• Analytical Science and Technology
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• v.23 no.1
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• pp.45-53
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• 2010

For the determination of chlorine in uranium compound, analytical methods by using a steam distillation and a pyrohydrolysis have been developed. The steam distillation apparatus was composed of steam generator, distilling flask and condenser etc. The samples were prepared with an aliquot of LiCl standard solution and a simulated spent nuclear fuel. A sample aliquot was mixed with a solution containing 0.2 M ferrous ammonium sulfate-0.5 M sulfamic acid 3 mL, phosphoric acid 6 mL and sulfuric acid 15 mL. The chloride was then distilled by steam at the temperature of $140^{\circ}C$ until a volume of $90{\pm}5\;mL$ is collected. The pyrohydrolysis equipment was composed of air introduction system, water supply, quartz reaction tube, combustion tube furnace, combustion boat and absorption vessel. The chloride was separated from powdered sample which is added with $U_3O_8$ accelerator, by pyrohydrolysis at the temperature of $950^{\circ}C$ for 1 hour in a quartz tube with a stream of air of 1 mL/min supplied from the water reservoir at $80^{\circ}C$. The chlorides collected in each absorption solution by two methods was diluted to 100 mL and measured with ion chromatography to determine the recovery yield. For the ion chromatographic determination of chlorine in molten salt retained in a metal ingot, the chlorine was separated by means of pyrohydrolysis after air and dry oxidation, and grinding for the sample.

• Journal of the Korean Chemical Society
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• v.28 no.5
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• pp.309-314
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• 1984

The species and equilibria of uranium and vanadium have been investigated in the various concentration of perchloric, hydrochloric and sulfuric acid by anion exchange chromatography. In the concentration range of $0.01\;{\sim}\;0.5M$ hydrochloric and $0.01\;{\sim}\;0.5M$ perchloric acid, uranium seems to be $UO_2^{2+}$species and in higher concentration than 0.5M hydrochloric acid $UO_2^{2+}$seems to form the chloride complex ion as $UO_2Cl^+$, $UO_2Cl_2$, $UO_2Cl_3^-$ and $UO_2Cl_4^{2-}$ according to the increase of the hydrochloric acid concentration. In the dilute(0.01N) sulfuric acid the adsorbability of uranium on anion exchange resin is strong and then decreases with increasing the sulfuric acid concentration. From this result we conclude that $UO_26{2+}$ formed the complex ion as $UO_2(SO_4)_2^{2-}$. In the perchloric acid of $0.01\;{\sim}\;0.5N$ concentration the existing equilibrium of vanadium and its constant calculated at $20^{\circ}C$ is $1.9{\times}108$ for $H_2V_{10}O_{28}^{4-}$ + $14H^+$ = $10VO_2^+ + 8H_2O$. The elution behaviors of vanadium in the hydrochloric and sulfuric acid are smiliar to those in perchloric acid.

• Journal of the Korean Chemical Society
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• v.27 no.4
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• pp.279-286
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• 1983

An apparatus was made for the electrodeposition of alpha emitting actinide nuclides, $^{207}Bi$ and $^{210}Po$. The electrodeposition was made on a polished stainless steel plate cathode. The anode was made of platinum wire and to stir the solution. With the ammonium chloride as electrolyte initial pH = 4, chloride concentration = 0.6M and solution volume = 15ml, a current of 1.5 ampere(current density = 0.59A/$cm^2$) was flowed for 100 minutes for the quantitative recovery of electrodeposition and on average recovery of 98.3% was obtained within ${\pm}$0.7% uncertainty. Alpha spectrometry of the electrodeposited sample showed alpha peaks from $^{210}Po, ^{234}U$ and $^{239}Pu$ having energy resolution (FWHM) of 18.3, 21.8 and 36.0 keV respectively. The electrodeposition and alpha spectrometry for a natural uranium sample of domestic origin gave $^{238}U : ^{234}U = 1 : 6.1{\times}10^{-5}$ and for a neutron-irradiated uranium sample did $^{238}U : ^{239}Pu : ^{241}Am = 100 : 0.0263 : 5.20{times}10^{-5}$. The result of $^{238}U$ determination in the irradiated sample by electrodeposition-alpha spectrometry was in accord within ${\pm}1.6%$ of relative error with the results of solid fluorimetry and mass spectrometry. For $^{239}Pu$ the result of electrodeposition-alpha spectrometry was in accord within ${\pm}$4.0% of relative error with the results of anion exchange separation and the thenoyltrifluoroacetone(TTA) extraction both followed by alpha spectrometries.

• Nuclear Engineering and Technology
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• v.54 no.2
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• pp.653-660
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• 2022

The interaction between UN and CdCl₂ in the LiCl-KCl molten eutectic was studied at 1023 K. The chlorination was monitored by sampling and recording the redox potential of the medium. At 1023 K the chlorination of UN with cadmium chloride in the molten LiCl-KCl eutectic proceeds completely and results in the formation of uranium chlorides. The melts of the LiCl-KCl-UCl₃ or LiCl-KCl-UCl₄ compositions can be obtained by the end of experiment depending on the presence of metallic cadmium in the reaction zone. The higher the concentration of the chlorinating agent, the faster the reaction rate. At [CdCl₂]/[UN] = 1.65 (10% excess) the reaction proceeds to completion in about 7.5 h. At [CdCl₂]/[UN] = 7 the complete chlorination takes 2.5-3 h.

• 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.14 no.3
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• pp.211-221
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• 2016

Waste salt generated from a pyro-processing for the recovery of uranium and transuranic elements has high volatility at vitrification temperature and low compatibility in conventional waste glasses. For this reason, KAERI (Korea Atomic Energy Research Institute) suggested a new method to de-chlorinate waste salt by using an inorganic composite named SAP ($SiO_2-Al_2O_3-P_2O_5$). In this study, the de-chlorination behavior of waste salt and the microstructure of consolidated form were examined by adding $B_2O_3$ and $Fe_2O_3$ to the original SAP composition. De-chlorination behavior of metal chloride waste was slightly changed with given compositions, compared with that of original SAP. In the consolidated forms, the phase separation between Si-rich phase and P-rich phase decreases with the amount of $Al_2O_3$ or $B_2O_3$ as a connecting agent between Si and P-rich phase. The results of PCT (Product Consistency Test) indicated that the leach-resistance of consolidated forms out of reference composition was lowered, even though the leach-resistance was higher than that of EA (Environmental Assessment) glass. From these results, it could be inferred that the change in the content of Al or B in U-SAP affected the microstructure and leach-resistance of consolidated form. Further studies related with correlation between composition and characteristics of wasteform are required for a better understanding.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.10 no.1
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• pp.45-53
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• 2012

The metal chloride wastes from a pyrochemical process to recover uranium and transuranic elements has been considered as a problematic waste difficult to apply to a conventional solidification method due to the high volatility and low compatibility with silicate glass. In this study, a dechlorination approach to treat LiCl-KCl waste for final disposal was adapted. In this study, a $SiO_2-Al_2O_3-P_2O_5$ (SAP) inorganic composite as a dechlorination agent was prepared by a conventional sol-gel process. By using a series of SAPs, the dechlorination behavior and consolidation of reaction products were investigated. Different from LiCl waste, the dechlorination reaction occurred mainly at two temperature ranges. The thermogravimetric test indicated that the first reaction range was about $400^{\circ}C$ for LiCl and the second was about $700^{\circ}C$ for KCl. The SAP 1071 (Si/Al/P=1/0.75/1 in molar) was found to be the most favorable SAP as a dechlorination agent under given conditions. The consolidation test revealed that the bulk shape and the densification of consolidated forms depended on the SAP/Salt ratios. The leaching test by PCT-A method was performed to evaluate the durability of consolidated forms. This study provided the basic information on the dechlorination approach. Based on the experimental results, the dechlorination method using a $SiO_2-Al_2O_3-P_2O_5$ (SAP) could be considered as one of alternatives for the immobilization of waste salt.