Separation of gram quantities of uranium from fission products by extraction chromatography

The separation of gram quantities of uranium from fission products has been investigated by extraction chromatography. The separation which is based on the difference in distribution coefficients between uranium and the fission products on a tributyl phosphate (TBP) resin in nitric acid medium, was carried out by means of high acidity feed and stepwise elution on a TBP chromatography column. The results show that this technique is capable to separate 5 g of uranium from a large quantity of fission products. The recovery of uranium is more than 99%. The decontamination factors of g- and b-activities were 2.1^.10³ and 2.3^.10³, respectively.     

Determination of gamma impurities in fission product99Mo

The methodology is given for determination of very low quantities of gamma impurities:⁹⁵Zr,⁹⁵Nb,¹⁰³Ru,¹³¹I,¹³²Te,¹³²I,¹⁴⁰Ba,¹⁴⁰La,¹⁴¹Ce,¹⁴⁴Ce in⁹⁹Mo produced by separation from other fission products, by means of different measurement conditions such as initial activity, decay time and attenuation with lead.Presented as a poster at the International Conference on Nuclear and Radiochemistry, Beijing, P.R. China, September, 1986.     

Separation of99Mo from132Te using thiourea as complexing agent. Application to the separation of99Mo from fission products

A radiochemical method to isolate⁹⁹Mo from¹³²Te, both produced in the fission of²³⁵U, has been developed. The method is based on the formation of a cationic complex of tellurium with thiourea in acid medium which is retained (98.7±0.5)% on a cation exchange resin (Dowex 50W-X8, 100–200 mesh), while (99.8±0.05)%⁹⁹Mo passes through it, due to the non-formation of such complex in the same experimental conditions. The radionuclidic purity of⁹⁹Mo was found to be suitable for the preparation of⁹⁹Mo–^99mTc generators. The retention of⁹⁹Mo on an alumina column as a function of pH was investigated and the best pH range for this purpose was found to be 4.0–4.5.     

Separation of 99Mo from a simulated fission product solution by precipitation with a-benzoinoxime

The formation property of Mo precipitate was investigated and improved the existing process was using H₂O₂ that acts as an interfering compound in a subsequent alumina adsorption process. The property of the Mo precipitate was investigated by using SEM, FTIR, TG-DTA, and XRD. The simulated solution consisted of 1M nitric acid containing seven elements (Mo, I, Ru, Zr, Ce, Nd, Sr) and their radioactive tracers. As a result, the precipitate was composed of the Mo precipitate and re-precipitated a-benzoinoxime which was added excessively for increasing the precipitation efficiency. It was confirmed that the Mo precipitate was formed by the reaction of two a-benzoinoxime molecules and one MoO₂ ²⁺. Molybdenum precipitate was dissolved in 0.4M NaOH solution within 5 minutes without H₂O₂. Hydrogen peroxide induced only the rapid dissolution of the a-benzoinoxime re-precipitate. Also, the dissolution method without H₂O₂ was favorable in the purification aspect because Zr and Ru were contained as a small fraction of 1.3% and 7.7%, respectively, in the dissolving solution.     

Separation of fission and corrosion products from boric acid solutions by solvent extraction

Extractive purification of boric acid from radioactive corrosion and fission products dissolved in aqueous solutions modelling nuclear reactor coolants has been studied. Aliphatic 1,3-diols containing 8 and 9 carbon atoms per molecule were used as extractants fro boric acid. The behaviour of some representative corrosion and fission products as well as various factors affecting their distribution between the organic and aqueous phases have been investigated under the conditions of boric acid extraction. Conditions for the effective separation of boric acid from most of the radioactive contaminants are presented.     

Determination of trace level impurities in uranium compounds by ICP-AES after organic extraction

The determination was studied of Al, B, Be, Cd, Ca, Co, Cu, Mg, Mn, Mo, Pb, Si, Sn, V, Cr, Ni, and Fe as trace level impurities in uranium compounds by ICP-AES after extraction of uranium with three different mixtures of di-(2-ethyl-hexyl) phosphate (D2EHP) and tri-(2-ethyl-hexyl)-phosphate (T2EHP) in solvents like toluene, carbon tetrachloride, hexane and cyclohexane. The study was carried out in presence of different concentrations of HCl and HNO₃. A single extraction with D2EHP in cyclohexane using nitric acid as matrix was sufficient to reduce the U₃O₈ concentration from 100 g/l to 100 g/ml. The ICP-AES instrumentation applied, allowed the determination of metal concentrations ten-times lower than those usually found in nuclear grade U₃O₈. To check the efficiency of the extraction and the accuracy of the proposed method, Certified Reference Materials were used in the dissolution and extraction steps. The method described can be used for the determination of trace metals in nuclear grade U₃O₈.     

Determination of trace level impurities in uranium compounds by ICP-AES after organic extraction

The determination was studied of Al, B, Be, Cd, Ca, Co, Cu, Mg, Mn, Mo, Pb, Si, Sn, V, Cr, Ni, and Fe as trace level impurities in uranium compounds by ICP-AES after extraction of uranium with three different mixtures of di-(2-ethyl-hexyl) phosphate (D2EHP) and tri-(2-ethyl-hexyl)-phosphate (T2EHP) in solvents like toluene, carbon tetrachloride, hexane and cyclohexane. The study was carried out in presence of different concentrations of HCl and HNO(3). A single extraction with D2EHP in cyclohexane using nitric acid as matrix was sufficient to reduce the U(3)O(8) concentration from 100 g/l to 100 microg/ml. The ICP-AES instrumentation applied, allowed the determination of metal concentrations ten-times lower than those usually found in nuclear grade U(3)O(8). To check the efficiency of the extraction and the accuracy of the proposed method, Certified Reference Materials were used in the dissolution and extraction steps. The method described can be used for the determination of trace metals in nuclear grade U(3)O(8).     

Selective separation of99Mo from fission products in chloride media on activated alumina

The radioisotope⁹⁹Mo generated through the fission of neutron-irradiated uranium targets was separated in an extremely radiochemically pure state. The target dissolution mixture was run on a silica gel column whereby the⁹⁵Zr−⁹⁵Nb activity, the serious radiocontaminants of⁹⁹Mo, was adsorbed on the gel. The effluent from the gel column was processed and treated with sodium dihydrogen phosphate. The processed solution was run on an activated alumina column whereby⁹⁹Mo was adsorbed as phospho-molybdate complex ion, then desorbed from the column as the molybdate ion by eluting with 10% NaOH solution. By recycling the adsorption and desorption steps on alumnia,⁹⁹Mo was finally obtained totally free from all other radiocontaminants.     

99Mo提取后的裂变残液中铀回收技术初步研究

本文对裂变99Mo提取后残液中铀的回收进行了不同类型萃取溶液的效率对比,最终选择了萃取效率最好的30%二-(2-乙基乙基)磷酸的正十二烷溶液进行了条件实验,结果表明体系的HNO3浓度在4.0mol/L附近铀的分配比达到最大值,萃取过程为放热反应,且提高搅拌强度有利于加快萃取速率。     

Separation of iodine produced from fission with a porous metal silver column in99Mo production

In Argentina, at the Ezeiza Atomic Center,¹³¹I is produced by wet distillation of natural tellurium dioxide irradiated with thermal neutrons in a pool-type reactor. In order to recover the¹³¹I present in the production process of fission⁹⁹Mo obtained by irradiation of UAL_x/Al targets (with 90% enriched uranium) a separation method was developed. Iodine isotopes can be separated from a sodium hydroxide solution containing fission products using a column filled with alternate beds of glass microspheres and porous metal silver. Tests with tracers were performed in radiochemical laboratory. Following this results, a series of tests with higher activities (3 TBq of⁹⁹Mo and 0.7 TBq of¹³¹I) were carried out in hot cells. Molybdenum passes through the silver column, while¹³¹I retention was 92–97% in tracer test and 90% in optimised hot cell tests. This result depends on several facts that are discussed. An initial separation of iodine isotopes diminishes radiation damage on ion-exchange resin used in the subsequent molybdenum purification, improving its retention and elution yield.     

Separation of99mTc from parent99Mo by solid-phase column extraction as a simple option for a new99mTc generator concept

Evidence is obtained to show that the liquidliquid extraction separation of^99mTc from⁹⁹Mo with methyl ethyl ketone, methyl propyl ketone and methyl isobutyl ketone can be transformed into a solid-phase column extraction procedure. The aqueous alkaline⁹⁹molybdate solution is immobilized on a column of a granular large-pore diatomaceous earch support, which is the neluted with the abovementioned extractants. Rapid and clean separation of^99mTc can be with all three solvents. The^99mTc can be back-extracted from the organic phase on a column filled with distilled water /or saline/ loaded granular diatomaceous earth /Extrelut^®/. The possibility of using the abovementioned procedure as a basis for a new^99mTc/⁹⁹Mo generator concept is envisaged.     

Production of fission 131I

Summary A method of iodine separation from other radionuclides generated by ²³⁵U fission has been developed in order to explore the possibilities to obtain ¹³¹I as by-product of the ⁹⁹Mo routine production in the Ezeiza Atomic Centre. The experiments were designed to remove this element to gas phase, and the recoveries were investigated both with and without carrier addition. High volatilization percentages were achieved in the presence of iodine carrier. Some other alternatives to increase the iodine displacement to the gaseous phase, namely vacuum distillation, addition of hydrogen peroxide and use of a carrier gas, were also studied. The method developed, which employs a carrier gas stream, without carrier addition, allows the recovery of about 97% of the ¹³¹I, with high specific activity, in a simple and clean way.     

Separation and purification of 99mTc from 99Mo produced by electron linear accelerator

The medical radionuclide ⁹⁹Mo was produced by the ¹⁰⁰Mo(γ,n) reaction using bremsstrahlung photons generated by an electron linear accelerator. The amount of ⁹⁹Mo produced was compared to that predicted by calculation using the particles and heavy ion transport code system. From the ⁹⁹Mo produced, highly pure ^99mTc was separated using the so-called technetium master milker, and the chemical yield of ^99mTc was 83–99 %. The installation of a new complex using this method and the electron linear accelerator with the preferable specification was suggested, and a possibility to supply the demand of ^99mTc was discussed and shown.

     

Radiochemical determination of fission products of uranium

An analysis has been elaborated to determine the long-living γ-emitting fission products of uranium. It consists of a sodium bisulphate melt of the fission product solution or the U-fuel, followed by liquid-liquid extractions. Afterwards the isotopes are absolutely counted with a standardized 3″×3″ NaI crystal. The total γ-spectrum of the original fission product solution, taken with a NaI crystal or a Ge−Li detector, is also analyzed mathematically by mixed γ-spectrometry. From a short post-irradiation of the fission product solution the concentrations of both²³⁵U and²³⁸U are determined. The absolute amount of fission products related to the U-concentration allows the calculation of the percent atomic burn-up, the irradiation time, the cooling period, the flux of the reactor and the original degree of enrichment of the uranium. Research associate of the I. I. K. W.     

Determination of certain trace impurities in uranium concentrates by activation analysis

A method is presented for the simultaneous determination of chromium, iron, cobalt and zinc in samples of uranium concentrates, oxides and metallic uranium by neutron-activation analysis. The method involves adequate decontamination of gross fission product activities by adsorption on silica gel, removal of uranium by solvent extraction, separation of most carrier-free rare-earth activities by coprecipitation with aluminium chloride, and, finally, fractional separation of the elements concerned by ion-exchange chromatography. The method can assay ppm of such elements in limited quantities of samples by scintillation gamma-ray spectrometric analysis with a reproducibility of 10-15%.     

Separation of trace rare earths and other metals from uranium by liquid-liquid extraction with quantitation by inductively-coupled plasma/mass spectrometry

N,N-Dihexylacetamide in toluene was used to extract uranium selectively from an aqueous phase containing 30 elements at 10 or 100 μg l^?1 concentrations. After three extractions, the uranium level fell from 119 000 mg l^?1 (0.5 M) to less than 3 mg l^?1. An inductively-coupled plasma/mass spectrometer (i.c.p./m.s.) was used to determine recoveries of the trace elements in the aqueous phase, which, in most cases, were in the range 90–110%. This combination of liquid-liquid extraction with i.c.p./m.s. offers determinations at the 10 ng g^?1 level in uranium for most of the elements studied.     

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.     

Species dependent extraction of 99Mo

The liquid–liquid extraction profile of molybdenum has been studied with di-(2-ethylhexyl) phosphoric acid from different HCl media. The careful study of extraction profile clearly indicates various species of molybdenum at different acid strengths, which have been interpreted with reference to established data.     

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.