Atsuhiro Shibata

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.

Batch Crystallization of Uranyl Nitrate

Batch crystallization of uranyl nitrate is carried out in order to obtain fundamental data required for the development of reprocessing involving crystallization. Particular attention is paid to the development of a method for predicting the concentrations of uranium and nitric acid in the mother liquor and the amount of uranyl nitrate crystals produced. Initial concentrations of uranyl nitrate and nitric acid are 500–600 g/l and 4–6 mol/l, respectively, corresponding to the condition of a dissolver solution of spent fuel. Steady-state mass balance equations including the correlation equation for the equilibrium solubility of uranium nitrate are applied to the prediction. The calculated concentrations of uranium and nitric acid are in close agreement with the experimental ones. The recovery of uranium is accurately predicted by the calculated concentrations, with an error of less than 10%.

Uranium Crystallization Test with Dissolver Solution of Irradiated Fuel

The crystallization process has been developed as a part of the advanced aqueous process, NEXT (New Extraction System for TRU recovery) for fast reactor (FR) cycle. In this process, a large part of U is separated from dissolver solution by crystallization as UO2(NO3)2.6H2O. The U crystallization test was carried out with real dissolver solution of irradiated FR fuel to investigate the influence of cooling rate on the crystal size and the behavior of fission product (FP) compared with that of Pu(IV). In regard to the influence of the cooling rate, it was confirmed that the crystal size was smaller as the cooling rate is faster. Although it was expectable that the decontamination performance was improved by diminishing the specific surface of the crystals, it was suggested that a large crystal produced by crystallization was not always high purity. Concerning the behavior of FPs, Eu behaved similarly to Pu(IV). Cs accompanied with U into the crystals under the condition in this test.

Flowsheet Study of U-Pu Co-Crystallization Reprocessing System

A U-Pu co-crystallization reprocessing system is proposed for light water reactor fuels and its flowsheet study is carried out. This reprocessing system is based on experimental evidence indicating that Pu(VI) in a nitric acid solution is co-crystallized with uranyl nitrate, whereas it is not crystallized when uranyl nitrate is not present in the solution. The system consists of five steps: dissolution of spent fuel, Pu oxidation, U-Pu co-crystallization, re-dissolution of the crystals, and U re-crystallization. The proposed system does not require the use of organic solvents, resulting in a relative increase in safety and cost-effectiveness. The system requires recycling of the mother liquor from the U-Pu co-crystallization step to recover almost the entire amount of U and Pu at this step. The appropriate recycling ratio is determined, such that satisfactory decontamination is achieved. A consistent ratio of Pu to U in the mother liquor from the U re-crystallization is maintained by regulating the temperature, suggesting that the quality of the liquor, which can be a source of mixed oxide fuels, can be controlled despite differences in the composition of the spent fuel. The size of a plant utilizing the proposed system is estimated to be about 30% less than that of the PUREX system.

Experimental Study on U-Pu Cocrystallization Reprocessing Process

A new reprocessing system with a 2-stage crystallization process has been developed. In the first stage of the system, U and Pu are recovered from dissolver solution by U-Pu cocrystallization. Laboratory-scale experiments were carried out with U and Pu mixed and irradiated fuel dissolver solutions to obtain fundamental data on the U-Pu cocrystallization process. Pu(VI) was cocrystallized with U, but crystallization yields of Pu were lower than those of U. FPs were separated from U and Pu by cocrystallization, and decontamination factors of Cs and Eu to U in crystals were over 100.

Dissolution behavior of irradiated mixed oxide fuel with short stroke shearing for fast reactor reprocessing

An efficient dissolution process was established for future reprocessing in which mixed-oxide (MOX) fuels with high plutonium contents and dissolver solution with high heavy-metal (HM) concentrations (more than 500 g dm−3) will be treated. This dissolution process involves short stroke shearing of fuels (∼10 mm in length). The dissolution kinetics of irradiated MOX fuels and the effects of the Pu content, HM concentration, and fuel form on the dissolution rate were investigated. Irradiated fuel was found to dissolve as 102–103 times fast as non-irradiated fuel, but the rate decreased with increasing Pu content. Kinetic analysis based on the fragmentation model, which considers the penetration and diffusion of nitric acid through fuel matrices prior to chemical reaction, indicated that the dissolution rate of irradiated fuel was affected not only by the volume ratio of liquid to solid (L/S ratio) but also by the exposed surface area per unit mole of nitric acid (A/m ratio). The penetration rate of nitric acid is expected to be decreased at high HM concentrations by a reduction in the L/S ratio, but enhanced by shearing the fuel pieces with short strokes and thus enlarging the A/m ratio.

Estimation of the inventory of the radioactive wastes in Fukushima Daiichi NPS with a radionuclide transport model in the contaminated water

ABSTRACT Quantification of the radioactive waste inventory remaining inside the reactors at Fukushima Daiichi NPS is necessary to effectively plan their recovery, treatment, and disposal. Analysis of radionuclide concentrations and secondary wastes in the contaminated water treatment system can provide a means to estimate the radioactive waste inventory, which is not possible by more direct methods due to problems of accessibility and high levels of radiation. A predictive model has therefore been developed to estimate the radioactive waste inventory from the radionuclide concentrations and throughputs in the contaminated water. Model fitting has enabled the estimation of the key parameters, such as the initial radionuclide concentration C0, the continuous release rate F, and inventory of source of continuous release IS0. An estimated one-third of the total 137Cs inventory has already made its way into the water treatment system as secondary wastes, whereas half still remains inside the damaged reactors as of 13 March 2014.

Purification of uranium products in crystallization system for nuclear fuel reprocessing

Uranium crystallization system has been developed to establish an advanced aqueous reprocessing for fast breeder reactor (FBR) fuel cycle. In the crystallization system, most part of uranium in dissolved solution of spent FBR-MOX fuels is separated as uranyl nitrate hexahydrate (UNH) crystals by a cooling operation. The targets of U yield and decontamination factor (DF) on the crystallization system are decided from FBR cycle performance and plutonium enrichment management. The DF is lowered by involving liquid and solid impurities on and in the UNH crystals during crystallization. In order to achieve the DF performance (more than 100), we discuss the purification technology of UNH crystals using a Kureha Crystal Purifier (KCP). Results show that more than 90% of uranium in the feed crystals could be recovered as the purified crystals in all test conditions, and the DFs of solid and liquid impurities on the purified UNH crystals are more than 100 under longer residence time of crystals in the column of KCP device. The purification mechanism is mainly due to the repetition of sweating and recrystallization in the column under controlled temperature.

Development of Crystallizer for Advanced Aqueous Reprocessing Process

Crystallization is one of the remarkable technologies for future fuel reprocessing process that has safety and economical advantages. Japan Atomic Energy Agency (JAEA) (former Japan Nuclear Cycle Development Institute), Mitsubishi Material Corporation and Saitama University have been developing the crystallization process. In previous study, we carried out experimental studies with uranium, MOX and spent fuel conditions, and flowsheet analysis was considered. [1, 2, 3] In association with these studies, an innovative continuous crystallizer and its system was developed to ensure high process performance. From the design study, an annular type continuous crystallizer was selected as the most promising design, and performance was confirmed by small-scale test and engineering scale demonstration at uranium crystallization conditions. In this paper, the design study and the demonstration test results are described.Copyright

Flowsheet Analysis of U-Pu Co-Crystallization Process as a New Reprocessing System

A new fuel reprocessing system by U-Pu co-crystallization process is proposed and examined by flowsheet analysis. This reprocessing system is based on the fact that hexavalent plutonium in nitric acid solution is co-crystallized with uranyl nitrate, whereas it is not crystallized when uranyl nitrate does not exist in the solution. The system consists of five steps: dissolution of spent fuel, plutonium oxidation, U-Pu co-crystallization as a co-decontamination, re-dissolution of the crystals, and U re-crystallization as a U-Pu separation. The system requires a recycling of the mother liquor from the U-Pu co-crystallization step and the appropriate recycle ratio is determined by flowsheet analysis such that the satisfactory decontamination is achieved. Further flowsheet study using four different compositions of LWR spent fuels demonstrates that the constant ratio of plutonium to uranium in mother liquor from the re-crystallization step is achieved for every composition by controlling the temperature. It is also demonstrated by comparing to the Purex process that the size of the plant based on the proposed system is significantly reduced.Copyright