness could be controlled, up to about 40 microm, by limiting the time of the electrodeposition reaction. At monomer concentrations below 1.0 x 10(-2) mol/dm3, the emeraldine form of the intercalated polymer was obtained. Electrodeposition thus provides a thick film alternative to layer-by-layer assembly for intercalation compounds of alpha-zirconium phosphate with a conducting polymer.     

Separation of uranium from iron in ground water samples using ion exchange resins

Uranium determination in environmental samples is faced with problems due to presence of iron and other major elements. Iron is also used many a times for pre-concentration of uranium and actinides. Separation of milligram quantity of Fe from microgram quantity of uranium becomes essential during the estimation step. A simple two step procedure has been standardized for separating uranium and iron using anion exchange in 0.025 M H₂SO₄. Quantitative recovery of uranium was obtained as well as good separation from iron. This method was applied for estimation of uranium in water samples.     

Recovery of uranium from phosphate by carbonate solutions

Uranium concentrations were analyzed in the Syrian phosphate deposits. Mean concentrations were found between 50 and 110 ppm. As a consequence, an average phosphate dressing of 22 kg/ha phosphate would charge the soil with 5–20 g/ha uranium when added as a mineral fertilizer. Fine grinding phosphate produced at the Syrian mines was used for uranium recovery by carbonate leaching. The formation of the soluble uranyl tricarbonate anion UO₂(CO₃)₃ ⁴⁻ permits using alkali and sodium bicarbonate salts for the nearly selective dissolution of uranium from phosphate. Separation of iron, aluminum, titanium, etc., from uranium during leaching was carried out. Formation of some small amounts of molybdates, vanadates, phosphates, aluminates, and some complex metals was investigated. This process could be used before the manufacture of Tri-Super Phosphate (TSP) fertilizer, and the final products would contain less uranium quantities.     

Precipitation and purification of uranium from rock phosphate

This study was carried-out to leach uranium from rock phosphate using sulphuric acid in the presence of potassium chlorate as an oxidant and to investigate the relative purity of different forms of yellow cakes produced with ammonia, magnesia and sodium hydroxide as precipitants, as well as purification of the products with TBP and matching its impurity levels with specifications of the commercial products. Alpha-particle spectrometry was used for determination of activity concentration of uranium isotopes in rock phosphate, resulting phosphoric acid, and in different forms of the yellow cake. Likewise, atomic absorption spectroscopy was used for determination of impurities. On the average, the equivalent mass concentration of uranium was 119.38 ± 79.66 ppm (rock phosphate) and 57.85 ± 20.46 ppm (phosphoric acid) with corresponding low percent of dissolution (48 %) which is considered low. The isotopic ratio (²³⁴U:²³⁸U) in all stages of hydrometallurgical process was not much different from unity indicating lack of fractionation. Upon comparing the levels of impurities in different form of crude yellow cakes, it was found that the lowest levels were measured in hydrated trioxide (UO₃·xH₂O). This implies that saturated magnesia is least aggressive relative to other precipitants and gives relatively pure crude cake. Therefore, it was used as an index to judge the relative purity of other forms of yellow cakes by taking the respective elemental ratios. The levels of impurities (Fe, Zn, Mn, Cu, Ni, Cd and Pb) in the purified yellow cake were found comparable with those specified for commercial products.     

Separation of antimony from synthetic cloth: Application in forensic science using neutron activation analysis

Summary A simple ion-exchange separation procedure was developed for selective removal of antimony from synthetic cloth to facilitate determination of several trace elements frequently used to identify gunshot residues by neutron activation analysis. Radiotracers of Sb, Ba, Cu, Co, As, Zn, Hg and Ag were employed to optimize the developed procedure. The method involves the quantitative retention of the above elements, except of Sb, from 0.2M ammonium carbonate solution using Chelex 100 resin and subsequent quantitative elution of the elements of interest with 2M nitric acid for gamma-ray spectrometry. The procedure was tested by simulated gunshot residues.     

Separation of uranium from soils for its determination

A method has been developed for the determination of microamounts of uranium in soils, which is based on application of the rapid and effective removing of luminescence quenchers from liquid preparations with subsequent uranium determination by laser-induced luminescence registration of its polysilicate complexes. To remove the luminescence quenchers, they were precipitated in strongly basic carbonate medium in the presence of activated charcoal (as a collector of the precipitate).     

Acidity of crystalline zirconium phosphate

The acid strength distribution has been measured for the crystalline zirconium phosphate thermally treated at various temperatures. There are two types of acids with remarkably different strength of acidity from one another; +4.8 ≥ Ho ≥ + 3.3 and −3.0 ≥Ho ≥−5.6. When the crystalline zirconium phosphate is thermally treated below 400°C, the total amount of acid is close to the ion exchange capacity and the number of POH groups. The amount of the strong acid gradually increases with temperature of thermal treatment up to 400°C. The amount of acid abruptly decreases around 450°C, and it becomes negligible after the thermal treatment above 490°C. An IR spectrum of pyridine adsorbed on crystalline zirconium phosphate indicates that the strong acid site is Brönsted type. TG-DSC curves and X-ray diffraction patterns also have been measured for the crystalline zirconium phosphate thermally treated at various temperatures. The amount of residual zeolitic water gradually decreased with increasing temperature of thermal treatment. The amount of residual POH groups remains constant up to 445°C, and it abruptly decreases around 480°C. From these results, it has been concluded that both the strong and the weak acid sites are the POH groups.     

Recovery of uranium and thorium from zirconium oxychloride by solvent extraction

A solvent extraction process is proposed to recover uranium and thorium from the crystal waste solutions of zirconium oxychloride. The extraction of iron from hydrochloride medium with P350, the extraction of uranium from hydrochloride with N235, and the extraction of thorium from the mixture solutions of nitric acid and the hydrochloric acid with P350 was investigated. The optimum extraction conditions were evaluated with synthetic solutions by studying the parameters of extractant concentration and acidity. The optimum separation conditions for Fe (III) are recognized as 30% P350 and 4.5 to 6.0 M HCl. The optimum extraction conditions for U (VI) are recognized as 25% N235 and 4.5 to 6.0 M HCl. And the optimum extraction conditions for Th (VI) are recognized as 30% P350 and 2.5 to 3.5 M HNO₃ in the mixture solutions. The recovery of uranium and thorium from the crystal waste solutions of zirconium oxychloride was investigated also. The results indicate that the recoveries of uranium and thorium are 92 and 86%, respectively.     

Separation of uranium from molybdenum using a diamine functional group bonded to controlled-pore glass

A method for selective extraction of uranium from carbonate solutions containing molybdate is reported. A liquid chromatography column, packed with N-β-aminoethyl-γ-ammopropyltrimethoxysilane immobilized on a glass substrate, was utilized in a continuous How system. The selective retention of the uranyl carbonate species [UO₂(CO₃)₂? 2H₂O]^2- and UO₂(CO₃)^4- on protonated immobilized diamine is the basis for this separation Recoveries of uranium and molybdenum from synthetic samples ranged from 96.7 to 113.4% for uranium and from 96.7 to 110.5% for molybdate for a range of recommended conditions.     

Separation of uranium from uraniferous coaly clays using a selective ion-exchange two-step elution system

Summary An ion-exchange process for the selective separation and enrichment of uranium from the main elements Si, Al, Fe, Ca, Mg, Na, K as well as from Mo and V, which are present in uraniferous coaly clays, has been developed. After a selective carbonate leaching of the roasted ore, a 0.5 mol/l Na₂CO₃/0.5 mol/l NaHCO₃ solution was passed through the macroporous ion-exchanger AG MP-1, which at pH10 absorbed uranium quantitatively in form of a carbonato complex. Remaining absorbed amounts of Mo and V were eluted with 0.1 mol/l EDTA in 0.5 mol/l Na₂CO₃/0.5 mol/l NaHCO₃, while U was quantitatively separated by a second elution step with 0.5 mol/l HNO₃ and was afterwards precipitated with NH₄OH as a high-grade yellow cake. Differential pulse polarography (DPP), atomic absorption spectroscopy (AAS), X-ray fluorescence (XRF), instrumental neutron activation analysis (INAA) and inductively coupled plasma mass spectrometry (ICP-MS) had been used to determine the uranium content in the raw materials and to investigate the effectivity of the different steps of the developed process.