Solvent Extraction of Pentavalent Neptunium with n-Octyl(phenyl)-N,N-Diisobutyl- carbamoylmethylphosphine Oxide

Solvent extraction of Np(V) from HNO₃ solution was experimentally studied with n-octyl(phenyl)-N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) as an extractant mixed with TBP and n-dodecane. In the low HNO₃ concentration, the Np(V) is weakly extractable, but effectively extracted in the high HNO₃ concentration (>4M) due to the disproportionation of Np(V) to Np(IV)and Np(VI). The distribution ratio of Np was increased by use of H₂O₂as a reductant of Np(V). More than 95% of Np was extracted with 0.8 M H₂O² in 2.2 M HNO₃ solution. It was shown that most of the Np extracted is in tetravalent state as expected from redox mechanism. The Np(IV) extracted in the organic phase was effectively stripped to the aqueous phase with H₂C₂O₄.     

Solvent Extraction of Np (V) with CMPO from Nitric Acid Solutions Containing U (VI)

The extraction of Np(V) in the presence of U(VI) or Nd(III) was studied with 0.2 M CMPO- decalin and with 0.2 M CMPO-1.4 M TBP-n-dodecane. Distribution ratios of Np(V) decreased with increasing the concentration of Nd(III), which was considered to be explained by the decrease in the concentration of free CMPO. On the other hand, distribution ratios increased as the concentration of U(VI) increased. The absorption spectrum of Np(V) in organic solution showed a new absorption peak which was probably attributable to the formation of cation-cation complexes of Np(V) and U(VI). Assuming the formation of cation-cation complexes, the dependence of distribution ratio of Np(V) on the concentration of U(VI) was found to be semi-quantitatively explained.     

Extraction of Some Elements by Mixture of DIDPA-TBP and Its Application to Actinoid Partitioning Process

Effect of TBP on the extraction of Pu(IV), Zr(IV), Nb(V), Nd(III) and Am (III) was studied with diisodecylphosphoric acid(DIDPA) as an extractant. Hydrolyzable elements contained in the high-level liquid waste of fuel reprocessing,i.e. Pu(IV), Zr(IV) and Nb(V), could be extracted with mixtures of DIDPA and TBP of different compositions. Addition of TBP to DIDPA causes an increase and a decrease of respectively distribution rate and ratio of Zr(IV). These elements extracted were completely stripped with the aid of oxalic acid. An effect of TBP on separation of transplutonides (III) from lanthanoids(III) in the DIDPA and DTPA extraction system was also studied.

Based on the results, a process flow sheet utilizing the extractant of DIDPA and TBP mixture was contrived for partitioning actinoids in the high-level liquid waste.     

Solvent extraction of uranium(VI) and europium(III) from nitrate media by picolinamide

The solvent extraction of uranium(VI) and europium(III) from nitric acid solution was studied with pi- colinamide dissolved in ethylene dichloride. The distribution ratios of U(VI) and Eu(III) as a function of aqueous HNO3 concentration , extractant concentration in organic phase and temperature as well as the salting-out agent con- centration have been measured. The experiment results show that picolinamide has higher extractability for U(VI) than for Eu(III). The composi…     

Pressure dependence of extraction behavior of plutonium(IV) and uranium(VI) from nitric acid solution to supercritical carbon dioxide containing tributylphosphate

Plutonium(IV) and uranium(VI) were extracted into supercritical CO₂ fluid phase (SF-CO₂) containing tributylphosphate (TBP) with equilibrium distribution ratios, D, e. g., D_Pu(IV) = 3.1 and D_U(IV) = 2.0, for the extraction of 2 × 10⁻³ M Pu(IV) and U(VI) from 3 M HNO₃ into SF-CO₂ containing 0.3 M TBP at 60 °C and 15 MPa. A simple linear relation between D and density of CO₂; long D = a log + b (a,b; constants), was observed, which was explained theoretically by the formulation of the extraction equilibrium taking into account the phase distribution behavior of extractant TBP and extracted species, i.e. Pu(IV)- and U(VI)-TBP complexes involved in the extraction reaction. The slopes a of the log D vs. log plots were −(1.6 ± 0.1) and −(2.7 ± 0.5) for the extraction of Pu(IV) and U(VI), respectively. The differences in D as well as the slope a between Pu(IV) and U(IV) make it possible to design the U and Pu separation method by which one can achieve an enhancement of the extraction efficiency and selectivity by tuning the operation pressure.     

Toward Innovative Actinide Separation Processes: Sequential Reduction Scheme of Uranium,Neptunium, and Plutonium in 3 M HNO3 by External Ultrasound Irradiation

An innovative remote valency control technique for actinide ions induced by external ultrasound irradiation was reported in the present study. It is known that ultrasound irradiation to water causes the oxidation and/or reduction of the solute by H? or OH? There were some reports on the redox behavior of actinide elements under ultrasound irradiation. Nevertheless, they showed that the ability of ultrasound is not sufficient for the use of the actinide separation processes. However, very recently we found that a noble metal catalyst drastically enhances the sonochemical effect and that even highly stable U(VI) is reduced to U(IV) by ultrasound irradiation. Employing this catalytic reaction, we are developing low-emission actinide ion separation schemes driven by external ultrasound irradiation. In the present work, U(VI), Np(VI) and Pu(VI) in 3 M HNO₃ medium were chosen as target ions. Their valency was first adjusted to U(VI)/Np(V)/Pu(IV) by external ultrasound irradiation and, then, further sonochemical reduction to U(IV)/Np(IV)/Pu(III) was carried out. The present results confirmed the possibility to design the low-emission U/Np/Pu mutual separation scheme driven by external ultrasound irradiation.     

A study on selective precipitation ability of cyclic urea to U(VI) for developing reprocessing system based on precipitation method

We have proposed a new reprocessing system based on precipitation method. In order to find out precipitants with high selectivity to U(VI) and to investigate factors controlling precipitation ability to U(VI) and U(IV), properties of 3,4,5,6-tetrahydro-1,3-dimethyl-2(1H)-pyrimidinone (DMPU) as a precipitant have been examined by using U(VI), U(IV) as a simulant of Pu(IV), and simulated fission products (FPs). We have evaluated precipitation ratios (P.R.) for U(VI) and U(IV), solubility of U(VI) precipitates to 3.0 mol dm^?3 (M) HNO₃ solution, melting points (MPs) of U(VI) precipitates, log P (distribution ratio of a substance in 1-octanol/water biphasic system, a measure of hydrophobicity) of precipitants, and decontamination factors (DFs) of FPs. The properties of DMPU were compared with those in systems using N-n-butyl-2-pyrrolidone (NBP), N-cyclohexyl-2-pyrrolidone (NCP), and other pyrrolidone derivatives as the precipitant. The P.R. values of DMPU to U(VI) and U(IV) in 3.0 M HNO₃ solutions were around 99% at [DMPU]/[U(VI)] = 2.0 and 0% at [DMPU]/[U(IV)] = 5.0, respectively. In DMPU system, the DF values of the most of simulated FPs [Rb(I), Cs(I), Sr(II), Ba(II), Ru(III), Rh(III), La(III), Ce(III), Pr(III), Nd(III), and Sm(III)] used in the present study were found to be more than 100. Even in U(VI)–U(IV) coexisting system, the selectivity of DMPU to U(VI) was higher than those of NBP and NCP. This selective precipitation ability of DMPU to U(VI) was evaluated by the solubility of U(VI) precipitates on the basis of their MPs and the log P values of precipitants. As a result, it was found that the precipitants having low hydrophobicity and forming the U(VI) precipitates with high MPs have highly selective precipitation ability to U(VI).     

Neptunium Valence Adjustment through Photochemically Induced Redox Reactions at Low Concentrations

Photochemically induced redox reactions of Np(VI) and Np (IV) to Np (V) are experimentally studied in nitric acid solution of low Np concentration less than 10^?4 mo].dm⁸ using a Kr-F excimer laser. The preparations of the initial solution of Np (VI) or Np (IV) are based on the addition of chemical redox reagents. The extraction chromatography is used to analyze the fraction of the neptunium valences. The result of redox experiments with laser radiation shows that the fractions of Np(V)/Np(VI) or Np(V)/Np(IV) photochemically increase up to the steady-state values against initially oxidizing or reducing conditions respectively. The steady- state values are different from those at thermal equilibrium states. It is concluded that, in low Np concentration as is observed in the normal Purex process, laser application to valence adjustment of Np gives another redox condition which is different from that determined thermochemically.     

Selective uptake properties of metal ions by hybrid microcapsules enclosed with TBP

The granulation of TBP extractant is effective for the enhancement of uptake efficiency. The granulation was accomplished by microencapsulating techniques using alginate gel polymers (alginate and alginic acid gel polymers; calcium alginate, barium alginate and nitric alginate (CaALG, BaALG and HALG)). The characterization of hybrid microcapsules was examined by SEM/EPMA, and the uptake properties and the selectivity of various nuclides, Fe(III), Sr(II), Co(II), U(VI) and Pu(IV), were examined by batch methods. A relatively high uptake (%) of Fe(III), Sr(II) and Co(II) above 80% was obtained in the presence of 10⁻³ M HNO₃, and the uptake equilibrium was attained within 5 h. The uptake rate of U(VI) and Pu(IV) attained equilibrium within 1 h and 3 h, respectively. At higher HNO₃ concentration ranging from 10⁻³ M to 5 M, the uptake (%) of Fe(III), Sr(II) and Co(II) was considerably lowered. In contrast, the uptake (%) of U(VI) and Pu(IV) about 60% was obtained even in the presence of 5 M HNO₃. The uptake of U(VI) for MCs (TBP–CaALG) was governed by the extraction with TBP micro droplets and ion-exchange reaction in the CaALG matrices. Energy dispersive spectra (EDS) showed that U(VI) ions were incorporated into both phases of TBP and CaALG in microcapsules.     

Separation of Actinide Elements by Solvent Extraction Using Centrifugal Contactors in the NEXT Process

Using the advanced aqueous reprocessing system named NEXT process, actinides recovery was attempted by both a simplified solvent extraction process using TBP as an extractant for U, Pu and Np co-recovery and the SETFICS process for Am and Cm recovery from the raffinate. In U, Pu and Np co-recovery experiments a single cycle flow sheet was used under high nitric acid concentration in the feed solution or scrubbing solution. High nitric acid concentration in the feed solution aided Np oxidation not only in the feed solution, but also at the extraction section. This oxidation reaction accomplished Np extraction by TBP with U and Pu. Most of Np could be recovered into the product solution. In the SETFICS process, a TRUEX solvent of 0.2 mol/dm³ CMPO and 1.4 mol/dm³ TBP in n-dodecane was employed instead of 0.2 mol/dm³ CMPO and 1.0 mol/dm³ TBP in n-dodecane in order to increase the loading of metals. Instead of sodium nitrate, hydroxylamine nitrate was applied to this experimental flow sheet in accordance with a “salt-free” concept. The counter current experiment succeeded with the Am and Cm product. On the high-loading flow sheet, compared with the previous flow sheet, the flow of the aqueous effluents and spent solvent were expected to decrease by about one half. Two solvent extraction experiments for actinides recovery demonstrated the utility of the flow sheet of these processes in the NEXT process.     

Integrated sorption and diffusion model for bentonite. Part 2: porewater chemistry,sorption and diffusion modeling in compacted systems

It is important to understand the coupled processes of sorption and diffusion of radionuclides (RNs) in compacted bentonite, and to develop mechanistic models that can aid in the prediction of the long-term performance of geological disposal systems of radioactive waste. The integrated sorption and diffusion (ISD) model was developed based on the consistent combination of clay–water interaction, sorption and diffusion models. The diffusion model based on the electrical double layer theory describing relative ionic concentrations and viscoelectric effects at the negatively charged clay surface was coupled with porewater chemistry and sorption models. This ISD model was successfully tested for various actinides with a complex chemistry (Np(V), Am(III), U(VI) under conditions where variably charged carbonate complexes are formed) considered in Part 1, by using published diffusion and sorption data (D_a, D_e, K_d) as a function of partial montmorillonite density. Quantitative agreements were observed by considering uncertainty in porewater chemistry and dominant aqueous species. It can therefore be concluded that the ISD model developed here is able to adequately explain the sorption and diffusion behavior of various RNs with a complex chemistry in compacted bentonites. The performed modeling indicates that uncertainties are mainly related to porewater chemistry and RN speciation and that these parameters need to be carefully evaluated.     

Solvent Extraction of Americium(VI) by Tri-n-Butyl Phosphate

Solvent extraction of Am(VI) by tri-n-butyl phosphate (TBP) from nitric acid solutions was investigated to develop a novel method for partitioning americium from high level liquid waste generated through spent nuclear fuel reprocessing. Am(VI) was prepared using ammonium peroxodisulfate and silver nitrate. The distribution coefficients of Am(VI) were determined for extraction systems of various concentrations of nitric acid and TBP. Sufficiently stable Am(VI) could be extracted and the extraction reaction of Am(VI) was found to be the same as for other hexavalent actinides. The apparent equilibrium constant varied with the concentration of peroxodisulfate used for the valence control, which was ascribed to the competitive reaction of the extraction of Am(VI) and the complex formation of Am(VI) with sulfate ion produced by the decomposition of peroxodisulfate. A distribution coefficient of Am(VI) above 1 was obtained with undiluted TBP and the separation factor between Am(VI) and Nd(III) was 87±9. TBP extraction of Am(VI), after implementing valence control, was proved to be an effective method for the partitioning of americium from fission products such as rare earth elements.     

Measurement of CO2 Laser Pulse Narrowing in CF2HCl

The oxidation of Np(V) by nitrous acid was investigated spectroscopically in 0.2 M CMPO—1.4 M TBP—n-dodecane and the oxidation rate constant of Np(V) was estimated assuming the first-order reaction. By using the obtained oxidation rate constant as well as taking account of the Np(V) oxidation in aqueous phase and the distribution ratios of Np(V) and Np(VI) cited from literature, extraction kinetics of Np from 4 M nitric acid solution was calculated, and was compared with the extraction kinetics measured experimentally.     

A study on selective precipitation of U(VI) by hydrophilic cyclic urea derivatives for development of a reprocessing system based on precipitation method

Selective precipitation ability of 2-imidazolidone (EU) and tetrahydro-2-pyrimidinone (PU) for U(VI) species in HNO₃ solutions containing U(VI), U(IV) (simulant of Pu(IV)), and simulated fission products (FPs) was investigated. As a result, it was found that these compounds precipitate almost quantitatively U(VI) as UO₂(NO₃)₂L₂ (L = EU, PU) from 3.0 M HNO₃ solution. In contrast, these urea derivatives form neither solid precipitates nor oily products with U(IV) in HNO₃ solutions containing only U(IV) species and even in U(VI)–U(IV) admixture system. Therefore, the separation of U(VI) from U(IV) was demonstrated to be achieved in use of EU and PU. Furthermore, EU and PU are capable to remove most of simulated FPs[Sr(II), Ru(III), Rh(III), Re(VII) La(III), Ce(III), Pr(III), Nd(III), and Sm(III)] from U(VI) to give their decontamination factors (DFs) higher than 100, while those values of Zr(IV), Mo(VI), Pd(II), and Ba(II) are necessary to be improved in both systems. From these results, it is expected that EU and PU are the promising precipitants for selective separation of U(VI) from HNO₃ solutions dissolving spent FBR fuels.     

Solvent extraction of nitric acid,uranium（VI） and thorium（IV） by N,N,N‘,N’—tetrahexylsuccinylamide

A new kind of diamide N,N,N‘,N‘-tetrahexylsuccinylamide(THSA) was synthesized,characterized and used for the extraction of HNO3,U(VI)and Th(IV) in a diluent composed of 0.5 volume fraction 1,2,4-trimethy benzene(TMB) and 0.5 volume fraction kerosene(OK),Extraction distribution coefficients of U(VI) and Th(IV) as functions of aqueous nitric acid concentation,extractant concentration.temperature and salting-out agent (LiNO3) have been studied,and it is found that THSA as an extractant is superior to TBP for extraction of U(VI) and Th(IV),Back Extraction was also studied.At low acidity,the main adduct of THSA and NHO3 is HNO3 is HNO3.THSA,THSA.(HNO3)2 and THSA.(HNO3)3 are also found at high acidity.The compositions of extracted species.apparent equilibrium constants and enthalpies of extraction reactions have also been calculated.     

Low-Temperature Partitioning of Plutonium with High U(VI)-Loading for Fuel Reprocessing

Measurement of the distribution ratios of Pu(IV), U(VI) and HNO₃ at low temperatures and its treatment with DIST code revealed that a high U (VI)-loading of 30% TBP in n-dodecane splits Pu(IV) down to the aqueous phase more strongly than do at 25°C. Based on these findings, flowsheet conditions to separate Pu(IV) from U(VI) were investigated with EXTRA.M code including the distribution equations obtained above. And tentative flowsheets for non-reductive Pu-splitting process at a temperature of 5°C were proposed for fuel reprocessing mainly based on the effects of U (VI)-loading in the solvent and temperature on distribution ratios of Pu(IV) and U(VI). Distribution ratios of the fission products, Zr, Nb, Ru and Ce were also measured to assess their decontamination from U or Pu products in the above process. Finally behavior of Np, in the proposed partitioning process was discussed by analysis with EXTRA. M code and a redox reaction model.     

Separation of Am(III) from Eu(III) by extraction based on in situ extractant formation of dithiocarbamate derivatives

A new solvent-extraction technique based on in situ formation of dithiocarbamate derivatives in order to separate Am(III) from Eu(III) was carried out. In this technique, the extractant is formed during the extraction course by the reaction between the organic materials, which are needed to synthesize the extractant. The synthesis of extractant in in situ extractant-formation method was carried out as follows. Di-substituted amine, such as dioctylamine (DOA), dibenzylamine (DBzA) and so on, and carbon disulfide (CS₂) were mixed in organic solvents, such as nitrobenzene, to produce dioctylammonium dioctyldithiocarbamate (DOA⁺·DODTC⁻), dibenzylammonium dibenzyldithiocarbamate (DBzA⁺·DODTC⁻), or so on. These organic solutions are also the organic phase in the solvent extraction, whereas the aqueous phase is 1.00 mol/dm³ (H, Na)NO₃ solution. The elements of Am(III) and Eu(III) were extracted into organic phase from different hydrogen ion concentrations of aqueous phase. The SF of Am(III)/Eu(III) is 3.2 × 10⁴ at pH_eq = 6.25 in DOA–CS₂/nitrobenzene system. This separation technique of Am(III) from Eu(III) by extraction based on in situ extractant formation has the following advantages. (a) It is unnecessary to take the chemical stability of extractant into account for storage purpose, and (b) Am(III) can be completely separated from Eu(III) by a single extraction procedure.     

The chemical reduction of neptunium to the trivalent state

It was established spectrometrically that 1–1.5 M nitric and hydrochloric acid solutions of sodium formaldehyde sulfoxylate (rongalite) reduce Np (IV) to Np (III). The reduction proceeds both in an atmosphere of nitrogen and in air, but the degree of reduction and the stability of Np (III) are increased in an atmosphere of nitrogen. It is known that an increase in the total amount of the reducing agent in the solution (hydrazine + rongalite) promotes the reduction of neptunium to the trivalent state; neptunium is reduced on the average by 70% in nitric acid solutions and by 95% in hydrochloric acid solutions.It was found that reduction of Np (V) with rongalite gave a mixture of Np (III) and Np (IV). In the Np (IV) and Np (III) mixture, the latter shows a noticeable stability to oxidation with aerobic oxygen.     

Supposed existence of Np4+ in a genuine dissolver solution from the results of extraction simulation by PARC-L code

With a genuine spent fuel solution (a dissolver solution), a laboratory-scale reprocessing experiment of an extraction–separation process was performed using mixer-settlers as extractors. In the experiment, n-butyraldehyde was utilized as a reducing reagent of Np^(VI)O₂²⁺ to Np^(V)O₂⁺ for the purpose to distinguish Np^(VI)O₂²⁺ from Np⁴⁺. From the Np concentration in the aqueous phase, Np would be extracted from the dissolver solution together with U and Pu. The scrutiny of Np behavior was performed utilizing 66 cases of calculation results by a Japan Atomic Energy Agency open extraction simulation code, the Program for Advanced Extraction with Radiation Effect Calculation–Lightened version. From the scrutiny, the authors found that the calculation result with 60% of Np⁴⁺ in the dissolver solution represented the best experimental extraction–separation behavior of Np. Therefore, it was supposed that the dissolver solution contained sufficient proportion of Np⁴⁺ to affect the extraction–separation behavior of Np.     

用于锕系元素提取分离的萃取剂——TiAP

对磷酸三异戊酯(TiAP)和磷酸三丁酯(TBP)萃取体系的物理性质、萃取能力、耐辐照等方面进行了比较,结果表明,TiAP作为萃取剂在物理性质、萃取Pu(Ⅳ)和Np(Ⅳ)的能力以及辐照稳定性能等方面明显好于TBP。提出TiAP是一种很好的并有可能用于锕系元素提取分离的萃取剂。