干法后处理废盐中活泼裂片元素的净化工艺研究进展

doi:10.19964/j.issn.1006-4990.2021-0577

Abstract

Abstract:

With the rapid development of fast reactor research,dry post-treatment process has gradually become the focus of research.Molten salt electrolysis dry post-treatment is the core link and key technology of advanced nuclear fuel cycle system in the future.LiCl-KCl eutectic salt is the most commonly used molten salt system in the dry post-processing process.In order to extract actinides,lanthanides and strontium cesium elements from spent fuel,it is necessary to conduct long time electrolysis in the molten salt.In the process of separation and extraction of actinides,active fragment elements such as lanthanides,strontium and cesium accumulate in molten salt,which not only changes the physical and chemical properties of molten salt system,but also affects the purification effect of subsequent actinides products.In order to realize the reuse of solvent salt and minimize radioactive waste,it is necessary to regularly purify the lanthanide,cesium,strontium and other active fission elements in the waste molten salt.The principles,characteristics and development progress of the purification processes of lanthanide,strontium and cesium in LiCl-KCl waste molten salt by dry post-treatment were reviewed and compared,including molten salt extraction,molten salt electrolysis,precipitation and regional refining.The purification effects of lanthanide and active fragment elements such as strontium and cesium in waste molten salt were discussed in order to reuse solvent salt and reduce the generation of radioactive waste in the above process.It was pointed out that research of China′s waste salt purification will focus on maximizing the utilization of rare earth resources,protecting the environment and reducing waste emission to the greatest extent.

Key words: dry reprocessing, LiCl-KCl, purification, fission elements, precipitation method

CLC Number:

TL24

WU Sida,LIN Rushan,ZHANG Lei,JIA Yanhong. Research progress on purification process for active crack elements in waste salt by dry post-treatment[J]. Inorganic Chemicals Industry, 2022, 54(4): 81-87.

Figures/Tables 9

Fig.1

Fig.2

Fig.3

Fig.4

Fig.5

Fig.6

Fig.7

Fig.8

Table 1

References 50

[1]	林如山, 何辉, 唐洪彬, 等. 我国乏燃料干法后处理技术研究现状与发展[J]. 原子能科学技术, 2020(S1):115-125.
[2]	王有群, 何辉, 林如山, 等. 无机氯化物熔盐在乏燃料干法后处理中的应用进展[J]. 无机盐工业, 2016, 48(8):1-5.
[3]	叶国安, 郑卫芳, 何辉, 等. 我国核燃料后处理技术现状和发展[J]. 原子能科学技术, 2020, 54(z1):75-83.
[4]	刘海军, 陈晓丽. 国内外乏燃料后处理技术研究现状[J]. 节能技术, 2021, 39(4):358-362.
[5]	CHOI J H, LEE K R, KANG H W, et al. Reactive-crystallization method for purification of LiCl salt waste[J]. Journal of Radioanalytical and Nuclear Chemistry, 2020, 325(2):485-492. doi: 10.1007/s10967-020-07235-0
[6]	INOUE T, KOCH L. Development of pyroprocessing and its future direction[J]. Nuclear Engineering and Technology, 2008, 40(3):183-190. doi: 10.5516/NET.2008.40.3.183
[7]	梁红彦. 乏燃料电冶金废熔盐中放射性核素的脱除与固化[D]. 南宁:广西大学, 2015.
[8]	孙鹏院. 熔盐/液态金属(Bi-Li)还原萃取稀土Ce和Sm[D]. 哈尔滨:哈尔滨工程大学, 2015.
[9]	EUN H C, CHOI J H, CHO I H, et al. Purification of LiCl-KCl eutectic waste salt containing rare earth chlorides delivered from the pyrochemical process of used nuclear fuel using a reactive distillation process[J]. Journal of Radioanalytical and Nuclear Chemistry, 2016, 30:1419-1425.
[10]	贾艳虹, 何辉, 林如山, 等. 用于熔盐体系的氮化硼隔膜Ag/AgCl参比电极性能[J]. 无机盐工业, 2015, 47(5):67-71.
[11]	MURAKAMI T, SAKAMURA Y, UOZUMI K, et al. Rare earth silicide formation on Si electrode in LiCl-KCl melt to establish a novel used salt treatment process[J]. ECS Transactions, 2020, 98(10):33-46.
[12]	张凯, 肖益群, 林如山, 等. 俄罗斯氧化物乏燃料电沉积流程研究进展[J]. 核化学与放射化学, 2019, 41(3):233-241.
[13]	SOUČEK P, MALMBECK R, MENDES E, et al. Exhaustive electrolysis for recovery of actinides from molten LiCl-KCl using solid aluminium cathodes[J]. Journal of Radioanalytical and Nuclear Chemistry, 2010, 286:823-828. doi: 10.1007/s10967-010-0739-6
[14]	SONG K C, LEE H, HUR J M, et al. Status of pyroprocessing technology development in Korea[J]. Nuclear Engineering and Technology, 2010, 42(2):131-144. doi: 10.5516/NET.2010.42.2.131
[15]	聂春晨. 稀土金属提纯现状及发展趋势[J]. 化工设计通讯, 2019, 45(5):67-68.
[16]	IVANOV A B, BYZOVA E D, VOLKOVICH V A, et al. Application of phosphate precipitation for removing strontium and barium from alkali chloride based melts[J]. ECS Transactions, 2020, 98(10):283-294. doi: 10.1149/09810.0283ecst
[17]	CHO Y Z, PARK G H, YANG H C, et al. Minimization of eutectic salt waste from pyroprocessing by oxidative precipitation of lanthanides[J]. Journal of Nuclear Science and Technology, 2009, 46(10):1004-1011. doi: 10.1080/18811248.2009.9711610
[18]	LEE T K, CHO Y Z, EUN H C, et al. Study on the phosphate reaction characteristics of lanthanide chlorides in molten salt with operating conditions[J]. Journal of Nuclear Science and Technology, 2013, 50(7):742-750. doi: 10.1080/00223131.2013.799396
[19]	CHO Y Z, LEE T K, EUN H C, et al. Purification of used eutectic (LiCl-KCl) salt electrolyte from pyroprocessing[J]. Journal of Nuclear Materials, 2013, 437(1/2/3):47-54. doi: 10.1016/j.jnucmat.2013.01.344
[20]	RILEY B J. Electrochemical salt wasteform development:A review of salt treatment and immobilization options[J]. Industrial and Engineering Chemistry Research, 2020, 59(21):9760-9774. doi: 10.1021/acs.iecr.0c01357
[21]	CHOI J H, EUN H C, LEE K R, et al. Fabrication of rare earth calcium phosphate glass waste forms for the immobilization of rare earth phosphates generated from pyrochemical process[J]. Journal of Non-Crystalline Solids, 2016, 434:79-84. doi: 10.1016/j.jnoncrysol.2015.12.017
[22]	KIM E H, PARK G I, CHO Y Z, et al. A new approach to minimize pyroprocessing waste salts through a series of fission product removal process[J]. Nuclear Technology, 2008, 162(2):208-218. doi: 10.13182/NT08-A3949
[23]	LAN Y P, SOHN H Y, MURALI A, et al. The formation and growth of CeOCl crystals in a molten KCl-LiCl flux[J]. Applied Physics A, 2018, 124(10).Doi: 10.1007/s00339-018-2122-3. doi: 10.1007/s00339-018-2122-3
[24]	LIU Y, LIU K, LUO L, et al. Direct separation of uranium from lanthanides (La,Nd,Ce,Sm) in oxide mixture in LiCl-KCl eutectic melt[J]. Electrochimica Acta, 2018, 275:100-109. doi: 10.1016/j.electacta.2018.04.140
[25]	LEE H S, GYU-HWAN O H, LEE Y S, et al. Concentrations of CsCl and SrCl₂ from a simulated LiCl salt waste generated by pyroprocessing by using Czochralski method[J]. Journal of Nuclear Science and Technology, 2009, 46(4):392-397. doi: 10.1080/18811248.2007.9711545
[26]	KIM I S, CHUNG D Y, PARK M S, et al. Evaporation of CsCl,BaCl₂, and SrCl₂ from the LiCl-Li₂O molten salt of the electrolytic reduction process[J]. Journal of Radioanalytical and Nuclear Chemistry, 2015, 303(1):223-227. doi: 10.1007/s10967-014-3330-8
[27]	YOO T S, FRANK S M, SIMPSON M F, et al. Salt-zeolite ion-exchange equilibrium studies for a complete set of fission products in molten LiCl-KCl[J]. Nuclear Technology:A journal of the American Nuclear Society, 2010, 171(3):306-315.
[28]	SACHDEV P, SIMPSON M F, FRANK S M, et al. Selective separation of Cs and Sr from LiCl-based salt for electrochemical processing of oxide spent nuclear fuel[J]. Separation Science and Technology, 2008, 43(9/10):2709-2721. doi: 10.1080/01496390802122212
[29]	LEXA D, JOHNSON I. Occlusion and ion exchange in the molten (lithium chloride-potassium chloride-alkali metal chloride) salt+zeolite 4A system with alkali metal chlorides of sodium,rubidium,and cesium[J]. Metallurgical and Materials Transactions B, 2001, 32(3):429-435. doi: 10.1007/s11663-001-0028-4
[30]	LEXA D. Occlusion and ion exchange in the molten(lithium chloride+potassium chloride+alkaline-earth chloride) salt+zeolite 4A system with alkaline-earth chlorides of calcium and strontium and in the molten(lithium chloride+potassium chloride+actinide chloride) salt+zeolite 4A system with the actinide chloride of uranium[J]. Metallurgical and Materials Transactions B, 2003, 34(2):201-208. doi: 10.1007/s11663-003-0007-z
[31]	SHALTRY M, PHONGIKAROON S, SIMPSON M F. Ion exchange kinetics of fission products between molten salt and zeolite-A[J]. Microporous and Mesoporous Materials, 2012, 152:185-189. doi: 10.1016/j.micromeso.2011.11.035
[32]	CHO Y Z, LEE T K, CHOI J H, et al. Study on LiCl waste salt treatment process by layer melt crystallization[C]// Salt Lake City.International nuclear fuel cycle conference,GLOBAL 2013:Nuclear energy at a crossroads, 2013:297-299.
[33]	POGLYAD S S, ANKUDINOVA N S, NECHAEV P I, et al. The cesium precipitation from the spent electrolyte LiCl-KCl composition simulator[J]. Journal of Physics:Conference Series, 2018, 1133(1):12-22.
[34]	CHO Y Z, AHN B G, EUN H C, et al. Melt crystallization process treatment of LiCl salt waste generated from electrolytic reduction process of spent oxide fuel[J]. Energy Procedia, 2011, 7(1):525-528. doi: 10.1016/j.egypro.2011.06.072
[35]	VERSEY J R, PHONGIKAROON S, SIMPSON M F. Separation of CsCl from LiCl-CsCl molten salt by cold finger melt crystallization[J]. Nuclear Engineering and Technology, 2014, 46(3):395-406. doi: 10.5516/NET.06.2013.082
[36]	CHOI J H, CHO Y Z, LEE T K, et al. Inclusion behavior of Cs,Sr, and Ba impurities in LiCl crystal formed by layer-melt crystallization:Combined first-principles calculation and experimental study[J]. Journal of Crystal Growth, 2013, 371:84-89. doi: 10.1016/j.jcrysgro.2013.02.013
[37]	CHOI J H, LEE T K, LEE K R, et al. Melt-crystallization monitoring system for the purification of 10 kg-scale LiCl salt waste[J]. Nuclear Engineering and Design, 2018, 326:1-6. doi: 10.1016/j.nucengdes.2017.10.016
[38]	任永胜, 李军, 马睿, 等. 区域熔融法提纯工业黄磷的数学模型与实验研究[J]. 高校化学工程学报, 2009(6):933-938.
[39]	GHOSH K, MANI V N, DHAR S. Numerical study and experimental investigation of zone refining in ultra-high purification of gallium and its use in the growth of GaAs epitaxial layers[J]. Journal of Crystal Growth, 2009, 311(6):1521-1528. doi: 10.1016/j.jcrysgro.2009.01.102
[40]	CHO Y Z, LEE T K, CHOI J H, et al. Eutectic(LiCl-KCl) waste salt treatment by sequencial separation process[J]. Nuclear Engineering and Technology, 2013, 45(5):675-682. doi: 10.5516/NET.06.2013.022
[41]	WILLIAMS A N, PACK M, PHONGIKAROON S. Separation of SrCl₂ and CsCl from ternary SrCl₂-LiCl-KCl and quaternary SrCl₂-CsCl-LiCl-KCl molten salts via melt crystallization[J]. Transactions of the American Nuclear Society, 2014, 111(1):431-433.
[42]	周骏宏, 李军, 任永胜. 区域熔融法净化磷酸的初步研究[J]. 无机盐工业, 2010, 42(7):23-25.
[43]	张先锋. 区域熔融温度场数值模拟与实验研究[D]. 沈阳:东北大学, 2006.
[44]	CHO Y Z, LEE T K, EUN H C, et al. Purification of used eutectic (LiCl-KCl) salt electrolyte from pyroprocessing[J]. Journal of Nuclear Materials, 2013, 437(1/2/3):47-54. doi: 10.1016/j.jnucmat.2013.01.344
[45]	SHIM M, CHOI H G, CHOI J H, et al. Separation of Cs and Sr from LiCl-KCl eutectic salt via a zone-refining process for pyroprocessing waste salt minimization[J]. Journal of Nuclear Materials, 2017, 491:9-17. doi: 10.1016/j.jnucmat.2017.04.036
[46]	CHOI H G, SHIM M, LEE J H, et al. Numerical analysis of impurity separation from waste salt by investigating the change of concentration at the interface during zone refining process[J]. Journal of Crystal Growth, 2017, 474:69-75. doi: 10.1016/j.jcrysgro.2016.12.083
[47]	SHIM M, KIM Y M, LEE H H, et al. Separation behavior of impurities and selenium reduction by the reactive zone refining process using high-frequency induction heating to purify Te[J]. Journal of Crystal Growth, 2016, 455:6-12. doi: 10.1016/j.jcrysgro.2016.09.032
[48]	CHO Y Z, PARK G H, LEE H S, et al. Concentration of cesium and strontium elements involved in a LiCl waste salt by a melt crystallization process[J]. Nuclear Technology, 2010, 171(3):325-334. doi: 10.13182/NT09-7
[49]	WILLIAMS A N, PHONGIKAROON S, SIMPSON M F. Separation of CsCl from a ternary CsCl-LiCl-KCl salt via a melt crystallization technique for pyroprocessing waste minimization[J]. Chemical Engineering Science, 2013, 89:258-263. doi: 10.1016/j.ces.2012.12.012
[50]	付海英, 耿俊霞, 杨洋, 等. 乏燃料干法后处理中的熔盐减压蒸馏技术[J]. 核技术, 2018(4):5-12.

净化方法		净化对象	优点	缺点
熔盐萃取法		镧系元素	回收率高、净化效果好	需要严格控制Li用量
熔盐电解法		镧系元素	操作简单、效率高	电解产生大量氯气,腐蚀设备,处理困难,有污染的风险
沉淀法	磷酸盐沉淀法	镧系元素	反应高效、快捷	引入新杂质,分离Cs、Sr的效率低
	碳酸盐沉淀法	镧系元素、碱土金属	不引入新杂质,可以沉淀碱土金属	除去碱土需要控制用量,且产生CO₂废气
	氧化物沉淀法	镧系元素	操作简单、不引入新杂质、净化效率高	反应时间长、操作复杂、温度高;无法分离Cs、Sr
离子交换法		镧系元素、Cs、Sr	低温熔盐离子交换技术成熟	分离产生大量废物,且难以适应高温熔盐
结晶法	冷指分离法	Cs、Sr	不引入新的化学组成	操作效率低,分离的量有限,难以实现工程应用
结晶法	区域熔融/结晶法	Cs、Sr	不引入新的化学组成,且分离效果好,效率高	需要长时间的区域熔融/结晶过程才能得到较纯的分离盐

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Research progress on purification process for active crack elements in waste salt by dry post-treatment

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 9

References 50

Related Articles 15

Metrics

Comments

Recommended 0

[1]	BAI Chaopeng, PENG Hui, CHEN Yuting, LUO Jiang, ZHANG Shengming. Research progress of recovery，purification and recycling of ruthenium from scrap ruthenium materials [J]. Inorganic Chemicals Industry, 2024, 56(4): 24-33.
[2]	TAO Longhai, WANG Yongjie, DUAN Jiatang, SHU Yizhou, WAN Banglong, HUANG Chengdong, ZHANG Yueqiang, LU Zhenya. Research progress and prospect of sludge acid and raffinate acid by-product of wet-process phosphoric acid [J]. Inorganic Chemicals Industry, 2024, 56(3): 12-18.
[3]	SU Xin, LAI Dongmei, ZHOU Yuan, ZHU Xiaping. Study on preparation process of strontium rich functional salt from Zigong underground brine [J]. Inorganic Chemicals Industry, 2024, 56(3): 45-50.
[4]	WANG Zihan, LI Jun, CHEN Ming, ZHOU Qingyu. Study on preparation of battery grade ferric phosphate by co-precipitation of ferric nitrate and phosphoric acid [J]. Inorganic Chemicals Industry, 2023, 55(7): 51-57.
[5]	CHEN Xinyi, ZHANG Hua, FANG Wei, XU Xiaofeng. Application of metal-organic frameworks in fields of natural gas purification and storage [J]. Inorganic Chemicals Industry, 2023, 55(4): 13-19.
[6]	LAN Yinghua, CHEN Yanmei, MA Ruixiao, ZHANG Yanhui. Preparation and photocatalytic performance of Ce-Ti oxide-attapulgite composites [J]. Inorganic Chemicals Industry, 2023, 55(4): 133-140.
[7]	WU Hao,LI Xi,ZHANG Jun,DUAN Siyu. Study on impurity removal process of prereduction-oxalic acid precipitation in stainless steel coloring ageing liquid [J]. Inorganic Chemicals Industry, 2023, 55(2): 119-125.
[8]	HU Guangshou, LI Huping, ZHOU Wanchun, LI Xiangdong, MA Xuhua. Study on origin of tetravalent cerium in extraction and separation of rare earth [J]. Inorganic Chemicals Industry, 2023, 55(11): 64-69.
[9]	HE Zhengyan,LI Changwei,TIAN Peng,BI Shengnan,ZHU Peihan,LI Xinzhu,YE Junwei,NING Guiling. Investigation on holding mechanism and removal method of trace calcium in high purity boric acid prepared by esterification method [J]. Inorganic Chemicals Industry, 2022, 54(7): 49-54.
[10]	YIN Huibin,LI Jun,ZHENG Zhuochao. Research on deep purification process of glauberite gypsum [J]. Inorganic Chemicals Industry, 2022, 54(11): 104-111.
[11]	Su Shu,Xu Dehua,Li Chaorong,Yang Xiushan,Wang Xinlong,Zhang Zhiye. Study on defluorination of phosphoric acid by nitric acid process [J]. Inorganic Chemicals Industry, 2021, 53(9): 24-29.
[12]	Zhang Xin,Zhang Li. Study on the treatment of cadmiμm plating wastewater by electrocoagulation with Al-Fe electrode [J]. Inorganic Chemicals Industry, 2021, 53(8): 87-90.
[13]	Hou Yifei,Bai Ni,Sun Jian,Jiao Lina,Ju Dianchun. Effects of ZrO₂ on the physicochemical properties of NaCl-KCl molten salt system for the purification of crude ZrCl₄ [J]. Inorganic Chemicals Industry, 2021, 53(7): 63-67.
[14]	Li Ningyu,Sun Xiaolei,Zou Mingjing,Sun Xiuyun,Han Weiqing,Wang Lianjun. Study on purification of phosphorus waste salt produced by medicine [J]. Inorganic Chemicals Industry, 2021, 53(3): 73-77.
[15]	Shao Qiang,Guo Yiqiong,Zhu Chunyu. Development status and prospect of precipitated silica industry in China [J]. Inorganic Chemicals Industry, 2020, 52(7): 8-11.