Separation of carrier-free 90Y from high level waste by supported liquid membrane using KSM-17

A generator system has been developed for the preparation of carrier-free ⁹⁰Y from ⁹⁰Sr present in the high level waste (HLW) of the Purex process by employing a supported liquid membrane (SLM) using 2-ethylhexyl-2-ethylhexyl phosphonic acid (KSM-17 equivalent to PC 88A) supported on a polytetrafluoro ethylene (PTFE) membrane. When uranium depleted Purex HLW at appropriate acidity is passed sequentially through octyl (phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) sorbed on chromosorb-102 (abbreviated as CAC) and Zeolite AR1 (synthetic mordenite) columns, all the trivalent, tetravalent and hexavalent metal ions and monovalent ¹³⁷Cs ions are sorbed. After adjusting to pH 2 with NaOH the resulting effluent is used as feed in a single stage membrane cell partitioned with a PTFE membrane impregnated with KSM-17 and having a feed and receiver compartment with 5.0 ml capacity each. The receiver compartment was filled with a 0.5M HNO₃ or 0.5M HCl stripping solution. ⁹⁰Y alone is preferentially transported across the membrane leaving behind all the impurities viz. ⁹⁰Sr, ¹²⁵Sb, ¹⁰⁶Ru, ¹⁰⁶Rh, etc. in the feed compartment. This technique can yield ⁹⁰Y in mCi levels in a pure and carrier-free form for medical applications. The feed can be reused repeatedly after allowing for ⁹⁰Y buildup.     

Biosorption of actinides from dilute waste actinide solution by egg-shell membrane

Removal of radioactive elements from the effluent and waste aqueous solutions is an important problem. In previous laboratory batch experiments, hen egg-shell membrane (ESM) was stable as an insoluble protein and was very capable of binding heavy metal ions from aqueous solution. Batch laboratory pH profile, time dependency, and capacity experiments were performed to determine the binding of uranium (U) and thorium (Th) to ESM. Batch pH profile experiments indicated that the optimum pH for binding these actinides was approx 6.0 (U) or 3.0 (Th). The adsorption isotherms were developed at pH 5.0 (U) or 3.0 (Th) at 25°C, and the adsorption equilibrium data fitted both Langmuir and Freundlich models. The maximum uptakes by the Langmuir model were about 240 mg U/g and 60 mg Th/g dry weight ESM. In addition, their adsorption capacities increased as salt concentration increased. ESM could also accumulate uranium from dilute aqueous solution by adjusting to the optimum pH. These results showed that ESM was effective for removing actinides from solution and would be useful in filtration technology to remove actinides from aqueous solution. S.-I. Ishikawa is a research fellow at the Japan Society for the Promotion of Science.     

An advanced partitioning process for key elements separation from high level liquid waste

To separate MA(Am,Cm) and some fission product elements(FPs) such as Tc,Pd,Cs and Sr from high level liquid waste(HLLW) systematically,we have been studying an advanced aqueous partitioning process,which uses selective adsorption as the separation method.For this process,we prepared several novel adsorbents which were immobilized in a porous silica/polymer composite support(SiO 2-P).Adsorption and separation behavior of various elements was studied experimentally in detail.Small scale separation tests using simulated HLLW solutions were carried out.Pd(II) was strongly adsorbed by the AR-01 anion exchanger and effectively eluted off by using thiourea.Successful separation of Pd(II) from simulated HLLW was achieved.Tc(VII) also exhibited strong adsorption on AR-01 and could be eluted off by using U(IV) as a reductive eluent.Am(III) presented significantly high adsorbability and selectivity onto R-BTP/SiO 2-P adsorbents over various FPs including Ln(III).The R-BTP adsorbents were fairly stable in 3 M HNO 3,but instable against-irradiation-3M HNO 3.An advanced partitioning process consisting of three separation columns for the target elements separation from HLLW was proposed and the obtained experiment results indicated that the proposed process is essentially feasible.     

高放废液中分离回收镧系-锕系元素萃取剂的研究进展

概述了近十几年来国内外有关用于高放废液镧系-锕系元素萃取分离中新萃取剂的研究进展,并对酰胺类、硫代磷类、硫代吡唑啉酮类等新萃取剂的设计筛选等进行了讨论。     

Scaling-up experience of actinides partitioning from intermediate level high salted alkaline waste streams of Purex process using Versatic-10 extractant

Partitioning of minor alpha-emitting actinides, especially U, Pu and Am from medium active alkaline waste is possible from intermediate level liquid wastes (ILLW) produced during spent fuel reprocessing following Purex process. This paper deals with the efficient removal of alpha-activity from ILLW by solvent extraction process. Counter current batch extraction with O/A ratio 2:1 as well as multistage mixer settler has demonstrated that most of the alpha-activity was removed from the alkaline effluents using 20% Versatic-10 (V-10) in dodecane after giving 3 to 4 contacts, thus converting alkaline waste as non-alpha waste. Under the optimum conditions (pH 9.0-9.5 and VA-10), both Pu(IV) and Am(III) are highly extractable whereas U(VI) is relatively poorly extracted. To assess the applicability of this process for regular treatment of the waste, a feasibility study on pilot plant scale using six stage mixer settler was operated to treat the ILLW. The results indicated that almost >99.90% alpha-emitting actinides are removed. Dilute nitric acid (0.5M HNO₃) served as the most efficient strippant for all these actinides. This facilitate an easy regeneration of the extractant which can be recycled. This method is useful in obtaining alpha-free wastes and had positive impact on ease and safety aspects during subsequent waste treatment and long term storage.     

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.     

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.     

A novel partitioning process for treatment of high level liquid waste using macroporous silica-based adsorbents

To separate the long-life and significant fission product elements from high level liquid waste (HLLW), a novel partitioning process for the treatment of HLLW has been studied experimentally based on column separation technique using macroporous silica-based adsorbents. This process consists of (1) Cs and Rb are removed by the first separation column packed with (calix[4] + dodecanol)/SiO₂–P adsorbent; (2) Sr and Ba are eluted out by the second separation column packed with (DtBuCH18C6 + dodecanol)/SiO₂–P adsorbent; (3) Pd is partitioned by the third separation column packed with MOTDGA–TOA/SiO₂–P adsorbent; (4) Ru, Rh and Mo can be separated by the fourth separation column packed with TODGA/SiO₂–P adsorbent; (5) Am is separated from RE by the fifth column is packed with isobutyl-BTP/SiO₂–P adsorbent. The experimental results indicated that this partitioning process is essentially feasible.     

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...     

Carrier facilitated transport of thorium from HCl medium using Cyanex 923 in n-dodecane containing supported liquid membrane

Present studies deal with supported liquid membrane (SLM) technique for the separation of thorium from hydrochloric acid (HCl) medium using Cyanex 923 as a carrier. Effects of feed acidity, strippant, and membrane pore size and membrane thickness on the transport of thorium have been studied in detail. The optimized parameters were applied for separation of thorium from a radioanalytical waste. Stability of the membrane and membrane support was investigated. Transport of thorium increased from 78.3 to about 93.7 % with increase in acidity from 0.5 to 2 M using 0.3 M Cyanex 923 in n-dodecane as carrier and 2 M ammonium carbonate as stripping phase. The transport of thorium decreased above 2 M HCl. An attempt was made to model the physicochemical transport of thorium in SLM and understand the mechanism of thorium transport.     

Application of hollow fiber supported liquid membrane for the separation of americium from the analytical waste

Americium from analytical solid waste containing U and metallic impurities was separated using hollow fiber supported liquid membrane (HFSLM) technique impregnated with DHOA–TODGA from nitric acid medium. An aliquot of 5 g of the solid waste containing Am (19.95 mg) as minor actinide and of U (2,588 mg), Fe (1,360 mg), Ca (1,810 mg) and Na (3,130 mg) as major impurities was processed. The feed solution obtained after the dissolution of the residue in ~4 M HNO₃ was passed through HFSLM module. In the first stage using 1 M DHOA–dodecane U was recovered while Am and other impurities were left in the raffinate. In the second stage, 0.5 M DHOA + 0.1 M TODGA/dodecane was used for the separation of Am from other impurities. Though, majority of the elements were separated in this cycle, Ca was co extracted along with the americium. CMPO extraction chromatographic technique was used for further separation of americium from Ca. Significant decontamination factors were achieved in this three step separation process with respect to U, Fe, Na and Ca with ~77 % recovery of americium.     

Simultaneous separation of mercury and lignosulfonate from aqueous solution using supported liquid membrane

This paper presents an experimental investigation on facilitated and simultaneous transport of mercury and lignosulfonate (LS) through a flat sheet supported liquid membrane (SLM) having Nylon 6,6 as support, trioctylamine (TOA) as carrier and dichloroethane as solvent. The experiments were performed at various operating conditions such as strip phase concentration, feed pH, carrier concentration and feed concentration to find the best set of parameters that would yield the maximum separation of pure mercury as well as its mixture with LS. The experiments were performed in co-transport mode using NaOH as the strip phase. It was observed that extraction of mercury as well as its mixture increases with increase in concentration of NaOH up to a certain limit 0.1 M NaOH in case of pure solution and 0.2 M NaOH in case of mixture). Feed phase pH significantly affects the mercury separation process. However, initial feed concentration does not affect the extraction process appreciably. Separation of mixture of mercury and LS behaves in a similar way as their pure solution; however the extraction is low in comparison to pure solution. The extraction of mercury from its pure solution is about 81% in 1 h. The extraction of mercury and LS from their mixture is about 52.6% and 50.2%, respectively at optimum condition and in a period of 2 h.     

Extraction and extraction chromatographic separation of minor actinides from sulphate bearing high level waste solutions using CMPO

Bench-Scale studies on the partitioning and recovery of minoractinides from the actual and synthetic sulphate-bearing high level waste (SBHLW) solutions have been carried out by giving two contacts with 30% TBP to deplete uranium content followed by four contacts with 0.2M CMPO+1.2M TBP in dodecane. The acidity of the SBHLW solutions was about 0.3M. In the case of actual SBHLW, the final raffinate contained about 0.4% -activity originally present in the HLW, whereas with synthetic SBHLW the -activity was reduced to the background level.¹⁴⁴Ce is extracted almost quantitative in the CMPO phase,¹⁰⁶Ru about 12% and¹³⁷Cs is practically not extracted at all. The extraction chromatographic column studies with synthetic SBHLW (aftertwo TBP contacts) has shown that large volume of waste solutions could be passed through the column without break-through of actinide metal ions. Using 0.04M HNO₃>99% Am(III) and rare earths could be eluted/stripped. Similarly >99% Pu(IV) and U(VI) could be eluted.stripped using 0.01M oxalic acid and 0.25M sodium carbonate, respectively. In the presence of 0.16M SO ₄ ^2– (in the SBHLW) the complex ions AmSO ₄ ⁺ , UO₂SO₄, PuSO ₄ ²⁺ and Pu(SO₄)₂ were formed in the aqueous phase but the species extracted into the organic phase (CMPO+TBP) were only the nitrato complexes Am(NO₃)₃·3CMPO, UO₂(NO₃)₂·2CMPO and Pu(NO₃)₄·2CMPO. A scheme for the recovery of minor actinides from SBHLW solution with two contacts of 30% TBP followed by either solvent extraction or extraction chromatographic techniques has been proposed.     

Use of organophosphorus extractants impregnated on silica gel for the extraction chromatographic separation of minor actinides from high level waste solutions

Silica-gel has been used as an inert support for the extraction chromatographic separation of actinides and lanthanides from HNO₃ and synthetic high level waste (HLW) solutions. Silica-gel was impregnated with tri-butyl phosphate (TBP), to yield STBP; 2-ethylhexyl phosphonic acid, mono 2-ethylhexyl ester (KSM-17, equivalent to PC-88A), SKSM; octyl(phenyl)-N,N-diisobutyl carbamoylmethylphosphine oxide (CMPO), SCMPO; and trialkylphosphine oxide (Cyanex-923), SCYN and sorption of Pu(IV), Am(III) and Eu(III) from HNO₃ solutions was studied batchwise. Several parameters, like time of equilibration, HNO₃ and Pu(IV) concentrations were varied. The uptake of Pu(IV) from 3.0M HNO₃ followed the order SCMPO>SCYN>SKSM>STBP. With increasing HNO₃ concentration, D _Pu increased up to 3.0M of HNO₃ for STBP, SKSM and SCMPO and then decreased. In the case of Am and Eu with SCMPO, the D values initially increased between 0.5 to 1.0M of HNO₃, remained constant up to 5.0M and then slightly decreased at 7.5M. Also, the effects of NaNO₃, Nd(III) and U(VI) concentrations on the uptake of Am(III) from HNO₃ solutions were evaluated. With increasing NaNO₃ concentration up to 3.0M, D _Am remained almost constant while it was observed that it decreases drastically by adding Nd(III) or U(VI). The uptake of Pu and Am from synthetic pressurized heavy water reactor high level waste (PHWR-HLW) in presence of high concentrations of uranium and after depleting the uranium content, and finally extraction chromatographic column separation of Pu and Am from U-depleted synthetic PHWR-HLW have been carried out. Using SCMPO, high sorption of Pu, Am and U was obtained from the U-depleted HLW solution. These metal ions were subsequently eluted using various reagents. The sorption results of the metal ions on silica-gel impregnated with several phosphorus based extractants have been compared. The uptake of Am, Pu and rare earths by SCMPO has been compared with those where CMPO was sorbed on Chromosorb-102, Amberchrom CG-71 and styrene divinylbenzene copolymer immobilized in porous silica particles.     

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...     

Studies on evaluation of modified TRUEX solvent for the partitioning of minor actinides

An attempt to modify the TRUEX solvent has been initiated by replacing TBP with long-chain alcohols such as isodecanol. Solvent extraction experiments have been carried out determining distribution ratios for Am(III) as a function of concentrations of nitric acid and isodecanol. Acid uptake constant for the combined organic phase has also been arrived at which strongly suggests the interaction of CMPO and isodecanol. The suitability of the organic phase was tested for simulated high-level waste solutions.     

Selective separation of cesium from simulated high level liquid waste solution using 1,3-dioctyloxy calix[4]arene-benzo-crown-6

The 25,27-di(octyloxy)calix[4]arenebenzocrown-6 (CBC) in 1,3-alternate conformation was synthesized indigenously starting from its intermediates in good yield and purity. The extraction studies of CBC were carried out by using two different phase modifiers namely isodecyl alcohol and ortho-nitrophenyl hexyl ether. Detailed investigations on the effect of various parameters like, concentration of phase modifiers, aqueous phase acidity, ligand concentration, nitrate ion concentration and effect of temperature on extraction of cesium have been carried out. The concentration of phase modifiers was optimized to be 30 % in n-dodecane to ensure optimum extraction of cesium. Stoichiometry of the extracted complex determined by slope analysis method reveals 1:1:1 molar ratio for CsNO₃:CBC:HNO₃. The extraction process was found to be exothermic as determined from the plot of log K _ex versus 1/T. The solvent system with a composition 0.01 M CBC/30 % phase modifier/n-dodecane was found to be effective for selective separation of cesium from simulated high level liquid waste solution.     

Selective transport of silver ion through a supported liquid membrane using hexathia-18-crown-6 as carrier.

A facile supported liquid membrane (SLM) system for the selective and efficient transport of silver ion is introduced. The SLM used is a thin porous polyvinyldifluoride membrane impregnated with hexathia-18-crown-6 (HT18C6) dissolved in nitrophenyloctyl ether. HT18C6 acts as a specific carrier for the uphill transport of Ag+ ion as its picrate ion paired complex through the SLM. In the presence of thiosulfate ion as a suitable stripping agent in the strip solution, transport of silver occurs almost quantitatively after 4 h. The selectivity and efficiency of silver transport from aqueous solutions containing other Mn+ cations such as Mg2+, Ca2+, Co2+, Ni2+, Cu2+, Zn2+, Pb2+, Cd2+, Hg2+, Fe3+ and Cr3+ ions were investigated.     

Extraction of lutetium(III) from aqueous solutions by employing a single fibre‐supported liquid membrane

Transport behaviour of Lu(III) across a polypropylene hollow fibre‐supported liquid membrane containing di(2‐ethylhexyl)phosphoric acid (DEHPA) in dihexyl ether as a carrier has been studied. The donor phase was LuCl₃ in the buffer solution consisting of 0.2 M sodium acetate at pH 2.5–5.0. A miniaturised system with a single hollow fibre has been operated in a batch mode. The concentration of Lu(III) was determined by indirect voltammetric method using Zn–EDTA complex. The effect of pH and volume of the donor phase, DEHPA concentration in the organic (liquid membrane) phase, the time of extraction and the content of the acceptor phase on the Lu(III) extraction and stripping behaviour was investigated. The results were discussed in terms of the pertraction and removal efficiency, the memory effect and the mean flux of Lu(III). The optimal conditions for the removal of ¹⁷⁷Lu(III) from labelled ¹⁷⁷Lu‐radiopharmaceuticals were discussed and identified. The removal efficiency of Lu(III) greater than 99% was achieved at pH of the donor phase between 3.5 and 5.0 using DEHPA concentration in the organic phase of 0.47 M and the ratio of the donor to the acceptor phase of 182.