Removal of Ruthenium from PUREX Process, (II) Fundamental Research of Electrolytic Oxidation of Ruthenium

A new method was developed for the removal of ruthenium from nitric acid solutions. Ruthenium in 3 M nitric acid solution is oxidized electrolytically to ruthenium tetraoxide, and the tetraoxide is extracted into n-paraffin. The ruthenium tetraoxide extracted in paraffin is readily reduced to ruthenium dioxide by the solvent as black suspension, and it can be easily filtered off through an ordinary cellulose fiber filter. By this method, ruthenium, one of the most troublesome fission elements in PUREX Process, can be removed.     

Development and Validation of a Flowsheet Simulation Model for Neptunium Extraction in an Advanced PUREX Process

An Advanced PUREX process has been developed for separation and recycling of neptunium from spent nuclear fuel. This work presents a new flowsheet simulation model for the extraction of neptunium using centrifugal contactors, where mass transfer is modeled using two-film theory and a linear driving force. Distribution coefficients and neptunium redox reactions are modeled using published models. Mass transfer between the organic and aqueous phases in the phase separation zone is shown to have a negligible effect. The model is applied to a previously tested flowsheet and its predictions are shown to be in good agreement with the experimental results.     

Studies on the Development of a Two Stage SLM System for the Separation of Carrier‐free 90Y using KSM‐17 and CMPO as Carriers

Abstract

Solvent extraction studies of Y³⁺ and Sr²⁺ with 2‐ethylhexyl 2‐ethylhexyl phosphonic acid (KSM‐17) and octyl(phenyl)‐N,N‐diisobutylcarbamoylmethylphosphine oxide (CMPO) are carried out from aqueous media containing a wide range of nitric acid and other potential reagents to arrive at the operating conditions for the selective transport of ⁹⁰Y using supported liquid membrane (SLM) containing these reagents as carriers. Since the transport data of ⁹⁰Y using single cell SLM with KSM‐17 was available from our earlier experiments, single cell transport studies with CMPO carrier are only carried out to optimize the strippant phase. Transport studies with pure ⁹⁰Y is carried out using a transport cell with two SLMs one with KSM‐17 and the other CMPO carriers to optimize the transport parameters. Based on these data the development of a two stage SLM system for the generation of carrier free ⁹⁰Y from ⁹⁰Sr source is described. The procedure described is amenable for automation and scale up.     

PUREX流程中Tc(Ⅶ)对U(Ⅳ)反萃Pu(Ⅳ)的影响

研究了Tc()对U()还原反萃Pu()的影响。研究结果表明,在单级反萃中,有机相中锝的初始质量浓度高达441mgL时,Pu()的反萃率无明显改变;两相混合放置时间足够长时,Pu()的反萃率会降低,而且开始降低的时间随锝浓度增加而缩短;体系中有机相和水相的酸浓度、Pu浓度、U()及U()浓度的变化在所研究的范围内对Pu()反萃率的影响都不大。逆流萃取的串级实验结果表明,当1BF中Tc()的质量浓度大于135mgL时,会严重影响Pu()的反萃;小于70mgL时,对Pu()的反萃无明显影响。研究还表明,引起Pu()反萃率降低的原因是肼在低价锝的催化作用下的破坏。降低Tc()含量和缩短放置时间都有助于减小PUREX流程中锝对U()反萃Pu()的影响。     

Distribution of technetium in PUREX process streams

Extraction of technetium has been carried out from the aqueous medium containing nitric acid under different experimental conditions to investigate its extraction behaviour in 30% tri-n-butyl phosphate in n-dodecane. In order to study the distribution behaviour of technetium in different streams of PUREX process, experiments were carried out under process conditions. The distribution of technetium was also studied using anion-exchange resin. Based on these results, the path of technetium in the PUREX process streams has been established which will be useful in the development of an advanced PUREX flow-sheet for containment and isolation of technetium in an environmental friendly fuel cycle.     

Speciation of Molybdenum (VI) In Aqueous and Organic Phases of Selected Extraction Systems

Abstract

The extraction study of molybdenum (VI) by 30% tri-n-butyl phosphate in n-dodecane and 0.2 M octyl (phenyl)-N,N-di-isobutylcarbamoylmethylphosphine oxide in 30% tri-n-butyl phosphate extraction systems was performed from aqueous solution containing HCl, HNO₃ and acetohydroxamic acid. Depending on extraction conditions, acetohydroxamic acid can significantly affect the speciation of molybdenum and can increase or decrease its distribution ratio. Our investigation confirmed the strong ability of the acetohydroxamic acid to form complexes with Mo even in highly acidic solutions. UV absorption spectra confirmed that a fraction of the Mo(VI)-AHA species can be present in the organic phase after extraction.     

基于多级混合澄清槽的PUREX流程的计算模型

主要通过建立分配比模型、化学反应模型、传质模型构建了一套基于混合澄清槽的PUREX流程中关键循环过程的计算模型(mathematical model for main PUREX process based on mixer-settler,简称MPMS),用于计算各级单元的物料浓度。通过检验两组具有代表性的PUREX工艺流程,模拟结果较好地匹配实验数据,表明该计算模型具有良好的精确性。该计算模型将为基于多级混合澄清槽的PUREX流程模拟提供有益帮助。     

Simulation of Neptunium Extraction in an Advanced PUREX Process—Model Improvement

Routing neptunium to a single product in spent nuclear fuel reprocessing is a significant challenge. In this work, we have further improved the simulation of neptunium extraction in an advanced PUREX flowsheet by applying a revised model of the Np(V)–Np(VI) redox reaction kinetics, a new nitric acid radiolysis model, and by evaluating various models for the nitrous acid distribution coefficient. The Np disproportionation reaction is shown to have a negligible effect. The models are validated against published ‘cold test’ experimental results; the ‘hot test’ simulation suggests that high neptunium radiolysis could help to achieve high recoveries using this flowsheet.     

Studies on Transport of Anionic Complex of Plutonium From Nitric Acid Medium across ALIQUAT 336/n-Paraffin Liquid Membrane

The present studies deal with the application of the supported liquid membrane (SLM) technique for the separation and purification of plutonium from other impurities in nitric acid medium using anion exchanger Aliquat 336 (a quaternary ammonium salt)/ n-paraffin as a carrier. The effects of feed acidity, stripping agent, and membrane pore size and membrane thickness on the transport behavior of anionic complex of plutonium have been studied in detail. An attempt has been made to establish the mechanism for plutonium transport and model the physicochemical transport of plutonium across SLM. Transport of anionic complex of plutonium increased with increase in carrier concentration upto 10% (w/v), while with further increase in carrier concentration, decrease in transport of plutonium was observed. The PTFE membrane with 0.45 µm pore size and 80 µm thickness was found to be most suitable for the transport of plutonium. The effect of membrane thickness indicates that the transport phenomenon is diffusion controlled. Transport behavior of plutonium, uranium, and other fission products from actual feed solution of ion exchange method obtained in PUREX process was also tested and the result clearly indicates that Aliquat 336 has high selectivity for plutonium and it can be used for the separation and purification of plutonium by the supported liquid membrane technique.     

30%TBP/煤油-硝酸溶液体系中镎的化学行为

为了解镎在萃取过程中的化学行为,采用单级萃取研究了硝酸溶液中Np(Ⅴ)氧化为Np(Ⅵ)的行为和此过程中TBP萃取Np(Ⅵ)的性能。实验结果表明,提高硝酸浓度有利于Np(Ⅴ)的氧化,提高了萃取体系对Np(Ⅵ)的萃取;提高亚硝酸浓度加快了Np(Ⅵ)和Np(Ⅴ)之间氧化还原反应的进行,但是会降低平衡后萃取系统中Np(Ⅵ)的比例;升高温度可以提高Np(Ⅴ)转化为Np(Ⅵ)的速率。通过模拟1AF料液的混合澄清槽台架实验表明,自1AX中引入0.01 mol/L HNO2,同时将萃取温度升高到45℃,在1AF硝酸浓度为3.5mol/L的条件下,1A槽镎的萃取率可以达到80%。