Abstract：The valence state of plutonium in nuclear fuel reprocessing liquid is a critical factor affecting the separation of elements, and it is of great significance for the recovery and purification of plutonium. Since the plutonium ions with various valence states have significant absorption peaks in the visible and near-infrared regions, spectrophotometry is still a commonly used analytical method, which can directly measure the sample without separation. The research progress of spectrophotometry in the analysis of plutonium valence in nuclear fuel reprocessing liquid was reviewed in this paper. The principle of spectrophotometric determination was introduced, and then the measurement of plutonium elements with various valence states by spectrophotometry as well as the influencing factors, long optical path flow cell and peak resolution technology were discussed in detail.
王志恒, 李力, 赵雅平, 刘权卫, 侯留东. 分光光度法用于核燃料后处理工艺料液中钚价态分析的研究进展[J]. 冶金分析, 2024, 44(5): 31-37.
WANG Zhiheng, LI Li, ZHAO Yaping, LIU Quanwei, HOU Liudong. Research progress on spectrophotometric analysis of plutonium valence states in nuclear fuel reprocessing liquid. , 2024, 44(5): 31-37.
[1] 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(Sl):75-83. YE Guoan,ZHENG Weifang,HE Hui,et al.Status and development of technology on reprocessing spent nuclear fuel in China[J].Atomic Energy Science and Technology,2020,54(Sl):75-83. [2] 张生栋,严叔衡.乏燃料后处理湿法工艺技术基础研究发展现状[J].核化学与放射化学,2015,37(5):266-275. ZHANG Shengdong,YAN Shuheng.Progress in research of hydrometrical processes in spent fuel reprocessing[J]. Journal of Nuclear and Radiochemistry,2015,37(5):266-275. [3] 叶国安,蒋云清.我国核燃料后处理技术的现状与发展[J].中国核工业(China Nuclear Industry),2015(12):26-30. [4] 廖映华,云虹,王春.乏燃料后处理技术研究现状[J].四川化工,2012,15(4):12-15. LIAO Yinghua,YUN Hong,WANG Chun.A survey of research on reprocessing technology of spent nuclear fuel′s[J].Sichuan Chemical Industry,2012,15(4):12-15. [5] 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. LIU Haijun,CHEN Xiaoli.Research status of spent fuel reprocessing technology at home and abroad[J].Energy Conservation Technology,2021,39(4):358-362. [6] Lines A M,Adami S R,Casella A J,et al.Electrochemistry and spectroelectrochemistry of the Pu (Ⅲ/Ⅳ) and (Ⅳ/Ⅵ) couples in nitric acid systems[J].Electroanalysis,2017,29(12):2744-2751. [7] Lines A M,Hall G B,Asmussen S E,et al.Sensor fusion:Comprehensive real-time, on-line monitoring for process control via visible,NIR,and Raman spectroscopy[J].ACS Sensors,2020,5(8):2467-2475. [8] 李定明,张永申,刘联伟,等.吸收光谱法直接测定乏燃料溶解液及1AF料液中Pu(Ⅵ)的含量[J].核化学与放射化学,2021,43(6):509-516. LI Dingming,ZHANG Yongshen,LIU Lianwei,et al.Determination of Pu(Ⅵ) in spent fuel solution and 1AF feed by absorption spectrophotometric[J].Journal of Nuclear and Radiochemistry,2021,43(6):509-516. [9] Paulenova A,Tkac P,Matteson B S.Speciation of plutonium and other metals under UREX process conditions[C]//Proceeding of GLOBAL 2007, Advanced Nuclear Fuel Cycles and Systems.Boise-Idaho(United Stated):American Nuclear Society,2007:723-727. [10] Jebaraj Mahildoss D,Ravi T N.Spectrophotometric determination of plutonium Ⅲ,Ⅳ,and Ⅵ concentrations in nitric acid solution (Conference Paper)[J].Journal of Radioanalytical and Nuclear Chemistry:An International Journal Dealing with All Aspects and Applications of Nuclear Chemistry,2012(1):87-91. [11] Bryan S A,Levitskaia T G,Johnsen A M,et al.Spectroscopic monitoring of spent nuclear fuel reprocessing streams:An evaluation of spent fuel solutions via raman,visible,and near-infrared spectroscopy[J].International Journal for Chemical Aspects of Nuclear Science & Technology,2011,99(9):563-572. [12] 孙学智,罗朝晖.全球乏燃料后处理现状与分析[J].核安全,2016,15(2):13-16. SUN Xuezhi,LUO Chaohui.Status of global spent fuel reprocessing[J].Nuclear Safety,2016,15(2):13-16. [13] Savosina,Agafonova Moroz M,Yaroshenko I,et al.Plutonium (Ⅳ) quantification in technologically relevant media using potentiometric sensor array[J].Sensors,2020,20(6):1604. [14] Saito A,Choppin G R.Separation of actinides in different oxidation states from neutral solutions by solvent extraction[J].Analytical Chemistry,1983,55(14):2454-2457. [15] Cleveland J M, Rees T F, Nash K L.Plutonium speciation in selected basalt, granite, shale, and tuff groundwaters[J].Nuclear Technology,1983,62(3):298-310. [16] Bernhard,Kuczewski,Christian,et al.Separation of plutonium and neptunium species by capillary electrophoresis-inductively coupled plasma-mass spectrometry and application to natural groundwater samples[J].Analytical Chemistry,2003,75(24):6769-6774. [17] Neu M P,Hoffman D C,Roberts K E,et al.Comparison of chemical extractions and laser photoacoustic spectroscopy for the determination of plutonium species in near-neutral carbonate solutions[J].Radiochimica Acta,1994,66-67(s1):251-258. [18] Wilson R E,Hu Y J,Nitsche H.Detection and quantification of Pu(Ⅲ, Ⅳ, Ⅴ, and Ⅵ) using a 1.0-meter liquid core waveguide[J].Radiochimica Acta,2005,93(4):203-206. [19] Lee M H,Kim J Y,Kim W H,et al.Investigation on the spectroscopic characteristics for Pu oxidation state in acid and alkali medium[J].Journal of the Korean Radioactive Waste Society,2007,5(2):103-108. [20] Lee M H,Park Y J,Kim W H.Absorption spectroscopic properties for Pu(Ⅲ, Ⅳ and Ⅵ) in nitric and hydrochloric acid media[J].Journal of Radioanalytical and Nuclear Chemistry,2007,273(2):375-382. [21] 武红英,仲敬荣,李英秋,等.盐酸中Pu(Ⅲ),Pu(Ⅳ),Pu(Ⅵ)的制备及紫外-可见吸收光谱[J].物理化学学报,2015(Z1):49-53. WU Hongying,ZHONG Jingrong,LI Yingqiu,et al.Preparation and ultraviolet-visible absorption spectra of Pu(Ⅲ),Pu(Ⅳ) and Pu(Ⅵ) in hydrochloric acid[J].Acta Physico-Chimica Sinica,2015(Z1):49-53. [22] 李定明,张丽华,龚焱平,等.后处理有机相料液中Pu(Ⅳ)和硝酸的同时快速分析[J].原子能科学技术,2016,59(2):235-241. LI Dingming,ZHANG Lihua,GONG Yanping,et al.Simultaneous and fast determination for Pu(IV) and nitric acid in organic feed solution of nuclear fuel reprocessing[J].Atomic Energy Science and Technology,2016,59(2):235-241. [23] 伊小伟,党海军,曾斌,等.吸收光谱法测定不同价态钚的含量[J].理化检验(化学分册),2017,53(2):160-164. YI Xiaowei,DANG Haijun,ZENG Bin,et al.Absorption spectrophotometric determination of plutonium in different oxidation states[J].Physical Testing and Chemical Analysis(Part B:Chemical Analysis),2017,53(2):160-164. [24] 彭曼舒,冯伟伟,曹骐,等.拉曼光谱技术在核燃料分析中的应用研究进展[J].光散射学报,2022,34(1):85-94. PENG Manshu,FENG Weiwei,CAO Qi,et al.Research progress and application of Raman spectroscopy on the analysis of nuclear fuel[J].The Journal of Light Scatering,2022,34(1):85-94. [25] 李定明,张永申,张彤,等.红外吸收光谱法测定铝靶后处理工艺料液中硝酸铝和硝酸[J].化学分析计量, 2021,30(12):18-25. LI Dingming,ZHANG Yongshen,ZHANG Tong,et al.Determination of aluminum nitrate and nitric acid in aluminum target reprocess feed by infrared absorption spectrophotometric[J].Chemical Analysis and Meterage,2021,30(12):18-25. [26] 李定明,张丽华,王玲,等.光纤光谱技术在后处理过程控制分析中的应用[C]//中国核学会2017年学术年会论文集第6册(核化工分卷、核化学与放射化学分卷、辐射物理分卷)》.威海:中国核学会,2017:85-94. [27] 李定明,王玲,张丽华,等.近红外光谱法直接测定后处理水相料液中硝酸浓度[J].核化学与放射化学,2013,35(2):96-105. LI Dingming,WANG Ling,ZHANG Lihua,et al.Determination of nitric acid in aqueous solution of uranium and plutonium purification process by near infrared spectroscopy[J].Journal of Nuclear and Radiochemistry,2013,35(2): 96-105. [28] 辛伍红.朗伯-比尔定律的适用条件与限制[J].化工时刊(Chemical Industry Times),2020,34(7):49-51. [29] Freudenberger B M, Gantner E, Steinert D,et al.Raman spectroscopic investigation of Pu(Ⅳ)-Pu(Ⅵ)-oxidation in the Pu(Ⅳ)-Ru(Ⅲ)-HNO3 system[J].Radiochimica Acta,1990,51(4):157-161. [30] Smith N A.Speciation and spectroscopy of the uranyl and tetravalent plutonium nitrate systems:Fundamental studies and applications to used fuel reprocessing [D]. Las Vegas:University of Nevada,2010. [31] 罗文宗,张文青.钚的分析化学[M].北京:原子能出版社,1991. [32] 钱红娟,张丽华,刘焕良,等.1BP中铀钚价态及其含量的分析方法[J].核化学与放射化学,2019,41(6):551-560. QIAN Hongjuan,ZHANG Lihua,LIU Huanliang,et al.Determination of valence and concentration of uranium and plutonium in 1BP solution[J].Journal of Nuclear and Radiochemistry,2019,41(6):551-560. [33] Kim S Y,Asakura T,Morita Y.Electrochemical and spectroscopic studies of Pu(Ⅳ) and Pu(Ⅲ) in nitric acid solutions[J].Journal of Radioanalytical & Nuclear Chemistry,2013,295(2):937-942. [34] Lines A,Adami S,Sinkov S,et al.Multivariate analysis for quantification of plutonium(Ⅳ) in nitric acid based on absorption spectra[J].Analytical Chemistry,2017,89(17):9354-9359. [35] 付建丽,吴继宗,张丽华,等.高灵敏钚价态分析仪的研制[J].核化学与放射化学,2013,35(1):8-13. FU Jianli,WU Jizong,ZHANG Lihua,et al.Development of high-sensitive plutonium valence state spectrometer[J].Journal of Nuclear and Radiochemistry,2013,35(1):8-13.
