• Korean Journal of Materials Research
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• v.27 no.12
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• pp.672-678
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• 2017

In the production of zirconium cladding tube, a pickling acid solution is used to remove surface contaminants, which generates tons of pickling acid waste. The waste pickling solution is a valuable resource of Hf-free Zr. Many studies have investigated separating the Hf-free Zr source from the waste pickling acid. The results showed that $Ba_2ZrF_8$ precipitates prepared from the waste pickling acid were useful as an electrolyte for the electrorefining of Zr in molten salt. In the present work, electrorefining was performed in a $Ba_2ZrF_8-LiF$ binary electrolyte to recover Zr from a Hf-free CuZr ingot anode prepared by electroreduction. Before electrorefining, two pretreatments are performed. First, electrolyte melting was carried out to determine the eutectic temperature, and second, the electrolyte was treated to eliminate impurities, mainly hydride. After electrorefining, the cathode deposits were analyzed by $O_2$ gas analyzer and SEM-EDX to explore the possibility of recovering nuclear-grade Zr metal. Moreover, the anode was analyzed by SEM-EDX to determine the Zr dissolution depth.

• Proceedings of the Korean Radioactive Waste Society Conference
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• 2004.06a
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• pp.319-329
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• 2004

The electrorefining experiments with an anode composed of U, Y, Gd, Nd and Ce (or U, Gd, Dy and Ce) were carried out in the KC1-LiCl eutectic melt at $500^{\circ}C$, Uranium was the major component in the cathode deposits at the high initial uranium concentration, and the separation factors of the uranium with respect to the rare earths (REs) were calculated according to the applied voltage and the uranium concentration in the molten salt. The current efficiency was inversely in proportion to the applied voltage in the range of 1.0 V to 1, 9 V (vs. STS304L). The dependency of the applied voltage on the current efficiency as well as the deposition rate was discussed in terms of the microstructural feature and crystal structure of the deposit.

• Journal of Korean Society on Water Environment
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• v.22 no.4
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• pp.658-665
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• 2006

The removal characteristics of silver ion from waste photographic solution have been investigated by recovering silver electrochemically. Cyclic voltammetry for synthetic and actual wastewater which containing silver ion was investigated to understand its electrochemical behavior. For both synthetic and actual wastewater, the recovery of silver according to the electrowinning time was observed to be increased as the applied potential was raised. In addition, the applicable potential for the electrowinning of silver was found to be lower for synthetic wastewater compared with actual wastewater. As the temperature was increased, more silver was recovered for both wastewater, which indicated the electrowinning reaction was endothermic. The electrowinned silver was refined electrochemically to increase its purity and the variation of the purity of silver was examined according to the electrorefining potential.

• Journal of the Korean institute of surface engineering
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• v.42 no.3
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• pp.103-108
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• 2009

The effect of Arsenic in copper-sulfate solutions during electrorefining of copper was investigated using scanning electron microscopy, X-ray diffraction and cyclic voltammetry analysis. Electrodeposition was carried out using Arsenic, Antimony and bismuth addition to sulfate electrolytes: 45 g/l $Cu^{2+}$ and 170 g/l $H_2SO_4$. Arsenic in sulfate electrolytes changed the morphology and structure of the copper deposits as compared with those obtained from impurity free solutions. When arsenic was present in the sulfate electrolytes, $Cu-3$As intermetallic phase was formed locally on the deposits.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.17 no.3
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• pp.347-353
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• 2019

The composition of the reduced fuel produced in the electrolytic reduction process of pyroprocessing affects the concentration change of $UCl_3$, an important operating variable of the electrorefining process. In this study, we examined the concentration change of $UCl_3$ in the electrorefiner according to the content of TRU and RE elements in the reduced fuel and the concentration of $Li_2O$ introduced in the electrorefiner accompanied with the reduced fuel. Considering only the TRU and RE elements, the concentration of $UCl_3$ decreased with increasing the number of electrorefining operation batch. In order to operate one campaign (20 batches) of electrorefining process, it was found that additional injection of $UCl_3$ should be conducted more than 3 times. On the other hand, the concentration of $UCl_3$ in the electrorefiner changed significantly depending on the concentration of $Li_2O$ and, accordingly the number of operable electrorefining batches decreased rapidly, showing that the concentration of $Li_2O$ is an important operating variable in electrorefining. Therefore, the results of this study show that to maintain the concentration of $UCl_3$ in the electrorefiner, the operation mode should be set by taking into account the effect of $Li_2O$ as well as the TRU and RE elements contained in the reduced fuel.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.5 no.1
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• pp.1-7
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• 2007

Electrorefining experiments were successfully carried out in LiCl-KCl eutectic molten salt with a graphite cathode. It was found that the formation of Uranium-Graphite intercalation compound(U-GIC) helped the self-scraping mechanism of the uranium dendrite and the efficiency of the electrorefiner increased due to an elimination of the stripping step. The contaminations of the uranium deposit by rare earth elements was negligible while about 300 ppm of carbon was observed. The carbon contamination is believed to be eliminated by further purification by yttrium reaction. The morphology characteristics of the recovered U deposit was compared to that of steel cathode. These are only qualitative preliminary experimental results, but we believe that further research on this type of activity change the direction of the electrorefining research on spent nuclear fuel.

• Nuclear Engineering and Technology
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• v.42 no.2
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• pp.131-144
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• 2010

The Korea Atomic Energy Research Institute (KAERI) has been developing pyroprocessing technology for recycling useful resources from spent fuel since 1997. The process includes pretreatment, electroreduction, electrorefining, electrowinning, and a waste salt treatment system. This paper briefly addresses unit processes and related innovative technologies. As for the electroreduction step, a stainless steel mesh basket was applied for adaption of granules of uranium oxide. This basket was designed for ready handling and transfer of feed material. A graphite cathode was used for the continuous collection of uranium dendrite in the electrorefining system. This enhances the throughput of the electrorefiner. A particular mesh type stirrer was designed to inhibit uranium spill-over at the liquid Cd crucible. A residual actinide recovery system was also tested to recover TRU tracer. In order to reduce the waste volume, a crystallization method is employed for Cs and Sr removal. Experiments on the unit processes were tested successfully, and based on the results, engineering-scale equipment has been designed for the PRIDE (PyRoprocess Integrated inactive DEmonstration facility).

• Applied Chemistry for Engineering
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• v.10 no.8
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• pp.1119-1123
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• 1999

In this paper, electrorefining of uranium metal was studied to develop pyrometallurgical processing technology in molten salt system. The reaction between uranium metal and $CdCl_2$ was taken about 3 hours and the uranium metal deposits were obtained in the form of dendrite grown on the cathode surface in every electrotransport experiment. The shapes of dendrite were changed according to the applied voltages. Current efficiency was decreased with the increase of current density. Deposition rate was not changed after 6 hours and its maxium was obtained at $100{\sim}150mA/cm^2$ of current density and about 75 rpm of stirring speed, respectively. Also, the current efficiency was increased with decrease of the pitch of spiral groove curved on cathode.

• Nuclear Engineering and Technology
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• v.54 no.2
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• pp.644-652
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• 2022

During the pyroprocessing operation, various signals can be collected by process monitoring (PM). These signals are utilized to diagnose process states. In this study, feasibility of using PM for nuclear safeguards of electrorefining operation was examined based on the use of machine learning for detecting off-normal operations. The off-normal operation, in this study, is defined as co-deposition of key elements through reduction on cathode. The monitored process signal selected for PM was cathode potential. The necessary data were produced through electrodeposition experiments in a laboratory molten salt system. Model-based cathodic surface area data were also generated and used to support model development. Computer models for classification were developed using a series of recurrent neural network architectures. The concept of transfer learning was also employed by combining pre-training and fine-tuning to minimize data requirement for training. The resulting models were found to classify the normal and the off-normal operation states with a 95% accuracy. With the availability of more process data, the approach is expected to have higher reliability.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.21 no.1
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• pp.9-22
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• 2023

Spin-off pyroprocessing technology and inert anode materials to replace the conventional carbon-based smelting process for critical materials were introduced. Efforts to select inert anode materials through numerical analysis and selected experimental results were devised for the high-throughput reduction of oxide feedstocks. The electrochemical properties of the inert anode material were evaluated, and stable electrolysis behavior and CaCu generation were observed during molten salt recycling. Thereafter, CuTi was prepared by reacting rutile (TiO₂) with CaCu in a Ti crucible. The formation of CuTi was confirmed when the concentration of CaO in the molten salt was controlled at 7.5mol%. A laboratory-scale electrorefining study was conducted using CuTi(Zr, Hf) alloys as the anodes, with a Ti electrodeposit conforming to the ASTM B299 standard recovered using a pilot-scale electrorefining device.