Separation of carrier-free 90Y from 90Sr using flat sheet supported liquid membranes containing multiple diglycolamide-functionalized calix[4]arenes

Abstract

Five diglycolamide-appended calix[4]arene (C4DGA) ligands, viz. C4DGA with no substituent (L-I), n-propyl (L-II), 3-pentyl (L-III), n-octyl (L-IV) and both side (L-V) substituents were evaluated for the separation of carrier free ⁹⁰Y from a ⁹⁰Y–⁹⁰Sr mixture using the flat sheet supported liquid membrane technique. Based on the results of earlier batch studies, the transport properties of the C4DGA ligands towards Y(III) and Sr(II) were monitored at two different feed acidities. The transport rates were significantly lower for 6 M HNO₃ as compared to 3 M HNO₃ as the feed. After 6 h, the observed trend of Y(III) transport with the C4DGA ligands using a feed of 3 M HNO₃ was: L-I ~ L-III > L-V > L-IV > L-II which changed to L-III > L-I > L-IV > L-V > L-II for 6 M HNO₃ as the feed. With 3 M HNO₃ as feed, >97% Y(III) transport was obtained with L-I and L-III in 6 h. Comparative Sr(II) transport was negligible resulting in high decontamination factors. In a one-step separation process, using L-I as the carrier ligand, pure ⁹⁰Y was obtained as the respective complex with either EDTA or DOTA. The highlights of this liquid membrane-based separation method comprise: its easiness, one-step separation, low ligand inventory, relatively pure product and continuous method.     

Separation of 99Tc from low level radioactive liquid waste using hollow fiber supported liquid membrane: optimisation and performance evaluation

Journal of Radioanalytical and Nuclear Chemistry - Low level radioactive liquid waste (LLW) obtained after treatment of Intermediate level radioactive waste (ILW) is highly alkaline and rich in...     

Separation of lignosulfonate from its aqueous solution using supported liquid membrane

This paper presents an experimental and theoretical study on facilitated transport of lignosulfonate (LS) through a flat sheet supported liquid membrane using trioctylamine (TOA) as carrier and dichloroethane as diluent. The studies were carried out with various support materials and operating conditions (viz. carrier concentration, strip phase concentration, salt concentration, etc.) and their effects on the transport of LS. The results were analyzed to identify a suitable combination of support and operating condition that would yield best performance of the supported liquid membrane (SLM) in terms of fast and efficient transport of LS. The stability of the SLM was assessed in terms of loss of liquid from the pores of membrane support. The SLM is found to be stable till 10 h. Co-transport mechanism has been adopted in this work by using NaOH as the strip phase. It was observed that extraction of LS is increased with increase in concentration of NaOH up to a limiting value of 0.5 M NaOH. Difference of salt concentration between feed and strip phase considerably affect the separation process. The diffusional resistances of organic membrane (Δorg) and aqueous solution (Δaq) calculated from the permeation model, which is again a combination of three unique mechanisms viz., diffusion through a feed aqueous layer, a fast interfacial chemical reaction, and diffusion of carrier–complex through the organic membrane, are found to be 609.9 and 176.6 s cm⁻¹, respectively. The values of the diffusion coefficient in the membrane (D_org) and in the bulk organic phase (D_complex) are 1.67×10⁻⁹ and 6.68 × 10⁻⁸ m²s⁻¹, respectively. The extraction of LS is about 90%. Nearly 43% of LS can be recovered at optimum condition.     

Studies on the separation of 90Y from 90Sr by solvent extraction and supported liquid membrane using TODGA: role of organic diluent

Solvent extraction and supported liquid membrane transport studies on Y(III) and Sr(II) were carried out using both nitric as well as hydrochloric acid feed conditions using N,N,N′,N′-tetra-octyldiglycolamide (TODGA) in several organic diluents. The solvent extraction studies indicated extremely large separation factor (SF) values with chloroform, carbon tetrachloride, 1-decanol and hexone when 6 M HNO₃ was used as the feed. On the other hand, the SF values were 1–2 orders of magnitude lower when the nitric acid concentration was 3 M HNO₃. Significantly large SF values were also obtained from 6 M HCl when xylene, carbon tetrachloride, n-dodecane and hexone were used as the diluent. Though mass transfer was not very promising in the supported liquid membrane studies with most of the diluent systems, quantitative Y(III) transport was observed with 0.1 M TODGA in xylene with negligible Sr(II) transport suggesting possibility of obtaining carrier free ⁹⁰Y. The purity of the radiotracer was checked by half-life method.     

Studies on the partitioning of actinides from high level liquid waste solution employing supported liquid membrane with Cyanex-923 as carrier

The present paper deals with the studies on the partitioning of actinides from high level liquid waste solution of PUREX origin employing supported liquid membrane technique. The process uses solution of Cyanex-923 in n-dodecane as a carrier with poly tetra fluoro ethylene support and a mixture of citric acid, formic acid and hydrazine hydrate as a receiving phase. Transport studies are carried out for ²⁴¹Am under different experimental conditions to optimize the transport parameters such as feed acidity, carrier concentration, effect of uranium, trivalent metal ion and salt concentration in the feed. Studies indicated good transport of actinides across the membrane from nitric acid medium. Under the optimized conditions the transport of ²⁴¹Am is studied from a uranium depleted synthetic PHWR-HLLW and finally the technique has been used for the partitioning of alpha emitters from an actual research reactor-HLLW. High concentration of uranium in the feed is found to retard the transport of americium, suggesting the need for prior removal of uranium from the waste.     

Extraction chromatographic separation of carrier-free90Y from90Sr/90Y generator by crown ether coated silica gels

A remarkable extraction chromatographic method for the preparation of⁹⁰Y of high radiochemical purity has been developed. The generator consists of silica gel coated crown ether. It functions as a strong adsorber for⁹⁰Sr and in the meantime high purity of⁹⁰Y is eluted with a dilute solution of picric acid after a suitable period. The experiments indicated that DC18C6 coated silica gel is better than that of DB18C6 coated. The extraction capacity of strontium on 3.8% DC18C6 coated silica gel is 5.6 mg Sr/g silica gel. Yttrium is obtained with more than 95% milking yield with radionuclide purity greater than 99.9%. The extraction chromatographic generator does not change its characteristics even after 5 elutions.     

The solvent extraction of carrier-free90Y from90Sr with crown ethers

A simple solvent extraction method has been developed for the separation of⁹⁰Y from⁹⁰Sr. Crown ether dissolved in chloroform was used as a selective reagent and organic picrate anion was chosen as a counter ion. The effect of various factors on the extraction separation of strontium and yttrium in the system have been studied. The extraction equilibrium constant of strontium logK _ex=9.15 was obtained from the study of the distribution coefficient versus the crown ether concentration. The separation method was simple, resulted high purity (>99.9%) and quantitative yield, and took less than half an hour.     

Cr(VI) ion removal from artificial waste water using supported liquid membrane

In this study, a novel flat-type synergic-supported liquid membrane was evaluated with a mixture of N-methyl-N,N,N-trioctylammonium chloride (Aliquat 336) and tributyl phosphate (TBP) as the carrier and kerosene as the diluent to remove Cr(VI) from synthetic waste water. The main parameters involved in the process were identified and optimised. The parameters were divided into two groups, those that were independent and those having an interaction. The parameters of the carrier/kerosene volumetric proportion and stirring rate were optimised individually due to their nature. The optimal values of these parameters were 0.5 and 500 min^?1, respectively, for a constant carrier/kerosene ratio and stirring rate in the designed experiments using the response surface method (RSM). The four parameters of TBP/Aliquat 336, chromium concentration in the feed phase, feed and product pH were optimised using RSM; it was observed that the TBP/Aliquat 336 ratio, feed pH, pH of the stripping phase and interaction of this parameter with feed concentration have the most important effects on the removal of Cr(VI). The optimal levels of these parameters were 0.61, 71.75 mg L^?1, 3.5 and 12.66 for the ratio of TBP/Aliquat 336, feed chromium concentration, pH of the feed and pH of the product, respectively. An experimental removal rate of 94.63 % at the optimized levels was obtained.     

Separation of 90Y from 90Sr using sequential multiple column extraction chromatography

The distribution coefficient measurements on Y(III) and Sr(II) were performed using ditertiarybutyl dicyclohexano 18-crown-6 (Sr-selective resin) and N,N,N′,N′-tetraoctyldiglycolamide (Y-selective resin) in HNO₃, HCl and HClO₄ media. Separation factors (⁹⁰Y/⁹⁰Sr) based on distribution coefficient data suggested that perchloric acid is distinctly better medium as compared to nitric acid/hydrochloric acid. The mechanism of extraction changes with the nature and concentration of acid and is responsible for the high selectivity in perchloric acid medium. Sequential column studies were carried out on tracers (radioactive/stable) employing Sr-selective/Y-selective extraction chromatographic resins as stationary phases. The final elution of ⁹⁰Y was done in 0.01 M EDTA at pH 4.0 which can be used for clinical applications after radiochemical processing.     

Separation of plutonium from intermediate level liquid waste by precipitation with alkyl-pyridinium nitrates

Summary Plutonium as hexanitrato complex can be separated from intermediate level liquid waste by precipitation with various alkylpyridinium nitrates. The residual concentrations of Pu are below 10^–6 mol/l.

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Abtrennung von Plutonium aus mittelaktivem flüssigen Abfall durch Fällung mit Alkylpyridiniumnitraten

Zusammenfassung Plutonium wird als Hexanitratokomplex aus einem mittelaktiven Abfall durch Fällung mit verschiedenen Alkylpyridiniumnitraten abgetrennt. Die Restkonzentrationen von Pu betragen weniger als 10^–6 mol/l.

     

Recovery of molybdenum by solvent extraction from simulated high level liquid waste

Journal of Radioanalytical and Nuclear Chemistry - In this study, simple and a rapid solvent extraction method is investigated to recover Mo(VI) from simulated HLLW. The (NH4)6Mo7O24·4H2O...     

Separation of cesium from intermediate level liquid radioactive waste by solvent extraction with antioxidants

The intermediate level liquid radioactive wastes (RAW) isussed from nuclear power plants have high salt contents ca 200 g·dm^–3, the pH of liquid RAW being 12.5–13.7. A convenient method for separation of cesium under these conditions is solvent extraction with substituted phenols. For this purpose weere tested antioxidants produced in Czechoslovakia: AO 2246 [2,2-methylene-bis-(4-methyl-6-tertbutyl)phenol]; AO 4 [2-tertbutyl-4-(2-phenylpropyl)phenol]; AO 4K [2,6-ditertbuty-4-methylphenol]; AO 301 [2,2-methylene-bis-(4-{2-phenylpropyl}-6-tert-butyl)phenol]; and one antioxidant imporoted from Japan—NOCRAC 2246. This antioxidant is equivalent to AO 2246. After the first experiment it was found that the extraction efficiency for antioxidants AO 4 and Ao 301 is very low and the following experiments were made with AO 2246 (NOCRAC 2246) and AO 4K. Some effects on extracton as, pH of water phase, influence of diluent, influence of concentration of antioxidants, extraction time, were studied. The best results gave antioxidant NOCRAC 2246 in nitrobenzene, the extraction efficiency was 92.3% with pH 13.23.     

Reduction and removal of neptunium from synthetic high level liquid waste by TRPO process

Valency control of neptunium is an important issue in the partitioning of high level liquid waste (HLLW) from power-reactor spent fuel treatment. The redox behavior of neptunium in HLLW is quite different from that in nitric acid because of the effect of the large amount of ions in HLLW. In order to remove neptunium from HLLW, we studied the reduction of neptunium in synthetic HLLW (SHLLW) to maintain its valency at IV so that it can be extracted by TRPO extractant in the well developed Chinese TRPO process. Five different reductants were tested and the reduction behavior was investigated. The influence of some active elements in SHLLW was studied. The mechanism that the reductants react with neptunium through Fe element was supposed and proved by experiments. The reduction rate of Np(V) was highly enhanced by Fe element. Finally, a hybrid reductant was suggested and good reduction efficiency was obtained.     

Separation of carrier-free arsenic from germanium

A method for the separation of carrier-free arsenic from bulk amount of germanium has been developed.^74,73As has been produced through the reaction^natGe(p,xn)^47,73As with 13 MeV protons obtained from Variable Energy Cyclotron, Calcutta. The separation is performed by the distillation of Ge followed by anion exchange separation of As(V) using Dowex 1×8 anion exchange resin. The overall chemical yield is found to be (87±3%).     

Separation of carrier-free silver from neutron-irradiated palladium

The use of a chelate-forming ion-exchange resin for the separation of carrier-free silver-111 from neutron irradiated palladium is described. On décrit l'emploi d'une résine échangeuse d'ions formant des chélates pour la séparation de l'argent-111 exempt d'entra?neur du palladium irradié aux neutrons.     

Separation of some carrier-free nuclides from matrices by chelate extraction

Separation procedures based on chelate extraction are described, which can be used in the course of production of carrier-free nuclides. The selectivities of the separations dealt with are fairly high, while the overall yield depends on the experimental conditions, primarily on whether the micro- or the macrocomponent of the system can be chelated. The problems encountered in the production of carrier-free⁶⁴Cu,⁶⁷Cu,⁸⁴Rb and¹¹¹Ag are briefly discussed.     

Recovery of actinides extracted by Truex solvent from high level waste using complexing agents

The sorption and migration of radiostrontium in a calcareous soil from Yu Zhong county of Gansu province (China) was studied using batch and column experiments. Sorption isotherms, breakthrough curves and concentration profiles for the untreated soil and the soil treated to remove CaCO₃ were determined, respectively. It was found that radiostrontium is a relatively mobile nuclide in calcareous soil and removal of CaCO₃ from the soil slightly increases the retention ability for radiostrontium. The breakthrough curves were fitted to the analytical solution of a one-dimensional convection-dispersion transport model that assumes a reversible linear isotherm. Good agreement was obtained between the measured and predicted concentration profiles.     

Recovery of actinides extracted by Truex solvent from high level waste using complexing agents

This work deals with the batch studies on stripping of actinides extracted by a mixture octyl(phenyl)-N,N-diisobutyl-carbamoylmethylphosphine oxide (CMPO) and tri-n-butyl phosphate (TBP) in n-dodecane (Truex solvent) from simulated high level waste (HLW) solution. The stripping of americium and plutonium from acid-bearing CMPO-TBP mixture is carried out using a mixture of weak acid, weak base and complexing agent as strippant. A mixture of formic acid, hydrazine hydrate and citric acid appeared to be best suited for efficient stripping of americium and plutonium. With appropriate modifications in the concentration of individual constitutents, this strippant can be used for the recovery of actinides from loaded Truex solvent with any acid content.     

Removal of137Cs from an intermediate level liquid waste by using various ion-exchange media

An intermediate level liquid waste (ILLW or Category III waste) stream was treated for the removal of radioactive Cs in pilot scale experiments, using three different ion exchange media. Results indicated that the polyacrylic fibre coated with cupric ferric hexacyanoferrate (CuFeHCF-fibre composite) was the most efficient, followed by cupric hexacyanoferrate loaded ion exchange resin (CuHCF-resin) and mixed zeolites (AR-1, 4A and 13X in the ratio 6:1:1). The mixed zeolites column and the CuFeHCF-fibre column were used in series in order to get a high total decontamination factor (DF). Leaching studies on the CuFeHCF-fibre composite loaded with¹³⁷Cs, in demineralised (DM) water, tap water and ground water media indicated a release of about 19.3%, 25.5% and 41.3% of¹³⁷Cs, respectively, in a period of about 8 months. XPS studies with CuFeHCF-fibre composite indicated some chemical interaction between the CuFeHCF precipitate and the polyacrylic fibre. Some of the possible disposal options for the CuFeHCF-fibre composite have also been discussed.