Research Progress on the Preparation and Recovery of Nuclear-Grade Zirconium Using Molten Salts

doi:10.6023/A25110360

Acta Chimica Sinica ›› 2026, Vol. 84 ›› Issue (3): 425-447.DOI: 10.6023/A25110360 Previous Articles Next Articles

Review

核级锆的熔盐制备与回收研究进展

周铭宇^a^,^c, 刘乐彬^a^,^c, 梅雷^a, 刘雅兰^a^,^*(), 石伟群^b^,^*()

^a 中国科学院高能物理研究所核能放射化学实验室北京 100049
^b 上海交通大学机械与动力工程学院核燃料循环与核材料研究所上海 200030
^c 中国科学院大学化学科学学院北京 100049

投稿日期:2025-11-06 发布日期:2025-12-31

作者简介:

周铭宇, 中国科学院高能物理研究所博士研究生, 主要从事金属锆的熔盐电化学研究.

刘乐彬, 中国科学院高能物理研究所硕士研究生, 主要从事干法后处理研究.

梅雷, 中国科学院高能物理研究所, 研究员. 主要研究方向为锕系元素化学与分离材料, 致力于将超分子识别与组装的理念和方法应用于锕系固体化学和放射性核素分离化学研究, 在锕系超分子配合物及其配位化学基础、基于协同识别的放射性核素分离新方法、新型锕系固相材料开发等方面开展了系列原创性工作, 为解决乏燃料后处理、环境放射性污染控制与资源回用研究等领域中的关键问题提供了新思路. 以通讯/第一作者身份在Nature Commun., J. Am. Chem. Soc., Angew. Chem. Int. Ed., Adv. Funct. Mater.等国际知名期刊发表研究论文130余篇. 目前担任中国化学会青年化学工作者委员会委员, 中科院青促会化学与材料分会委员, 中国核学会锕系化学与物理分会理事, 并担任《核化学与放射化学》期刊编委, SmartMat、Materials Research Letters、《结构化学》等学术期刊青年编委.

刘雅兰, 副研究员, 中国科学院高能物理研究所. 多年来致力于氧化物乏燃料干法后处理领域, 聚焦于锕-镧分离研究. 首先开展了锕、镧系氧化物在熔盐中的溶解及其电化学行为研究, 随后在固态活性铝阴极上进行了锕-镧的电化学分离, 并采用原位光谱技术监测了分离过程中锕、镧元素的化学种态变化, 发现了铀的循环电解并将其消除, 提高了电流效率. 最终成功实现了锕-镧元素的有效分离, 与传统的液态Cd阴极相比将分离因子提高了两个数量级. 在此基础上, 进一步总结了锕、镧氧化物在氯化物熔盐中的溶解规律, 提出了利用其溶解性差异实现一步分离的新方法. 基于相关工作, 在电化学领域与核能领域著名期刊Electrochim. Acta, J. Electrochem. Soc., Electrochem. Commun.和 J. Nucl. Mater.等上共发表论文40余篇, 其中第一作者及通讯作者论文20篇.

石伟群, 上海交通大学特聘教授, 核燃料循环与核材料研究所所长, 国家杰出青年科学基金获得者. 2007年1月在清华大学化学系获博士学位. 长期致力于核燃料循环化学相关基础研究, 在JACS、Angew. Chem、Chem.、CCS Chem.、Nat. Commun、Adv. Mater.等国际知名期刊发表SCI论文400余篇, 成果被国内外同行广泛关注和引用, 文章总引两万余次, H因子71 (Google Scholar), 2020~2024年连续入选Elsevier中国高被引学者榜单(核科学技术). 分别担任期刊《Supramolecular Materials》副主编, 《Industrial Chemistry & Materials》、《Chinese Chemical Letters》、《Journal of Nuclear Fuel Cycle and Waste Technology》、《International Journal of Advanced Nuclear Reactor Design and Technology》和《Journal of Nuclear Science and Technology》的编委与国际顾问编委, 中文期刊《化学学报》、《高等学校化学学报》、《核化学与放射化学》、《核动力》编委. 现为中国核工业教育学会副理事长、中国核学会锕系物理与化学分会副理事长、中国有色金属学会熔盐化学与技术专业委员会副主任委员、中国化学会核化学与放射化学专业委员会委员、中国核学会核化工分会常务理事兼副秘书长.

Research Progress on the Preparation and Recovery of Nuclear-Grade Zirconium Using Molten Salts

Zhou Mingyu^a^,^c, Liu Lebin^a^,^c, Mei Lei^a, Liu Yalan^a^,^*(), Shi Weiqun^b^,^*()

^a Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
^b Institute of Nuclear Fuel Cycle and Materials, School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200030, China
^c School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2025-11-06 Published:2025-12-31
Contact: *E-mail: liuyalan@ihep.ac.cn; shiwq@ihep.ac.cn

Nuclear-grade zirconium is a critical metallic material for nuclear power plants. It boasts a low neutron absorption cross-section and corrosion resistance that are far superior to those of ordinary commercial zirconium materials. With high economic value and vital strategic significance, it serves as a strategic reserve resource critical to national energy security. Consequently, the efficient and economical preparation and recovery of nuclear-grade zirconium have garnered increasing attention. Molten salt technology serves as a crucial pathway for the separation of zirconium and hafnium, the preparation of metallic zirconium, and the recycling of the used zirconium, offering advantages such as a simplified process and strong adaptability. This review outlines the key role of molten salts in the life cycle management of nuclear-grade zirconium, including the analysis and comparison of the application characteristics of different molten salt systems (fluoride, chloride, and fluorine-chloride mixed salt systems) in the preparation and recovery of metallic zirconium. In addition, it focuses on systematically sorting out and summarizing the electroreduction behavior of zirconium ions in molten salts, aiming to promote the green metallurgy and recycling of nuclear-grade zirconium.

Key words: nuclear-grade zirconium, molten salts, electrowinning, electrorefining

Cite this article

Zhou Mingyu, Liu Lebin, Mei Lei, Liu Yalan, Shi Weiqun. Research Progress on the Preparation and Recovery of Nuclear-Grade Zirconium Using Molten Salts[J]. Acta Chimica Sinica, 2026, 84(3): 425-447.

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Methods	Advantage	Challenges
Fractional Crystallization	Simplicity principle; Mild operating conditions	Low separation factor; Low productivity; Intermittent operation
Solvent Extraction	Large-scale production; Mature process; Separation efficiency	High consumption; High waste generation; Process complexity
Solid-phase Extraction	Eco-Friendly; Highly efficient	Adsorbent cost; Low stability
Molten Salt Distillation	Process simplicity; Simplifies downstream; Waste minimization	High temperature; Corrosivity; High energy consumption

Methods	Advantage	Challenges
Fractional Crystallization	Simplicity principle; Mild operating conditions	Low separation factor; Low productivity; Intermittent operation
Solvent Extraction	Large-scale production; Mature process; Separation efficiency	High consumption; High waste generation; Process complexity
Solid-phase Extraction	Eco-Friendly; Highly efficient	Adsorbent cost; Low stability
Molten Salt Distillation	Process simplicity; Simplifies downstream; Waste minimization	High temperature; Corrosivity; High energy consumption

Components	Melting/Eutectic Temp. (℃)	Characteristics/Properties	Primary Applications in Zr Industry
NaCl	801	Wide electrochemical window; High Zr-salt solubility; Low cost; Formation of dense, adherent Zr deposits.	Molten Salt Distillation; Molten Salt Electrolysis for Zr/Hf Separation; Electrowinning for Zirconium Production.
MgCl₂	714	Denser Kroll byproduct than molten Mg; Electrolytically regeneratable.	Kroll Process for Zirconium Production.
CaCl₂	772	High O²⁻ affinity/solubility; Efficient O²⁻ transport.	FFC Process for Zirconium Production.
NaCl-KCl	657	Powdery, non-adherent zirconium deposits; Favorable solubility for ZrC_xO_y anodes.	Molten Salt Distillation; Molten Salt Extraction for Zr/Hf Separation; Molten Salt Electrolysis for Zr/Hf Separation; Electrowinning for Zirconium Production; USTB Process for Zirconium Production.
LiCl-KCl	352	Multi-metallic processing capability; Highly purifiable; Wide/stable electrochemical window.	Molten Salt Electrolysis for Zr/Hf Separation; Electrowinning for Zirconium Production; Electrorefining for Zirconium Recovery.
LiF-KF	492	High Zr(IV) reduction efficiency; Dense Zr deposition; Fluoride-induced anode passivation; High viscosity and corrosivity.	Electrorefining for Zirconium Recovery.
LiF-NaF	649
LiF-NaF-KF	460

Components	Melting/Eutectic Temp. (℃)	Characteristics/Properties	Primary Applications in Zr Industry
NaCl	801	Wide electrochemical window; High Zr-salt solubility; Low cost; Formation of dense, adherent Zr deposits.	Molten Salt Distillation; Molten Salt Electrolysis for Zr/Hf Separation; Electrowinning for Zirconium Production.
MgCl₂	714	Denser Kroll byproduct than molten Mg; Electrolytically regeneratable.	Kroll Process for Zirconium Production.
CaCl₂	772	High O²⁻ affinity/solubility; Efficient O²⁻ transport.	FFC Process for Zirconium Production.
NaCl-KCl	657	Powdery, non-adherent zirconium deposits; Favorable solubility for ZrC_xO_y anodes.	Molten Salt Distillation; Molten Salt Extraction for Zr/Hf Separation; Molten Salt Electrolysis for Zr/Hf Separation; Electrowinning for Zirconium Production; USTB Process for Zirconium Production.
LiCl-KCl	352	Multi-metallic processing capability; Highly purifiable; Wide/stable electrochemical window.	Molten Salt Electrolysis for Zr/Hf Separation; Electrowinning for Zirconium Production; Electrorefining for Zirconium Recovery.
LiF-KF	492	High Zr(IV) reduction efficiency; Dense Zr deposition; Fluoride-induced anode passivation; High viscosity and corrosivity.	Electrorefining for Zirconium Recovery.
LiF-NaF	649
LiF-NaF-KF	460

Technique	Description/Formula Name	Equation	Applicable System & Notes
EFM^a	Nernst Equation	${-E}_{\mathrm{c}\mathrm{e}\mathrm{l}\mathrm{l}}^{\mathrm{\text{'}}}={E}_{\mathrm{Z}\mathrm{r}\left(n\right)/\mathrm{Z}\mathrm{r}\left(0\right)}^{{0}^{\mathrm{\text{'}}}}+$ $\frac{2.303RT}{nF}\mathrm{l}\mathrm{o}\mathrm{g}C$	E_cell: Measured potential (V) ${E}_{\mathrm{Z}\mathrm{r}\left(n\right)/\mathrm{Z}\mathrm{r}\left(0\right)}^{{0}^{\text{'}}}$: Formal potential (V) C: Concentration of the electroactive species (mol/L)
LSV/CV	Reversible System Half-Wave Potential	${E}_{P/2}={E}_{P}+2.2\left(\frac{RT}{nF}\right)$	Reversible System: Fast electron transfer. E_P/2: Half-wave potential (V) E_P: Peak potential (V) Constant 2.2 is characteristic of a reversible process.
LSV/CV	Irreversible System Half-Wave Potential	${E}_{P/2}={E}_{P}+1.85\left(\frac{RT}{nF}\right)$	Totally Irreversible System: Slow electron transfer. Constant 1.85 is characteristic of an irreversible process.
SWV	Peak Width at Half Height	${W}_{1/2}=\frac{3.52RT}{nF}$	W_1/2: Peak width at half height (V) Applicable when electron transfer is sufficiently fast.
CP	Sand's Equation	$i{\tau }^{1/2}=0.5nFCA{\left(\pi \nu \right)}^{1/2}$	Used to calculate the diffusion coefficient D or n. $\tau $: Transition time (s) i: Applied constant current (A) A: Electrode area (cm²) C: Bulk concentration (mol/cm³)
Calculation	Randles-Sevcik Equation	${i}_{\mathrm{p}}=0.4463nFAC{\left(\frac{nF\nu D}{RT}\right)}^{1/2}$	Primarily used in LSV/CV to calculate the diffusion coefficient D from the peak current i_p. i_p: Peak current (A) ν: Scan rate (V/s)

核级锆的熔盐制备与回收研究进展

Research Progress on the Preparation and Recovery of Nuclear-Grade Zirconium Using Molten Salts

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FLiNaK (LiF:NaF:KF)
Author	Time	Zr(IV) Ion Source	Electrode	Electroreduction behavior of Zr(IV)	D_(Zr4+)/(cm²•s⁻¹)
Mellors^[77]	1966	ZrF₄ & K₂ZrF₆	Mo	Zr(IV)→Zr	—
Li^[135]	2023	K₂ZrF₆	Cu	${\mathrm{Z}\mathrm{r}\mathrm{F}}_{x}^{4-x}$→Zr	—
Zuo^[140]	2025	ZrF₄	W	${\mathrm{Z}\mathrm{r}\mathrm{F}}_{8}^{4-}$→Zr	3.85×10⁻⁶ (600 ℃)
LiF-CaF₂
Gibilaro^[134]	2013	ZrF₄	Ta, Cu, Ni	Zr(IV)→Zr	9.96×10⁻⁶ (840 ℃)
Fabian^[139]	2022	ZrF₄	Mo, Ni	Zr(IV)→Zr0(sol)→Zr	2.6×10⁻⁵ (840 ℃)
LiF-KF
Mellors^[77]	1966	ZrF₄ & K₂ZrF₆	Mo	Zr(IV)→Zr	—
Park^[136]	2013	ZrF₄	Mo	Zr(IV)→Zr	—
Xu^[152]	2016	ZrF₄	Mo	Step 1: Zr⁴⁺→Zr²⁺ Step 2: Zr⁴⁺, Zr²⁺→Zr⁺ Step 3: Zr⁺, Zr²⁺, Zr⁴⁺→Zr	1.32×10⁻⁶~1.53×10⁻⁵ (600 ℃)
LiF-NaF
Groult^[153]	2007	ZrF₄	W, Mo, C, Ni	Zr(IV)→Zr	1.19×10⁻⁵ (694 ℃) 2.59×10⁻⁵ (730 ℃) 3.19×10⁻⁵ (762 ℃)
Groult^[154]	2011	n(LiF):n(KF):n(ZrF₄)= (26:37:37)	C	Zr(IV)→ZrC	—
Xu^[155]	2017	K₂ZrF₆	Mo	Zr(IV)→Zr(II) Zr(IV)/Zr(II)→Zr	8.14×10⁻⁶~1.91×10⁻⁵(750 ℃)
Quaranta^[87]	2018	ZrF₄	Ag	Zr(IV)→Zr	1.21×10⁻⁵~1.35×10⁻⁵ (750 ℃)

Author	Year	Technique/Method	Electrolyte	Electroreduction behavior of Zr(IV)	Temp.^a/℃
Mellors^[77]	1966	ED ^b	NaCl-KCl-ZrCl₄ NaCl-KCl-K₂ZrF₆	ZrCl₂ forms in electroreduction	600~900
Swaroop^[176]	1966	EFM	NaCl-KCl-ZrCl₂ NaCl-KCl-ZrCl₂-ZrCl₃ NaCl-KCl-ZrCl₃-ZrCl₄	Zr(IV)→Zr(III)→Zr(II)→Zr(0)	670~740
Sakakura^[177]	1976	CP	NaCl-KCl-ZrCl₂ NaCl-KCl-ZrCl₄	Zr(IV)→Low Valency→Zr(0)	700~900
Polyakova^[80]	1982	LSV	NaCl-KCl-ZrCl₄	Zr(IV)→Zr(II)→Zr(0)	735
Polyakova^[80]	1982	LSV	NaCl-KCl-K₂ZrF₆	${\mathrm{Z}\mathrm{r}\mathrm{F}}_{6}^{2-}$→Zr(0)	805
Guang-Sen^[68]	1990	LSV and CV	NaCl-KCl-ZrCl₄	${\mathrm{Z}\mathrm{r}\mathrm{F}}_{6}^{2-}$→Zr(II)→Zr(0)	760
Wu^[81]	2011	CV and SWV	NaCl-KCl-K₂ZrF₆	Zr(IV)→Zr(II)→Zr(0)	750
Ueda^[88]	2015	CV	AlCl₃-NaCl-KCl-ZrCl₄	Zr(IV)→Zr(II)→Zr(0)	175
Wang^[82]	2016	CV, CP and ED ^b	NaCl-KCl-K₂ZrF₆	Pathway 1: Zr(IV)→Zr(III)→Zr(II)→Zr(0) Pathway 2: Zr(IV)→Zr(0)	750
Tekeda^[111]	2018	CV and SWV	NaCl-KCl-ZrCl₄	Pathway 1: Zr(IV)→Zr(II)→Zr(0) Pathway 2: Zr(IV)→Zr(0)	800
Tekeda^[111]	2018	CV and SWV	NaCl-KCl-K₂ZrF₆	${\mathrm{Z}\mathrm{r}\mathrm{F}}_{6}^{2-}$→Zr(0)	800
Zhang^[83]	2022	CV	NaCl-KCl-K₂ZrF₆	Zr(IV)→Zr(II)→Zr(0)	750
Wang^[89]	2023	CV	NaCl-KCl-K₂ZrF₆	Pathway 1: Zr(IV)→Zr(III)→Zr(II)→Zr(0) Pathway 2: Zr(IV)→Zr(0)	750