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Reduction behaviors of zirconium oxide compounds in LiCl-Li$$_{2}$$O melt

LiCl-Li$$_{2}$$O溶融塩中でのジルコニウム酸化物の還元挙動

坂村 義治*; 飯塚 政利*; 小山 正史*; 北脇 慎一 ; 仲吉 彬  ; 小藤 博英  

Sakamura, Yoshiharu*; Iizuka, Masatoshi*; Koyama, Tadafumi*; Kitawaki, Shinichi; Nakayoshi, Akira; Kofuji, Hirohide

近年酸化物燃料の還元技術が開発されてきたが、希土類やジルコニウムが複合酸化物を形成する等、複雑な挙動が明らかになってきた。福島事故後、ZrO$$_{2}$$-UO$$_{2}$$を主成分とする燃料デブリへの金属電解法技術の適用性検討を開始した。本研究では、ZrO$$_{2}$$, ZrO$$_{2}$$-Li$$_{2}$$O, ZrO$$_{2}$$-UO$$_{2}$$を用いた実験により、LiCl溶融塩中でZrO$$_{2}$$はZrに還元されるが、容易に塩中のLi$$_{2}$$Oと反応し、Li$$_{2}$$ZrO$$_{3}$$を生成することが確認された。一旦、Li$$_{2}$$ZrO$$_{3}$$が形成されるとZrへの還元は難しいことが明らかになった。

An electrolytic reduction process of oxide fuels has recently been developed, however it was found that the behaviors of rare earth elements and zirconium are expected to be complicate because their oxides are stable and complex oxide compounds may form. After Fukushima- Daiichi reactor accident, studies on applicability of pyrometallurgical process to damaged fuel debris consisting of ZrO$$_{2}$$-UO$$_{2}$$ have been started. In this study, reduction behaviors of ZrO$$_{2}$$, ZrO$$_{2}$$-Li$$_{2}$$O and ZrO$$_{2}$$-UO$$_{2}$$ were investigated. It was proved that ZrO$$_{2}$$ can be reduced to metallic form in LiCl melt and that ZrO$$_{2}$$ easily reacts with dissolved Li$$_{2}$$O to give Li$$_{2}$$ZrO$$_{3}$$. After ZrO$$_{2}$$ is converted to Li$$_{2}$$ZrO$$_{3}$$, zirconium metal is hardly obtained even in a LiCl melt with low Li$$_{2}$$O concentration.

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