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Density of Molten Salt Mixtures of Eutectic LiCl-KCl Containing UCl3, CeCl3, or LaCl3

  • Zhang, C.;Simpson, M.F.
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.15 no.2
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    • pp.117-124
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    • 2017
  • Densities of molten salt mixtures of eutectic LiCl-KCl with $UCl_3$, $CeCl_3$, or $LaCl_3$ at various concentrations (up to 13 wt%) were measured using a liquid surface displacement probe. Linear relationships between the mixture density and the concentration of the added salt were observed. For $LaCl_3$ and $CeCl_3$, the measured densities were significantly higher than those previously reported from Archimedes' method. In the case of $LiCl-KCl-UCl_3$, the data fit the ideal mixture density model very well. For the other salts, the measured densities exceeded the ideal model prediction by about 2%.

MOLTEN SALT VAPORIZATION DURING ELECTROLYTIC REDUCTION

  • Hur, Jin-Mok;Jeong, Sang-Moon;Lee, Han-Soo
    • Nuclear Engineering and Technology
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    • v.42 no.1
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    • pp.73-78
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    • 2010
  • The suppression of molten salt vaporization is one of the key technical issues in the electrolytic reduction process developed for recycling spent nuclear fuel from light-water reactors Since the Hertz-Langmuir relation previously applied to molten salt vaporization is valid only for vaporization into a vacuum, a diffusion model was derived to quantitatively assess the vaporization of LiCl, $Li_2O$ and Li from an electrolytic reducer operating under atmospheric pressure. Vaporization rates as a function of operation variables were calculated and shown to be in reasonable agreement with the experimental data obtained from thermogravimetry.

Water Sorption/Desorption Characteristics of Eutectic LiCl-KCl Salt-Occluded Zeolites

  • Harward, Allison;Gardner, Levi;Oldham, Claire M. Decker;Carlson, Krista;Yoo, Tae-Sic;Fredrickson, Guy;Patterson, Michael;Simpson, Michael F.
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.20 no.3
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    • pp.259-268
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    • 2022
  • Molten salt consisting primarily of eutectic LiCl-KCl is currently being used in electrorefiners in the Fuel Conditioning Facility at Idaho National Laboratory. Options are currently being evaluated for storing this salt outside of the argon atmosphere hot cell. The hygroscopic nature of eutectic LiCl-KCl makes is susceptible to deliquescence in air followed by extreme corrosion of metallic cannisters. In this study, the effect of occluding the salt into a zeolite on water sorption/desorption was tested. Two zeolites were investigated: Na-Y and zeolite 4A. Na-Y was ineffective at occluding a high percentage of the salt at either 10 or 20wt% loading. Zeolite-4A was effective at occluding the salt with high efficiency at both loading levels. Weight gain in salt occluded zeolite-4A (SOZ) from water sorption at 20% relative humidity and 40℃ was 17wt% for 10% SOZ and 10wt% for 20% SOZ. In both cases, neither deliquescence nor corrosion occurred over a period of 31 days. After hydration, most of the water could be driven off by heating the hydrated salt occluded zeolite to 530℃. However, some HCl forms during dehydration due to salt hydrolysis. Over a wide range of temperatures (320-700℃) and ramp rates (5, 10, and 20℃ min-1), HCl formation was no more than 0.6% of the Cl- in the original salt.

Investigation on Dissolution and Removal of Adhered LiCl-KCl-UCl3 Salt From Electrodeposited Uranium Dendrites using Deionized Water, Methanol, and Ethanol

  • Killinger, Dimitris Payton;Phongikaroon, Supathorn
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.18 no.4
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    • pp.549-562
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    • 2020
  • Deionized water, methanol, and ethanol were investigated for their effectiveness at dissolving LiCl-KCl-UCl3 at 25, 35, and 50℃ using inductively coupled plasma mass spectrometry (ICP-MS) to study the concentration evolution of uranium and mass ratio evolutions of lithium and potassium in these solvents. A visualization experiment of the dissolution of the ternary salt in solvents was performed at 25℃ for 2 min to gain further understanding of the reactions. Aforementioned solvents were evaluated for their performance on removing the adhered ternary salt from uranium dendrites that were electrochemically separated in a molten LiCl-KCl-UCl3 electrolyte (500℃) using scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS). Findings indicate that deionized water is best suited for dissolving the ternary salt and removing adhered salt from electrodeposits. The maximum uranium concentrations detected in deionized water, methanol, and ethanol for the different temperature conditions were 8.33, 5.67, 2.79 μg·L-1 for 25℃, 10.62, 5.73, 2.50 μg·L-1 for 35℃, and 11.55, 6.75, and 4.73 μg·L-1 for 50℃. ICP-MS analysis indicates that ethanol did not take up any KCl during dissolutions investigated. SEM-EDS analysis of ethanol washed uranium dendrites confirmed that KCl was still adhered to the surface. Saturation criteria is also proposed and utilized to approximate the state of saturation of the solvents used in the dissolution trials.

Electrochemical Behavior for a Reduction of Uranium Oxide in a $LiCl-Li_{2}O$ Molten Salt with an Integrated Cathode assembly

  • Park, Sung-Bin;Park, Byung-Heung;Seo, Chung-Seok;Jung, Ki-Jung;Park, Seong-Won
    • Proceedings of the Korean Radioactive Waste Society Conference
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    • 2005.11b
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    • pp.39-50
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    • 2005
  • Electrolytic reduction of uranium oxide to uranium metal was studied in a $LiCl-Li_{2}O$ molten salt system. The reduction mechanism of the uranium oxide to a uranium metal has been studied by means of a cyclic voltammetry. Effects of the layer thickness of the uranium oxide and the thickness of the MgO on the overpotential of the cathode and the anode were investigated by means of a chronopotentiometry. From the cyclic voltamograms, the decomposition potentials of the metal oxides are the determining factors for the mechanism of the reduction of the uranium oxide in a $LiCl-3\;wt{\%} Li_{2}O$ molten salt and the two mechanisms of the electrolytic reduction were considered with regards to the applied cathode potential. In the chronopotentiograms, the exchange current and the transfer coefficient based on the Tafel behavior were obtained with regard to the layer thickness of the uranium oxide which is loaded into the porous MgO membrane and the thickness of the porous MgO membrane. The maximum allowable currents for the changes of the layer thickness of the uranium oxide and the thickness of the MgO membrane were also obtained from the limiting potential which is the decomposition potential of LiCl.

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A Study on the Electrolytic Reduction Mechanism of Uranium Oxide in a LiCl-Li$_2$O Molten Salt (LiCl-Li$_2$O 용융염계에서 우라늄 산화물의 전기화학적 금속전환 반응 메카니즘에 관한 연구)

  • 오승철;허진목;서중석;박성원
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.1 no.1
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    • pp.25-39
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    • 2003
  • This study proposed a new electrolytic reduction technology that is based on the integration of simultaneous uranium oxide metallization and Li$_2$O electrowinning. In this electrolytic reduction reaction, electrolytically reduced Li deposits on cathode and simultaneously reacts with uranium oxides to produce uranium metal showing more than 99% conversion. For the verification of process feasibility, the experiments to obtain basic data on the metallization of uranium oxide, investigation of reaction mechanism, the characteristics of closed recycle of Li$_2$O and mass transfer were carried out. This evolutionary electrolytic reduction technology would give benefits over the conventional Li-reduction process improving economic viability such as: avoidance of handling of chemically active Li-LiCl molten salt increase of metallization yield, and simplification of process.

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Recovery of $ZrO_2$ by Leaching from $LiF-BeF_2-ZrO_2$ Molten Salt in Distilled Water ($LiF-BeF_2-ZrO_2$ 용융염에서 증류수 침출에 의한 $ZrO_2$의 회수 - 증류수에서 $LiF-BeF_2-ZrF_4+ZrO_2$ 용융염의 용해현상 -)

  • Woo, Mun-Sik;Yoo, Jae-Hyung;Park, Hyun-Soo;Kang, Young-Ho;Kwon, Soo-Han
    • Analytical Science and Technology
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    • v.13 no.6
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    • pp.712-721
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    • 2000
  • $LiF-BeF_2-ZrF_4$(63-30-7 mol%) molten salt was dissolved up to 0.02g in 1ml of distilled water at room temperature. $ZrO_2$ oxide made from $ZrF_4$ through pyrohydrolysis was recovered by leaching in distilled water with $LiF-BeF_2-ZrF_4$molten salt including it at room temperature. The crystalline sharpness of recovered $ZrO_2$ oxide was not damaged.

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A Study on the Recovery of Lithium from Secondary Resources of Ceramic Glass Containing Li-Al-Si by Ca-based Salt Roasting and Water Leaching Process (Li-Al-Si 함유 유리세라믹 순환자원으로부터 Ca계열 염배소법 및 이에 따른 수침출 공정에 의한 리튬의 회수 연구)

  • Sung-Ho Joo;Dong Ju Shin;Dongseok Lee;Shun Myung Shin
    • Resources Recycling
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    • v.32 no.1
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    • pp.42-49
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    • 2023
  • The glass ceramic secondary resource containing Li-Al-Si is used in inductor, fireproof glass, and transparent cookware and accounts for 14% of the total consumption of Li, which is the second most widely used after Li-ion batteries. Therefore, new Li resources should be explored when the demand for Li is exploding, and extensive research on Li recovery is needed. Herein, we recovered Li from fireproof Li-Al-Si glass ceramic, which is a new secondary resource containing Li. The fireproof glass among all Li-Al-Si glass ceramics was used as raw material that contained 1.5% Li, 9.4% Al, and 28.9% Si. The process for recovering Li from the fireproof glass was divided into two parts: (1) calcium salt roasting and (2) water leaching. In calcium salt roasting, a sample of fireproof glass was crushed and ground below 325 mesh. The leaching efficiency was compared based on the presence or absence of heat treatment of the fireproof glass. Moreover, the leaching rates based on the input ratios of calcium salt, Li-Al-Si glass, and ceramics and the leaching process based on calcium salt roasting temperatures were compared. In water leaching, the leaching and recovery rates of Li based on different temperatures, times, solid-liquid ratios, and number of continuous leaching stages were compared. The results revealed that fireproof glass ceramics containing Li-Al-Si should be heat treated to change phase to beta-type spodumene. CaCO3 salt should be added at a ratio of 6:1 with glass ceramics containing Li-Al-Si, and then leached 4 times or more to achieve a recovery efficiency of Li over 98% from a solution containing 200 mg/L of Li.

Corrosion Behavior of Austenitic Alloys in the Molten Salts of $LiCl-Li_2O_2$ ($LiCl-Li_2O_2$ 용융염계에서 오스테나이트계 합금의 부식거동)

  • 오승철;윤기석;임종호;조수행;박성원
    • Proceedings of the Korean Radioactive Waste Society Conference
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    • 2003.11a
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    • pp.373-378
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    • 2003
  • As a part of assessment of the structural material for the molten salt handling system, corrosion behavior of austenitic alloys, Fe-base and Ni-base in the molten salt of $LiCl-Li_2O_2$ was investigated in the range of temperature; 650~$725^{\circ}C$, time; 24- 168h, $Li_2O$; 3wt%, mixed gas; Ar-10%$O_2$. In the molten salt of $LiCl-Li_2O_2$, Ni-base alloys showed higher corrosion resistance than Fe-base alloys. Fe-base alloy with low Fe and high Ni contents exhibited better corrosion resistance. The scales of $Cr_2O_3$, $FeCr_2O_4$ on Fe-base alloys were showed, and $Cr_2O_3$, $NiFe_2O_4$ on Ni-base alloys were also showed.

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AN EXPERIMENTAL STUDY ON AN ELECTROCHEMICAL REDUCTION OF AN OXIDE MIXTURE IN THE ADVANCED SPENT-FUEL CONDITIONING PROCESS

  • Jeong, Sang-Mun;Park, Byung-Heung;Hur, Jin-Mok;Seo, Chung-Seok;Lee, Han-Soo;Song, Kee-Chan
    • Nuclear Engineering and Technology
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    • v.42 no.2
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    • pp.183-192
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    • 2010
  • An electrochemical reduction of a mixture of metal oxides was conducted in a LiCl molten salt containing 3 wt% $Li_2O$ at $650^{\circ}C$. The oxide reduction was carried out by applying a current to an electrolysis cell, and the $Li_2O$ concentration was analyzed during each run. The concentration of $Li_2O$ in the electrolyte bulk phase gradually decreases according to Faraday's law due to a slow diffusion of the $O^{2-}$ ions. A hindrance effect of the unreduced metal oxides was observed for the reduction of the uranium oxide. Cs, Sr, and Ba of high heat-load fission products were diffused into and accumulated in the salt phase as predicted with thermodynamic consideration.