• Economic and Environmental Geology
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• v.56 no.5
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• pp.603-618
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• 2023

This study focused on evaluating the suitability of the WRK (waste repository Korea) bentonite as a buffer material in the SNF (spent nuclear fuel) repository. The U (uranium) adsorption/desorption characteristics and the adsorption mechanisms of the WRK bentonite were presented through various analyses, adsorption/desorption experiments, and kinetic adsorption modeling at various pH conditions. Mineralogical and structural analyses supported that the major mineral of the WRK bentonite is the Ca-montmorillonite having the great possibility for the U adsorption. From results of the U adsorption/desorption experiments (intial U concentration: 1 mg/L) for the WRK bentonite, despite the low ratio of the WRK bentonite/U (2 g/L), high U adsorption efficiency (>74%) and low U desorption rate (<14%) were acquired at pH 5, 6, 10, and 11 in solution, supporting that the WRK bentonite can be used as the buffer material preventing the U migration in the SNF repository. Relatively low U adsorption efficiency (<45%) for the WRK bentonite was acquired at pH 3 and 7 because the U exists as various species in solution depending on pH and thus its U adsorption mechanisms are different due to the U speciation. Based on experimental results and previous studies, the main U adsorption mechanisms of the WRK bentonite were understood in viewpoint of the chemical adsorption. At the acid conditions (＜pH 3), the U is apt to adsorb as forms of UO₂²⁺, mainly due to the ionic bond with Si-O or Al-O(OH) present on the WRK bentonite rather than the ion exchange with Ca²⁺ among layers of the WRK bentonite, showing the relatively low U adsorption efficiency. At the alkaline conditions (>pH 7), the U could be adsorbed in the form of anionic U-hydroxy complexes (UO₂(OH)₃^-, UO₂(OH)₄^2-, (UO₂)₃(OH)₇^-, etc.), mainly by bonding with oxygen (O^-) from Si-O or Al-O(OH) on the WRK bentonite or by co-precipitation in the form of hydroxide, showing the high U adsorption. At pH 7, the relatively low U adsorption efficiency (42%) was acquired in this study and it was due to the existence of the U-carbonates in solution, having relatively high solubility than other U species. The U adsorption efficiency of the WRK bentonite can be increased by maintaining a neutral or highly alkaline condition because of the formation of U-hydroxyl complexes rather than the uranyl ion (UO₂²⁺) in solution,and by restraining the formation of U-carbonate complexes in solution.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.12 no.3
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• pp.179-189
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• 2014

Pyroprocessing has been developed for the purpose of resolving the current spent nuclear fuel management issue and enhancing the recycle of valuable resources. An electrolytic reduction of the pyroprocessing is a process to reduce oxides into metals using LiCl as an electrolyte and requires a post-treatment process due to the inclusion of residual salt in porous metal products. A vacuum distillation has been adopted for various molten salt systems and could be applied to the post-treatment process of the electrolytic reduction. The residual salt in the metal products includes LiCl, alkali chlorides, and alkaline earth chlorides. In this paper, vapor pressures of chlorides have been estimated and the composition changes on the residual liquid during the vacuum distillation process have been calculated. A model combining a material balance and vapor-liquid equilibrium relations has been proposed under a constant vapor discharging flow rate and liquid composition changes have been calculated using the vapor pressures with respect to a dimensionless time. The behaviors have been compared with temperature and molten salt composition changes to simulate the process condition variation. The distillation of the residual salt has been dominated by LiCl which is the main component of the salt and CsCl of which vapor pressure is higher than that of LiCl would be readily removed. RbCl exhibits similar vapor pressure with LiCl and maintains its composition. However, $SrCl_2$ and $BaCl_2$ of which vapor pressures are much lower than that of LiCl are concentrated with time and expected to be possibly precipitated during the distillation when the initial compositions are increased.

• Journal of Radiation Protection and Research
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• v.9 no.1
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• pp.33-42
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• 1984

A great variety of nuclear gamma rays emitted from fission and activation products of spent nuclear fuel contains much information that can be elicited without affecting the integrity of the fuel elements. But the extraction of such information from the complex spectrum is difficult and requires computer codes. In the present work, a versatile code 'CAERI' was developed which locates peaks and calculates their areas for X-rays as well as gamma rays using elegant features of some widely used programs for gamma-ray peak fitting. 'CAERI' coded in FORTRAN used infinite series approximation more accurate than other workers various, simple, piecewise series approximations for evaluations of the Voigt function which represents the X-ray peak with non-negligible natural line width. 'CAERI' can handle even a complex multiplet consisting of peaks from X-rays and gamma rays in arbitrary mixture, which one often encounters in the isotopic analysis of heavy elements such as U and Pu. The results of the fitting performed on the test spectra of $^{177m}\;Lu\;{\gamma}-ray\;and\;^{235}U\;K_{\alpha}$X-ray show good agreement with those by previous workers.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.11 no.1
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• pp.55-61
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• 2013

The recovery of Zr from Zircaloy-4 (Zry-4) cladding hulls using a chlorination method was demonstrated for complete conversion of Zr into $ZrCl_4$. A chlorination reaction was performed by reacting Zry-4 hulls for 8 h under a 70 cc/min $Cl_2$ + 70 cc/min Ar flow at $380^{\circ}C$. The initial weight of the reactant (51.7 g) decreased to 0.49 g after 8 h of operation, which is only 0.95wt% of the initial weight. The weight of the total reaction products was 121.7 g with a high Zr purity of 99.80wt%. Fe and Sn were identified as major (0.18wt%) and minor (0.02wt%) impurities of the reaction products, respectively. It was also shown that Zr exhibited a high recovery ratio of 96.95wt% with a relatively small experimental loss of 2.34wt%. Observation of the reaction residues revealed that the chlorination reaction was dominant along the longitudinal direction, and surface oxide layers remained as reaction residues. The high purity and recovery ratio of Zr proposed the feasibility of the chlorination technique as an effective hull waste treatment method.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.7 no.4
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• pp.237-242
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• 2009

In the pyroprocessing of spent nuclear fuels, fuel materials are recovered by electrochemical reactions on the surface of electrodes as well as stirring the electrolyte in electrolytic cells such as electrorefiner, electroreducer and electrowinner. The system with this equipment should first be scaled-up in order to commercialize the pyroprocessing. So in this study, the scale-up for those electrolytic cells was studied to design a large-scale system which can be employed in a commercial process in the future. Basically the dimensions of both electrolytic cells and electrodes should be enlarged on the basis of the geometrical similarity. Then the criterion of constant power input per unit volume, characterizing the fluid behavior in the cells, was introduced in this study and a calculation process based on trial-and-error methode was derived, which makes it possible to seek a proper speed of agitation in the electrolytic cells. Consequently examples of scale-up for an arbitrary small scale system were shown when the criterion of constant power input per unit volume and another criterion of constant impeller tip speed were respectively applied.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.15 no.4
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• pp.321-332
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• 2017

In order to build a general model of a high-throughput uranium electrorefining process according to the electrode configuration, numerical analysis was conducted using the COMSOL Multiphysics V5.3 electrodeposition module with Ordinary Differential Equation (ODE) interfaces. The generated model was validated by comparing a current density-potential curve according to the distance between the anode and cathode and the electrode array, using a lab-scale (1kg U/day) multi-electrode electrorefiner made by the Korea Atomic Energy Research Institute (KAERI). The operating temperature was $500^{\circ}C$ and LiCl-KCl eutectic with 3.5wt% $UCl_3$ was used for molten salt. The efficiency of the uranium electrorefining apparatus was improved by lowering the cell potential as the distance between the electrodes decreased and the anode/cathode area ratio increased. This approach will be useful for constructing database for safety design of high throughput spent nuclear fuel electrorefiners.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.10 no.2
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• pp.105-115
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• 2012

Necessity of demonstration test to evaluate the structural integrity of a basket for accident conditions arose during license approval procedure for the WSPP's dry storage facility named MACSTOR/KN-400. A drop test facility for demonstration was constructed in KAERI site and demonstration tests for basket drop were conducted. As the upper welding region of a loaded basket was collided with a dropped basket during the drop test, the welding in this region was fractured and leakage happened after the drop test. The enhancement of basket design was needed since the existing basket design was not able to satisfy the performance requirement. The directions for design modification were determined and six enhanced designs were derived based on these directions. Structural analyses and specimen tests for each enhanced design were conducted. By evaluating structural analysis results and test results, one among six enhanced designs was decided as a final design for revision. The final design was the one to reduce the height of central post of a basket and to decrease the impact velocity with a dropped basket. Test basket models were fabricated with accordance with the final enhanced design. Additional demonstration test was performed for this test model and all the performance requirements were satisfied.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.2 no.4
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• pp.239-244
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• 2004

In order to enhance an oxidation resistance of the pure uranium metal under air condition, a small quantity of niobium(Nb) which is known to mitigate metal oxidation is added into uranium metal as an alloying element. A simulated metallic uranium alloy, U-Nb has been fabricated and then oxidized in the range of 200 to $300^{\circ}C$ under the environment of the pure oxygen gas. The oxidized quantity in terms of the weight gain(wt%) has been measured with the help of a thermogravimetric analyzer. The results show that the oxidation resistance of the U-Nb alloy is considerably enhanced in comparison with that of the pure uranium metal. It is revealed that the oxidation resistance of the former with the niobium content of 1, 2, 3, and 4 wt% is : 1) 1.61, 7.78, 11.76 and 20.14 times at the temperature of $200^{\circ}C$ ; 2) 1.45, 5.98, 10.08 and 11.15 times at $250^{\circ}C$ ; and 3) 1.33, 4.82, 8.87 and 6.84 times at $300^{\circ}C$ higher than that of the latter, respectively. Besides, it is shown that the activation energy attributable to the oxidation is 17.13~21.92 kcal/mol.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.12 no.1
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• pp.7-17
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• 2014

Molten salt electrorefining process achieves uranium deposits at cathode using an electrochemical processing of spent nuclear fuel. In order to recover pure uranium from cathode deposit containing about 30wt% salt, the adhered salt should be removed by cathode process (CP). The CP has been regarded as one of the bottle-neck of the pyroprocess as the large amount of uranium is treated in this step and the operation parameters are crucial to determine the final purity of the product. Currently, related research activities are mainly based on experiments consequently it is hard to observe processing variables such as temperature, pressure and salt gas behavior during the operation of the cathode process. Hence, in this study operation procedure of cathode process is numerically described by using appropriate mathematical model. The key parameters of this research are the amount of evaporation at the distillation part, diffusion coefficient of gas phase salt in cathode processor and phase change rate at condensation part. Each of these conditions were composed by Hertz-Langmuir equation, Chapman-Enskog theory, and interphase mass flow application in ANSYS-CFX. And physical properties of salt were taken from the data base in HSC Chemistry. In this study, calculation results on the salt gas behavior and optimal operating condition are discussed. The numerical analysis results could be used to closely understand the physical phenomenon during CP and for further scale up to commercial level.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.16 no.4
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• pp.397-410
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• 2018

When considering the long-term safety assessment of spent-nuclear fuel management, americium is one of the most radio-toxic actinides. Although spectroscopic methods are widely used for the study of actinide chemistry, application of those methods to americium chemistry has been limited. Herein, we purified $^{241}Am$ to obtain a highly pure stock solution required for spectroscopic studies. Quantitative and qualitative analyses of purified $^{241}Am$ were carried out using liquid scintillation counting, and gamma and alpha radiation spectrometry. Highly sensitive absorption spectrometry coupled with a liquid waveguide capillary cell and time-resolved laser fluorescence spectroscopy were employed for the study of Am(III) hydrolysis and oxalate (Ox) complexation. $Am^{3+}$ ions under acidic conditions exhibit maximum absorbance at 503 nm, with a molar absorption coefficient of $424{\pm}8cm^{-1}{\cdot}M^{-1}$. $Am(OH)_3(s)$ colloidal particles formed under near neutral pH conditions were identified by monitoring the absorbance at around 506-507 nm. The formation of ${Am(Ox)_3}^{3-}$ was detected by red-shifts of the absorption and luminescence spectra of 4 and 5 nm, respectively. In addition, considerable enhancements of the luminescence intensities were observed. The luminescence lifetime of ${Am(Ox)_3}^{3-}$ increased from 23 to 56 ns, which indicates that approximately six water molecules are replaced by carboxylate ligands in the inner-sphere of the Am(III). These results suggest that ${Am(Ox)_3}^{3-}$ is formed through the bidentate coordination of the oxalate ligands.