Citation: | WANG Sai, LIN Ru-shan, ZHANG Lei, DU Yu-xin, CHEN Zhi-hua. Simulation of Molten Salt Electrorefining Process of U-Pu-Zr Ternary Alloy[J]. Journal of Nuclear and Radiochemistry, 2024, 46(6): 553-562. DOI: 10.7538/hhx.2024.46.06.0553 |
The integrated closed-cycle fast reactor nuclear energy system is an important measure to accelerate the implementation of the “three-step” strategy of nuclear energy. Electrorefining dry reprocessing technology is suitable for the treatment of fast reactor spent fuel with high burn-up consumption, high plutonium content, strong radioactivity, etc., which is a key link and practical technology choice for fast reactor spent fuel reprocessing. The fast reactor closed fuel cycle not only improves the utilization rate of uranium resources, but also reduces the radioactive activity of minor actinides, which is the only way for the sustainable development of nuclear energy. Dry reprocessing is a key part of the fast reactor closed fuel cycle, which is a realistic technology choice for fast reactor spent fuel reprocessing. Molten salt electrorefining dry reprocessing technology is a pyroprocessing technology with sufficient research and high technical maturity. In the process of research on the electrorefining process of spent fuel, the experimental research is very expensive and time-consuming, the experimental conditions and variables cannot be carried out comprehensively, and it is difficult to obtain reliable data under extreme conditions. The electrochemical changes of high-temperature molten salt electrorefining process can be explored through computer simulation, which can reduce the investment of experimental time and capital cost in the research process of electrorefining. Based on the electrochemical theory and backward difference method, a model of the electrorefining process of U-Pu-Zr ternary alloy was established, the dissolution and deposition behavior of each element near the electrode was simulated, and the changes of electrode potential, partial current and material distribution of each element under different mass transfer coefficients and uranium ion concentration in the initial molten salt were analyzed. The results show that the mass transfer coefficient affects the current distribution between the elements in the process of anode uranium-plutonium co-dissolution and cathode uranium-zirconium co-deposition, and increasing the mass transfer coefficient can improve the separation efficiency reduce the power loss. When the uranium ion mass fraction in the initial molten salt is as low as 0.073%, the cathode potential is lower than the apparent potential of plutonium after 45 minutes of electrorefining, and the plutonium begins to be co-deposited with uranium at the solid cathode, and the deposition of the two elements is competitive. Therefore, in the process of electrorefining, enhanced mass transfer technology can be considered; at the same time, in order to avoid the deposition of Pu, it is necessary to reasonably control the uranium ion concentration in the initial molten salt.
[1] |
徐銤.我国快堆技术发展的现状和前景[J].中国工程科学,2008,10(1):70-76. doi: 10.3969/j.issn.1009-1742.2008.01.011
|
[2] |
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,2020,54(增刊1):115-125. doi: 10.7538/yzk.2020.zhuankan.0548
|
[3] |
刘学刚.乏燃料干法后处理技术研究进展[J].核化学与放射化学,2009,31(增刊1):35-44.
|
[4] |
唐浩,任一鸣,邵浪,等.熔盐电解法乏燃料干法后处理技术研究进展[J].核化学与放射化学,2017,39(6):385-396. doi: 10.7538/hhx.2017.39.06.0385
|
[5] |
Yoo T S, Vaden D. A new inventory tracking method for Mark-Ⅴ electrorefiner[J]. Ann Nucl Energy, 2019, 128: 406-413. doi: 10.1016/j.anucene.2019.01.008
|
[6] |
Kim J G, Lee S J, Park S B, et al. High-throughput electrorefining system with graphite cathodes and a bucket-type deposit retriever[J]. Procedia Chem, 2012, 7: 754-757. doi: 10.1016/j.proche.2012.10.114
|
[7] |
Tomczuk Z, Ackerman J P, Wolson R D, et al. Uranium transport to solid electrodes in pyrochemical reprocessing of nuclear fuel[J]. J Electrochem Soc, 1992, 139(12): 3523-3528. doi: 10.1149/1.2069109
|
[8] |
Srihari B K, Agarwal S, Reddy B P, et al. Modeling the molten salt electrorefining process for spent metal fuel using COMSOL[J]. Sep Sci Technol, 2015: 2276-2283.
|
[9] |
Bae J, Nam H O, Yi K W, et al. Numerical assessment of pyrochemical process performance for PEACER system[J]. Nucl Eng Des, 2010, 240(6): 1679-1687. doi: 10.1016/j.nucengdes.2010.02.005
|
[10] |
Choi S, Park J, Kim K R, et al. Three-dimensional multispecies current density simulation of molten-salt electrorefining[J]. J Alloys Comp, 2010, 503(1): 177-185. doi: 10.1016/j.jallcom.2010.04.228
|
[11] |
Ghosh S, Reddy B P, Nagarajan K, et al. Pragaman: a computer code for simulation of electrotransport during molten salt electrorefining[J]. Nucl Technol, 2010, 170(3): 430-443. doi: 10.13182/NT10-A10329
|
[12] |
Zhang J. Kinetic model for electrorefining, part Ⅰ: model development and validation[J]. Prog Nucl Energy, 2014, 70: 279-286. doi: 10.1016/j.pnucene.2013.03.001
|
[13] |
Zhang J. Kinetic model for electrorefining, part Ⅱ: model applications and case studies[J]. Prog Nucl Energy, 2014, 70: 287-297. doi: 10.1016/j.pnucene.2013.03.008
|
[14] |
Hoover R O, Phongikaroon S, Li S, et al. A computational model of the mark-Ⅳ electrorefiner: phase Ⅰ: fuel basket/salt interface[J]. J Eng Gas Turbines Power, 2009, 131(5): 941-946.
|
[15] |
Hoover R O, Phongikaroon S, Simpson M F, et al. Development of computational models for the Mark-Ⅳ electrorefiner: effect of uranium, plutonium, and zirconium dissolution at the fuel basket-salt interface[J]. Nucl Technol, 2010, 171(3): 276-284. doi: 10.13182/NT10-2A
|
[16] |
Sitompul Y P, Shin H S, Park S H, et al. Study on the time-dependent simulation and input parameter sensitivity of spent nuclear fuel electrorefining[J]. J Radioanal Nucl Chem, 2014, 299(3): 1241-1253. doi: 10.1007/s10967-013-2905-0
|
[17] |
Koyama T, Kinosmta K, Inoue T, et al. Study of molten salt electrorefining of U-Pu-Zr alloy fuel[J]. J Nucl Sci Technol, 2002, 39(sup3): 765-768. doi: 10.1080/00223131.2002.10875579
|
[18] |
Masset P, Konings R J M, Malmbeck R, et al. Thermochemical properties of lanthanides(Ln=La, Nd) and actinides(An=U, Np, Pu, Am) in the molten LiCl-KCl eutectic[J]. J Nucl Mater, 2005, 344(1-3): 173-179. doi: 10.1016/j.jnucmat.2005.04.038
|
[19] |
肖益群,王有群,林如山,等.LiCl-KCl熔盐中Zr(Ⅳ)于Mo电极上的电化学行为[J].核化学与放射化学,2018,40(2):100-104. doi: 10.7538/hhx.2018.YX.2017034
|
[20] |
Ahluwalia R K, Hua T Q, Geyer H K. Removal of zirconium in electrometallurgical treatment of experimental breeder reactor Ⅱ: spent fuel[J]. Nucl Technol, 2001, 133(1): 103-118. doi: 10.13182/NT01-A3162
|
[21] |
Johnson I. The thermodynamics of pyrochemical processes for liquid metal reactor fuel cycles[J]. J Nucl Mater, 1988, 154(1): 169-180. doi: 10.1016/0022-3115(88)90131-6
|
[22] |
衣峰,周文涛,王德忠.乏燃料熔盐电解后处理动力学模型研究[J].无机盐工业,2022,54(11):45-51.
|