• Proceedings of the Korean Radioactive Waste Society Conference
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• 2019.05a
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• pp.69-69
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• 2019

The distillation of liquid cathode is necessary to separate cadmium from the actinide elements in the pyroprocessing since the actinide deposits are dissolved or precipitated in a liquid cathode. It is very important to avoid a splattering of cadmium during evaporation due to the high vapor pressure. Several methods have been proposed to lower the splattering of cadmium during distillation. One of the important methods is an installation of crucible cover on the distillation crucible. A multi-layer porous round cover was proposed to avoid a cadmium splattering in our previous study. In this study, the effect of crucible cover on the cadmium distillation was examined to develop a splatter shield. Various surrogates were used for the actinides in the cadmium. The surrogates such as bismuth, zirconia, and tungsten don't evaporate at the operational temperature of the Cd distiller due to their low vapor pressures. The distillation experiments were carried out in a crucible equipped with cover and in a crucible without cover. About 40 grams of Cd was distilled at a reduced pressure for two hours at various temperatures. The mixture of the cadmium and the surrogate was heated at $470{\sim}620^{\circ}C$. Most of the bismuth remained in the crucible equipped with cover after distillation under $580^{\circ}C$ for two hours, whereas small amount of bismuth decreased in the crucible without cover above $580^{\circ}C$. The liquid bismuth escaped with liquid cadmium drop from the crucible without cover. It seems that the crucible cover played a role to prevent the splash of the liquid cadmium drop. The effect of the cover was not clear for the tungsten or zirconia surrogate since the surrogates remained as a solid powder at the experimental temperature. From the results of this work, it can be concluded that the crucible cover can be used to minimize the deposit loss by prevention of escape of liquid drop from the crucible during distillation of liquid cathode.

• Proceedings of the Korean Radioactive Waste Society Conference
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• 2018.11a
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• pp.103-103
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• 2018

The liquid cathode processing is necessary to separate cadmium from the actinide elements in the pyroprocessing since the actinide deposits are dissolved or precipitated in a liquid cathode. Distillation process was employed for the cathode processing owing to the compactness. It is very important to avoid a splattering of cadmium during evaporation due to the high vapor pressure. Several methods have been proposed to lower the splattering of cadmium during distillation. A multi-layer porous round cover was proposed to avoid a cadmium splattering in our previous study. In this study, distillation behavior of $Cd-ZrO_2$ and Cd - Bi systems were investigated to examine a multi-layer porous round cover for the development of the cadmium splatter shield of distillation crucible. It was designed that the cadmium vapor can be released through the holes of the shield, whereas liquid drops can be collected in the multiple hemisphere. The cover was made with three stainless steel round plates with a diameter of 33.50 mm. The distance between the hemispheres and the diameter of the holes are 10 and 1 mm, respectively. Bismuth or zirconium oxide powder was used as a surrogate for the actinide elements. About 40 grams of Cd was distilled at a reduced pressure for two hours at various temperatures. The mixture of the cadmium and the surrogate was distilled at 470, 570 and $620^{\circ}C$ in the crucible with the cover. Most of the bismuth or zirconia remained in the crucible after distillation at 470 and $570^{\circ}C$ for two hours. It was considered that the crucible cover hindered the splattering of the liquid cadmium from the distillation crucible. A considerable amount of the surrogate material reduced after distillation at $620^{\circ}C$ due to the splattering of the liquid cadmium. The low temperature is favorable to avoid a liquid cadmium splattering during distillation. However, the optimum temperature for the cadmium distillation should be decided further, since the evaporation rate decreases with a decreasing temperature.

• Proceedings of the Korean Radioactive Waste Society Conference
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• 2004.06a
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• pp.337-337
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• 2004

As one of researches for the P ＆ T purposes, a basic experiment on the recovery of actinide elements from the mixture with rare earth elements by means of electrorefining using a liquid cadmium cathode in the LiCl-KC1 eutectic melt was carried out. In order to examine the behaviors of electrodeposition of metal ions on a liquid electrode, recovery experiments of rare earth metals resulting from forming electrodeposits were performed by a galvanostatic electrolysis method at various current densities. A cyclic voltammetric technique was applied to determine reduction-oxidation potential of each metal element in the melt and to detect the changes of the multi component melt composition for on-line monitoring. Also, a collaboration study with RIAR was completed to test the preliminary feasibility on a recovery of actinide elements from the mixture with rare earth elements using a liquid cadmium cathode and actinide metals. Experimental results showed that the ratio of actinides to rare earths, 9: 0.5∼1 led to the rare earth content of about 5∼10 wt% in the deposit.

• Proceedings of the Korean Radioactive Waste Society Conference
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• 2018.05a
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• pp.57-57
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• 2018

The electrorefining process is generally composed of two recovery steps in pyroprocessing - the deposit of uranium onto a solid cathode and the recovery of the remaining uranium and TRU elements simultaneously by a liquid cadmium cathode. The liquid cathode processing is necessary to separate cadmium from the actinide elements since the actinide deposits are dissolved or precipitated in a liquid cathode. Distillation process was employed for the cathode processing. It is very important to avoid a splattering of cadmium during evaporation due to the high vapor pressure. In this study, a multi-layer porous round cover was proposed and examined to develop a splatter shield for the Cd distillation crucible. Cadmium vapor can be released through the holes of the shield, whereas liquid drops can be collected in the multiple hemisphere. The collected drops flow on the round surface of the cover and flow down into the crucible. The crucible cover was fabricated and tested in the Cd distiller. The cover was made with three stainless steel round plates with a diameter of 33.50 mm. The distance between the hemispheres and the diameter of the holes are 10 and 1 mm, respectively. About 40 grams of Cd and about 4 grams of Bi was distilled at a reduced pressure for two hours at $470^{\circ}C$. After the Cd distillation experiment, cadmium was not detected and more than 90 % of Bi remained in the ICP-OES analysis. Therefore the crucible cover can be a candidate for the splatter shield of the Cd distillation crucible. Further development of the crucible cover is necessary for the decision of the optimum cover geometry and the operating conditions of the Cd distiller.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.11 no.3
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• pp.199-206
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• 2013

Electrowinning process in pyroprocessing recovers U (uranium) and TRU (Trans Uranium) elements simultaneously from spent fuels using a liquid cadmium cathode (LCC). When the solubility limit of U deposits over 2.35wt% in Cd, U dendrites were formed on the LCC surface during the electrodeposition at $500^{\circ}C$. Due to the high surface area of dendritic U, the deposits were not submerged into the liquid cadmium pool but grow out of the LCC crucible. Since the U dendrites act as a solid cathode, it prevents the co-deposition of U and TRUs. In this study, the electrodeposition of U onto a LCC was carried out at 440 and $500^{\circ}C$ to compare the morphology and component of U deposits. The U deposits at $440^{\circ}C$ have a specific shape and were stacked regularly at the center of the LCC pool, while the U dendrites (i.e., ${\alpha}$-phase) at $500^{\circ}C$ were grow out of the LCC crucible. Through the microscopic observation and XRD analysis, the electrodeposits at $440^{\circ}C$, which have a round shape, were identified as an intermetallic compound such as $UCd_{11}$. It can be concluded that the LCC electrowinning operation at $440^{\circ}C$ achieves the co-recovery of U and TRU without the formation of U dendrites.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.8 no.1
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• pp.9-17
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• 2010

The LCC (Liquid Cadmium Cathode) structure to be developed for inhibiting the formation and growth of the uranium dendrite has been known as a key part in the electrowinning process for the simultaneous recovering of uranium and TRU (TRans Uranium) elements from spent fuels. A zinc-gallium (Zn-Ga) experimental system which is able to be functional in aqueous condition and normal temperature has been set up to observe the formation and growth phenomena of the metal dendrites on liquid cathode. The growth of the zinc dendrites on the gallium cathode and the performance of the existing stirrer type and pounder type cathode structure were observed. Although the mechanical strength of the dendrites appeared to be weak in the electrolyte and easily crashed by the various cathode structures, it was difficult to effectively submerge the dendrite into the bottom of the liquid cathode. Based on the results of the aqueous phase experiments, a lab-scale electrowinning experimental apparatus which are applicable to the development of LCC srtucture for the electrowinning process was established and the performance tests of the different types of LCC structure were conducted to prohibit the uranium dendrite growth on LCC surface. The experimental results of the stirrer type LCC structures have shown that they could not effectively remove the uranium dendrites growing at the inner side of the LCC crucible and the performances of the paddle and harrow type LCC structure were similar. Therefore a mesh type LCC structure was developed to push down the uranium dendrites to the bottom of the LCC crucible growing on the LCC surface and at the inner side of the crucible. From the experimental results for the performance test of the mesh type LCC structure, the uranium was recovered over 5 wt% in cadmium without the growth of uranium dendrites. After completion of the experiments, solid precipitates of the bottom of the LCC crucible were identified as an intermetallic compound (UCd11) by the chemical analysis.

• Journal of Advanced Engineering and Technology
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• v.4 no.4
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• pp.431-436
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• 2011

This study was carried out to reduce the problem during distillation process, which separate U, TRU (TRans Uranium) metal electro deposit, Cd and LiCl-KCl eutectic salt generating from LCC (Liquid Cadmium Cathode) electro winning process. The cadmium recovering apparatus was manufactured to separate for each metal using solid-liquid separation method. The apparatus consists of the first sieve for the separation of U and TRU metal electrodeposit, the second sieve for the separation of LiCl-KCl eutectic salt, cadmium collection basket, and a heating furnace. In addition, the size of each sieve is 2 mm to 3 mm. In this experiment, a metal wire was employed to replace TRU metal electrodeposit and U, which exist actually in a LCC crucible. In the solid state, The LiCl-KCl is separated at 340℃ at which the solid and the liquid of the remaining cadmium and LiCl-KCl eutectic salt coexists in each, after the metal wire separated at 500℃. As a result, it seems that it would be beneficial to set the processing condition in the distillation process with the additional treatment process of cadmium and LiCl-KCl eutectic salt.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.8 no.4
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• pp.261-267
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• 2010

The pyrometallurgical nuclear fuel recycle process, called pyroprocessing, has been known as a promising nuclear fuel recycling technology. Pyroprocessing technology is crucial to advanced nuclear systems due to increased nuclear proliferation resistance and economic efficiency. The basic concept of pyroprocessing is group actinide recovery, which enhances the nuclear proliferation resistance significantly. One of the key steps in pyroprocessing is "electrowinning" which recovers group actinides with lanthanide from the spent nuclear fuels. In this study, a vertical cadmium distiller was manufactured. The evaporation rate of pure cadmium in vertical cadmium distiller varied from 12.3 to $40.8g/cm^2/h$ within a temperature range of 773 923 K and pressure below 0.01 torr. Uranium - cadmium alloy was fabricated by electrolysis using liquid cadmium cathode in a high purity argon atmosphere glove box. The distillation behavior of pure cadmium and cadmium in uranium - cadmium alloy was investigated. The distillation behavior of cadmium from this study could be used to develop an actinide recovery process from a liquid cadmium cathode in a cadmium distiller.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.8 no.1
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• pp.1-7
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• 2010

In the present work, an electrowinning process in the LiCl-KCl/Cd system is considered to model and analyze the electrotransport of the actinide and rare-earth elements. A simple dynamic modeling of this process was performed by taking into account the material balances and diffusion-controlled electrochemical reactions in a diffusion boundary layer at an electrode interface between the molten salt electrolyte and liquid cadmium cathode. The proposed modeling approach was based on the half-cell reduction reactions of metal chloride occurring on the cathode. This model demonstrated a capability for the prediction of the concentration behaviors, a faradic current of each element and an electrochemical potential as function of the time up to the corresponding electrotransport satisfying a given applied current based on a galvanostatic electrolysis. The results of selected case studies including five elements (U, Pu, Am, La, Nd) system are shown, and a preliminary simulation is carried out to show how the model can be used to understand the electrochemical characteristics and provide better information for developing an advanced electrowinner.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.11 no.1
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• pp.23-29
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• 2013

LCC (Liquid cadmium cathode) is used for electrowinning in pyroprocessing to recover uranium and transuranic elements simultaneously. It is one of the core technologies in pyroprocessing with higher proliferation resistance than a wet reprocessing because LCC-cell does not separate TRU from uranium. The crucible which holds the LCC is technically important because it should be nonconducting material to prevent deposition of metallic elements on the crucible outer surface. The chemical stability is also crucial factor to choose crucible material due to the strong reactivities of TRU and possible incorporation of Li metal during the operation. In this study, the chemical stabilities of four kinds of representative ceramic materials such as $Al_2O_3$, MgO, $Yl_2O_3$ and BeO were thermodynamically and experimentally evaluated at $500^{\circ}C$ with simulated LCC. The contact angle of LCC on ceramic materials was measured as function of time to predict chemical reactivity. $All_2O_3$ showed poorest chemical stability and the pores in BeO contributed to a decreases in contact angle. MgO and $Y_2O_3$ have superior chemical stability among the materials.