Electrorefining of Zirconium from Zircaloy-4 Cladding Hulls in LiCl-KCl Molten Salts

Lee, Chang Hwa; Kang, Kweon Ho; Jeon, Min Ku; Heo, Chul Min; Lee, You Lee

doi:10.1149/05011.0491ecst

Cited by 9 publications

(6 citation statements)

References 5 publications

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“…These techniques are aimed at the selective recovery of Zr from the cladding hull waste because cladding materials employed in light water reactors in Korea contain about 98wt% of Zr. In the electrorefining process, Zr is selectively deposited on a cathode electrode by applying the appropriate current/potential in a molten salt bath [8]. The electro-refining method is beneficial for integrated operation with the pyro-processing because it employs similar operation conditions with those of pyro-processing unit operations.…”

Section: Introductionmentioning

confidence: 99%

Demonstration of Zr Recovery from 50 g Scale Zircaloy-4 Cladding Hulls using a Chlorination Method

Jeon¹,

Lee²,

Lee³

et al. 2013

Journal of the Korean Radioactive Waste Society

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The recovery of Zr from Zircaloy-4 (Zry-4) cladding hulls using a chlorination method was demonstrated for complete conversion of Zr into ZrCl 4 . A chlorination reaction was performed by reacting Zry-4 hulls for 8 h under a 70 cc/min Cl 2 + 70 cc/min Ar flow at 380 o C. The initial weight of the reactant (51.7 g) decreased to 0.49 g after 8 h of operation, which is only 0.95wt% of the initial weight. The weight of the total reaction products was 121.7 g with a high Zr purity of 99.80wt%. Fe and Sn were identified as major (0.18wt%) and minor (0.02wt%) impurities of the reaction products, respectively. It was also shown that Zr exhibited a high recovery ratio of 96.95wt% with a relatively small experimental loss of 2.34wt%. Observation of the reaction residues revealed that the chlorination reaction was dominant along the longitudinal direction, and surface oxide layers remained as reaction residues. The high purity and recovery ratio of Zr proposed the feasibility of the chlorination technique as an effective hull waste treatment method.

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Section: Introductionmentioning

confidence: 99%

Demonstration of Zr Recovery from 50 g Scale Zircaloy-4 Cladding Hulls using a Chlorination Method

Jeon¹,

Lee²,

Lee³

et al. 2013

Journal of the Korean Radioactive Waste Society

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“…Currently much attention is paid to studying zirconium electrochemistry in 3LiCl-2KCl eutectic based melts because this electrolyte is considered for the large scale pyrochemical SNF reprocessing. Electrorefining in molten salts was also considered as a possible mean of separating zirconium from irradiated fuel rods cladding (zirconium-based alloys) [5][6][7][8]. Transient electrochemical techniques (cyclic voltammetry being the most popular) were employed to characterize zirconium behavior but there is no full agreement in interpreting the experimental data [7][8][9][10][11][12].…”

Section: Introductionmentioning

confidence: 99%

“…Electrorefining in molten salts was also considered as a possible mean of separating zirconium from irradiated fuel rods cladding (zirconium-based alloys) [5][6][7][8]. Transient electrochemical techniques (cyclic voltammetry being the most popular) were employed to characterize zirconium behavior but there is no full agreement in interpreting the experimental data [7][8][9][10][11][12]. It is generally agreed that zirconium in 3LiCl-2KCl based melts (around 500 • C) can present in two soluble (Zr 4+ , Zr 2+ ) and two insoluble (ZrCl, Zr) forms.…”

Section: Introductionmentioning

confidence: 99%

“…It is generally agreed that zirconium in 3LiCl-2KCl based melts (around 500 • C) can present in two soluble (Zr 4+ , Zr 2+ ) and two insoluble (ZrCl, Zr) forms. From two to four oxidation waves and two or three reduction waves were reported on the cyclic voltammograms, each wave being assigned to a particular redox reaction [7][8][9][10].…”

Section: Introductionmentioning

confidence: 99%

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Application of Low Melting Metals for Separation of Uranium and Zirconium in a “Fused Chloride—Liquid Alloy” System

Volkovich

Maltsev

Soldatova

et al. 2021

Metals

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Closeness of electrochemical properties of uranium and zirconium makes separation of these metals in pyroelectrochemical reprocessing of spent nuclear fuels a challenging task. Varying electrode material can change metals’ deposition potentials. The study was aimed at assessing the effect of the cathode material on deposition potentials of zirconium and uranium from 3LiCl–2KCl based melts. Solid (tungsten) and liquid (gallium, zinc, Ga–Zn, Ga–Sn and Ga–In alloy) working electrodes were tested at 532–637 °C. Galvanostatic cathodic polarization was employed and the applied cathodic current varied from 0.0001 to 1 A. Gallium–zinc eutectic alloy demonstrated the largest difference of zirconium and uranium deposition potentials. Zirconium/uranium separation factors were experimentally determined in a “molten salt—liquid metal” system for gallium and Ga–Zn eutectic based alloys.

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“…The latter employs electrochemical reactions to dissolve and selectively recover metallic Zr by controlling an applied potential or current [6][7][8]. This technique has some advantages including recovery of Zr in its metallic form and relatively mild operation conditions, while the reaction rate, scale-up, and electrolyte treatment issues need verification.…”

Section: Introductionmentioning

confidence: 99%

Surface Analysis Study on ZIRLO Cladding Hulls Oxidized at Low Temperatures

Jeon

Choi²,

Lee³

et al. 2014

Journal of the Nuclear Fuel Cycle and Waste Technology

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Surface oxidation behavior of ZIRLO (ZIRconium Low Oxidation) hulls was investigated using an X-ray photoelectron spectroscopy (XPS) technique. The effects of oxidation time (10-336 h at 500℃) and temperature (400-700℃ for 10 h) were studied. Deconvolution results of the hulls oxidized at 500℃ revealed that a ZrO 2 phase appeared after 24 h (11.86%), and an increase in the ZrO 2 ratio was observed when the hulls were oxidized for 336 h (17.93%). On the other hand, the ZrO phase which employed 5.68% in the 10 h oxidized sample disappeared when the oxidation time increased to 24 h. The XPS results also showed that an increase in the oxidation temperature resulted in an increase in the ratio of ZrO, which increased from 0 to 5.68, 8.31, and 9.16% when the oxidation temperature increased from 400 to 500, 600, and 700℃, respectively. ZrO 2 phase was observed only in the sample that was oxidized at 700℃. The mechanism of ZrO formation was not conclusive, but it was suggested that a formation of hydroxide might have been accelerated at elevated temperatures leading to a formation of a Zr(OH) 4 phase. The relationship between the surface oxidation status of the hulls oxidized at 500℃ and their chlorination reaction feasibility was discussed, and it was suggested that the thickness of the oxide layer is an important parameter that determines the chlorination reaction feasibility.

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Electrorefining of Zirconium from Zircaloy-4 Cladding Hulls in LiCl-KCl Molten Salts

Cited by 9 publications

References 5 publications

Demonstration of Zr Recovery from 50 g Scale Zircaloy-4 Cladding Hulls using a Chlorination Method

Demonstration of Zr Recovery from 50 g Scale Zircaloy-4 Cladding Hulls using a Chlorination Method

Application of Low Melting Metals for Separation of Uranium and Zirconium in a “Fused Chloride—Liquid Alloy” System

Surface Analysis Study on ZIRLO Cladding Hulls Oxidized at Low Temperatures

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