• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.8 no.4
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• pp.303-309
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• 2010

For the pyrochemical process of spent nuclear fuels, recovery of LiCl-KCl eutectic salts is needed to reduce radioactive waste volume and to recycle resource materials. This paper is about recovery of residual LiCl-KCl eutectic salts in radioactive rare earth precipitates (rare earth oxychlorides or oxides) by using a vacuum distillation process. In the vacuum distillation test apparatus, the salts in the rare earth precipitates were vaporized and were separated effectively. The separated salts were deposited in three positions of the vacuum distillation test apparatus or were collected in the filter and it is difficult to recover them. To resolve the problem, a vacuum distillation and condensation system, which is subjected to the force of a temperature gradient at a reduced pressure, was developed. In a preliminary test of the vacuum distillation/condensation recovery system, it was confirmed that it was possible to condense the vaporized salts only in the salt collector and to recover the condensed salts from the salt collector easily.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.15 no.1
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• pp.83-90
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• 2017

The pyroprocessing of spent nuclear fuel generates LiCl-KCl eutectic waste salt containing radioactive rare earth nuclides. It is necessary to develop a simple process for the treatment of LiCl-KCl eutectic waste in a hot-cell facility. In this study, capture and solidification of a rare earth nuclide (Nd) in LiCl-KCl eutectic salt using an inorganic composite with a $Li_2O-Al_2O_3-SiO_2-B_2O_3$ system was conducted to simplify the existing separation and solidification process of rare earth nuclides in LiCl-KCl eutectic waste salt from the pyroprocessing of spent nuclear fuel. More than 98wt% of Nd in LiCl-KCl eutectic salt was captured when the mass ratio of the composite was 0.67 over $NdCl_3$ in the eutectic salt. The content of $Nd_2O_3$ in the Nd captured-composite reached about 50wt%, and this composite was directly fabricated into a homogeneous and chemical resistant glass waste in a monolithic form. These results will be utilized in designing a process to simplify the existing separation and solidification process.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.16 no.3
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• pp.309-313
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• 2018

In this study, we prepared Li-K-Cd alloy, which meets the requirement of eutectic ratio of Li:K, to maintain the operating temperature of the drawdown process at $500^{\circ}C$ and to achieve the reuse of LiCl-KCl molten salt. The prepared Li-K-Cd alloys were added to LiCl-KCl salt bearing U and Nd at $500^{\circ}C$ to investigate the removal of $UCl_3$ in the salt. The reduction of $UCl_3$ in the salt was examined by measuring the OCP value of salt and analyzing the salt composition by ICP-OES. Reduction was also visually confirmed by change of salt color from dark purple to white. The experimental results reveal that the prepared Li-K-Cd alloy has reductive extractability for $UCl_3$ in salt. By improving the preparation method, the Li-K-Cd alloy can be applied to the drawdown process.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.7 no.4
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• pp.207-212
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• 2009

In this study, a thermal behavior of $PrCl_3$ as one of the lanthanide chlorides in LiCl-KCl molten salts was investigated in an oxidizing condition. First, a thermo-gravimetric analysis (TGA) of $PrCl_3$ was carried out by an injection of $O_2$ gas. Based on the results, an oxidation of $PrCl_3$ in the molten salts was performed by sparging $O_2$ gas with changing temperatures. According to the TGA data of $PrCl_3$, a dissociation of $PrCl_3$ occurred rapidly by about $380^{\circ}C$ and a conversion of $PrCl_3$ to $PrCl_3$ was completed at about $600^{\circ}C$. The thermal behavior of $PrCl_3$ in LiCl-KCl molten salts by sparging $O_2$ gas was similar to that of $PrCl_3$ in the TGA test, and PrOCl as a insoluble compound in the molten salts was precipitated into the bottom of the molten salts. A conversion of $PrCl_3$ to PrOCl in the molten salts occurred actively at a higher temperature than $650^{\circ}C$. And it would be possible to estimate a conversion status of $PrCl_3$ to PrOCl by measuring a $Cl_2$ concentration in a flue gas generated from an oxidation test of $PrCl_3$ in LiCl-KCl molten salts.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.11 no.4
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• pp.325-332
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• 2013

Pyroporcessing of spent nuclear fuel generates a considerable amount of LiCl-KCl eutectic waste salt containing radioactive rare earth (RE) chlorides. In this study, a series of processes, which consist of a phosphorylation/distillation process and a solidification process, were performed to minimize volume of the LiCl-KCl eutectic waste salt and solidify a residual waste into a stable form at a relatively low temperature. Over 99wt% of RE chlorides in LiCl-KCl eutectic salt was converted and separated into $REPO_4$ in the phosphorylation/distillation process using a mixture of $Li_3PO_4-K_3PO_4$. The separated $REPO_4$ was solidified into a homogeneous and fine-grained form at $1,050^{\circ}C$ using LIP(Lead Iron Phosphate) as a solidification agent. The final waste volume was reduced below about 10% through the series of the processes.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.13 no.3
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• pp.181-186
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• 2015

It is necessary to develop an effective waste salt treatment technology for the minimization of radioactive waste generation from the pyroprocessing of spent nuclear fuel. For this reason, the separation characteristics of NdCl₃ from LiCl-KCl eutectic salt in a reactive distillation process using Li₂CO₃ or K₂CO₃ were observed. NdCl₃ was converted into oxychloride (NdOCl) or oxide (Nd₂O₃) in the reaction model between NdCl₃ and the carbonates using HSC-Chemistry, and this result was confirmed in the reactive distillation test of the LiCl-KCl-NdCl₃ system using the carbonates. Based on these results, the reactive distillation process conditions were determined to separate NdCl₃ into an oxide form (Nd₂O₃) which can be easily fabricated into a final waste form.

• Applied Chemistry for Engineering
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• v.18 no.4
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• pp.361-365
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• 2007

The precipitation reaction of some rare earth chlorides ($Ce/Nd/GdCl_3$) in a LiCl-KCl molten salt has been carried out by reaction with oxygen. Identification of rare earth precipitates by reaction with oxygen and effects of oxygen sparging time (max. 420 min) and molten salt temperature ($450{\sim}750^{\circ}C$) on conversion were investigated. In this study, regardless of the oxygen sparging time and the molten salt temperature, oxychlorides (REOCl) for $NdCl_3$ and $GdCl_3$, and an oxide ($REO_2$) for $CeCl_3$ are formed as a precipitate, which are identical with the estimation results of Gibbs free energy of reaction (${\Delta}G_r$). The conversion of rare-earth chlorides into insoluble precipitates was described by using a conversion ratio. The conversion ratio increased exponentially with the oxygen sparging time and finally showed asymptotic value, over 0.999 at $750^{\circ}C$ of the molten salt temperature and over 300 min of sparging time conditions. The conversion ratios were increased with the molten salt temperature. In case of $CeCl_3$, when the sparging time exceed 60 min, the values of the conversion ratio were nearly constant over 0.999 in all experimental temperature conditions.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.16 no.1
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• pp.59-64
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• 2018

In case of high contents of rare earths in the LiCl-KCl salt, it is not easy to recover U and TRU metals as a usable resource form from LiCl-KCl eutectic salts generated from the pyroprocessing of spent nuclear fuel. In this study, a conversion of $UCl_3$ into an oxide form using $K_2CO_3$ and an electrodeposition of $NdCl_3$ into a metal form in $LiCl-KCl-UCl_3-NdCl_3$ system were conducted to resolve the problem. Before conducting the conversion, experimental conditions for the conversion were determined by performing a thermodynamic equilibrium calculation. In this study, almost all of $UCl_3$ disappeared in the LiCl-KCl salt when the injection of $K_2CO_3$ reached theoretical equivalent for the conversion, and then $NdCl_3$ was effectively electrodeposited as a metal form using liquid zinc cathode. After that, the LiCl-KCl salt became transparent, and uranium oxides were precipitated to the bottom of the LiCl-KCl salt. These results will be utilized in designing a process to separate U and rare earths in LiCl-KCl salt.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.13 no.4
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• pp.263-269
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• 2015

It is necessary to investigate the electrodeposition behavior of uranium and other elements on the cathode in the electrorefining process to recover the uranium selectively from the reduced metals of the electrolytic reduction process since transuranic elements and rare earth elements is dissolved in the LiCl-KCl eutectic salt. Study on separation factors of U, Ce, Y and Nd based on U and Ce was performed to investigate the deposition behavior of the cathode with respect to the concentration of rare earth elements in LiCl-KCl eutectic salt. After electrorefining with constant current mode by using Ce metal as a sacrifice anode, the contents of U, Ce, Y and Nd in the salt phase and the deposit phase of the cathode were analyzed, and separation factors of the elements were obtained from the analyses. Securing conditions of pure uranium recovery in the elctrorefining process was investigated by considering the separation factors with respect to $UCl_3$ and $CeCl_3/UCl_3$ ratio.

• Proceedings of the Korean Radioactive Waste Society Conference
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• 2016.10a
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• pp.67-68
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• 2016