超临界流体络合萃取镧系和锕系元素的研究进展

超临界流体络合萃取是1种可用于萃取金属离子的新型分离技术，它应用于乏燃料后处理和核废物处理中的最大优点是能大幅减少二次废物的产生。文章主要介绍超临界流体的特点、超临界流体络合萃取的基本原理及其影响因素，并对超临界流体络合萃取镧系和锕系元素的研究进展及其在乏燃料后处理工艺研究中的应用进行综述。     

离子液体在镧系锕系元素萃取分离应用中的理论计算研究进展北大核心CSCD

离子液体在核燃料后处理萃取分离过程中被认为具有一定的应用前景。常规的萃取剂在离子液体中展现出比传统溶剂体系更优异的萃取分离性能,因此离子液体自身在其中的角色和作用值得研究。本论文综述了以分子动力学模拟和量子化学计算方法研究离子液体体系萃取分离镧系锕系元素的相关研究工作,重点关注金属离子和金属配合物在离子液体中与离子液体阴阳离子之间的相互作用。     

超临界流体萃取镧系和锕系元素研究进展北大核心CSCD

镧系和锕系元素的分离是核工业中研究的热点问题,常规的溶剂萃取法步骤复杂,在萃取过程中会产生大量的二次废液。超临界流体萃取(supercritical fluid extraction,SFE)技术是一种新型化工分离技术,由于其步骤简单、过程清洁,近年来该项技术应用于金属离子萃取方面的研究越来越多。本文综述了近十年来超临界流体(supercritical fluid,SCF)在镧系和锕系元素萃取方面的研究进展,发现目前的研究大部分集中在采用超临界萃取技术从各种复杂样品中萃取铀,通过对所用样品的对比与总结,分析了该技术在工业应用中的可能性。     

铝合金化技术在乏燃料干法后处理中的应用研究进展

干法后处理在未来先进核燃料循环中将发挥关键作用。由美国开发的熔盐电精炼流程是目前最具应用前景的干法后处理流程之一,但是锕系元素(An)与镧系元素(Ln)的高效分离仍然是该流程目前亟待解决的关键科学与技术问题之一。研究表明,An与Ln形成铝合金时沉积电位差较大,采用固态铝电极电解有望实现An与Ln的有效分离,从而更好地服务于分离-嬗变策略。本文针对铝合金化技术在乏燃料干法后处理中的应用研究进展进行综合阐述,重点介绍铝合金化在熔盐电精炼中的应用研究,主要包括Ln和An的铝合金化行为、An和Ln的铝合金化分离等几个方面。     

加速器驱动先进核能系统的乏燃料循环再生研究北大核心CSCD

乏燃料后处理是核燃料循环的关键环节,制约核电的可持续发展。借助于加速器驱动先进核能系统(ADANES)提供的高通量、硬能谱的外源中子,其乏燃料后处理只需除去乏燃料中的挥发性裂变产物和影响次锕系元素嬗变的中子毒物,长寿命的次锕系元素Np、Am、Cm可与二氧化铀一起转化为新的燃料元件在加速器驱动燃烧器中燃烧、嬗变、增殖和产能。基于此,本课题组提出了加速器驱动的乏燃料后处理及再生制备的技术路线,包括高温氧化粉化与挥发、选择性溶解分离和燃料再生制备。本文主要介绍了近几年本课题组在这三方面所取得的一些成就,希望能为加速器驱动先进核能系统的乏燃料后处理提供基础数据。     

镧系及锕系元素在离子液体中的电化学行为

乏燃料回收是核燃料循环的核心,对核安全和核能可持续发展具有重要的意义,其分为使用水溶液的湿法和不使用水溶液的干法处理。熔盐电解技术是乏燃料干法回收的重要方法之一,但其工艺温度往往在数百摄氏度,对设备和能耗要求都很高。离子液体具有电化学窗口宽、低熔点、低蒸汽压、热稳定性好等优点,有望替代高温熔盐用于乏燃料干法回收。本文概述了镧系元素和锕系元素在离子液体中电化学方面的研究状况,表明离子液体用于乏燃料干法回收是可行的,但需要更多的基础性研究。     

Nuclide separation from spent nuclear fuels by using tertiary pyridine resin

The newly nuclide separation system from spent nuclear fuels is proposed. The proposed separation system consists of recovery of nuclear fuel elements, separation of trivalent minor actinide from lanthanide, and separation of some fission products such as strontium. This separation system is based on the chromatographic technique using the tertiary pyridine resin. Separation experiments using mixed oxide fuel highly irradiated in fast reactor “Joyo” were carried out. The recovery of plutonium, the separation of minor actinide from fission products including lanthanides, and the separation of americium and curium were achieved. The recovery or removal of platinum group elements and technetium was also investigated, and the removal of these elements prior to the main reprocessing process has been proposed.     

Actinide recycling by pyro-process with metal fuel FBR for future nuclear fuel cycle system

Pyro-metallurgical technology is one of potential devices for future nuclear fuel cycle. Not only economic advantage but also environmental safety and strong resistance for proliferation are required for the fuel cycle. In order to satisfy the requirement, actinides recycling applicable to LWR and FBR cycles by pyro-process has been developed since more than ten years in CRIEPI. The main technology is electrorefining for U and Pu separation and reductive-extraction for TRU separation, which can be applied on oxide fuels through reduction process as well as metal fuels. The application of this technology on separation of TRU in HLLW through chlorination could contribute to the improvement of public acceptance on the geologic disposal.

The main achievements are summarized as follows:

• -|The elemental technologies, such as electrorefining, reductive extraction, injection casting and salt waste treatment and solidification, have been developed successfully with lots of experiments

• -|The fuel dissolution into molten salt and uranium recovery on solid cathode for electrorefining have been demonstrated by engineering scale facility in Argonne National Laboratory by using spent fuels and in CRIEPI by uranium tests.

• -|Single element tests, using actinides, showed the Li reduction to be technically feasible, remaining the subjects of technical feasibility on multi-elements system and on effective recycle of Li by electrolysis of Li₂O.

• -|Concerning on the treatment of HLLW for actinide separation, the conversion to chlorides through oxides has been also established through uranium tests.

• -|It is confirmed that more than 99% of TRU nuclides can be recovered from the high level liquid waste by TRU tests

• -|Through these studies, the process flow sheets for reprocessing of metal and oxide fuels and for partitioning of TRU separation have been established.

The subjects to be emphasized for further development are classified into three categories, that is, process development (demonstration), technology for engineering development, and supplemental technology.

The metal fuel FBR has a high potential for recycling actinides by integration with pyro-reprocessing. Alloys of U-Pu-Zr with minor actinides are investigated from points of fuel properties. The miscibility and other characteristics suggest that the maximum content up to ca. 5 wt% of minor actinides is allowable in the matrix. Nine pins of metal fuel including minor actinides are ready for irradiation at Phenix fast reactor.     

浊点萃取在锕系和镧系元素分离分析中的应用

浊点萃取（cloud point extraction, CPE）是一种安全环保同时兼具高富集系数和低成本的萃取方法,在分析化学中已经被广泛应用于金属离子分析等领域。锕系和镧系金属元素存在环境复杂,自身浓度相对较低,对其进行分离和分析一直是放射化学研究者所关注的问题。经过条件优化,CPE能够有选择性地分离和富集锕系和镧系金属元素。通过与多种技术联用,CPE能实现锕系和镧系元素的高灵敏度分析。本文在介绍浊点萃取机理的基础上,着重描述了不同萃取体系中各类萃取剂（β-二酮类、膦氧类、含氮类、含硫类）对于锕系和镧系元素的萃取效果,全面总结了其中使用的不同联用技术,同时简述了通过构筑超分子识别位点,修饰配体,使用不同表面活性剂及掩蔽剂等改良现有浊点萃取体系的尝试。最后,对浊点萃取在放射化学领域的应用进行了总结和展望。     

离子液体在金属离子萃取分离中的应用

离子液体作为绿色溶剂是溶剂萃取分离金属离子方面研究的热点.介绍了以离子液体为溶剂时,萃取分离各种金属离子的效果,包括碱金属、碱土金属、过渡金属、稀土及锕系金属,以及核燃料后处理涉及的铀、钚及裂变产物等多种离子,深入探讨了其萃取机理.展望了离子液体取代有毒、易挥发、易造成环境污染的有机溶剂的发展和应用前景.     

The reactor physics characteristics of a transuranic mixed oxide fuel in a heavy water moderated reactor

The reprocessing actinide materials extracted from spent fuel for use in mixed oxide fuels is a key component in maximizing the spent fuel repository utility. While fast spectrum reactor technologies are being considered in order to close the fuel cycle, and transmute these actinides, there is potential to utilize existing pressurized heavy water reactors such as the CANDU^®1 design to meet these goals. The use of current thermal reactors as an intermediary step which can burn actinide based fuels can significantly reduce the fast reactor infrastructure needed. This paper examines the features of actinide mixed oxide fuel, TRUMOX, in a typical CANDU nuclear reactor. The actinide concentrations used were based on extraction from 30 year cooled spent fuel and mixed with natural uranium in 4.75% actinide MOX fuel. The WIMS-AECL model of the fuel lattice was created and the two neutron group properties were transferred to RFSP in order to create a 3 dimensional time average full core model. The model was created with typical CANDU limits on bundle and channel powers and a burnup target of 45 MWd/kgHE. The TRUMOX fuel design achieved its goals and performed well under normal operations simulations. This effort demonstrated the feasibility of using the current fleet of CANDU reactors as an intermediary step in burning reprocessed spent fuel and reducing actinide burdens within the end repository. The recycling, reprocessing and reuse of spent fuels produces a much more sustainable and efficient nuclear fuel cycle using existing and proven reactor technologies.     

光谱学方法在锕系/镧系元素配位化学研究中的应用

锕系/镧系金属离子的配位化学对于控制其在后处理流程中的走向、开发新型萃取剂及反萃剂、预测长寿命锕系金属离子在环境中的迁移行为、降低其在生物体中的毒性均有重要意义。光谱学方法是配位化学研究的重要手段,不仅可用来测定配位反应热力学数据,还能提供配位模式、配合物键长、键角等信息。本文在概述光谱学方法用于锕系/镧系元素配位化学研究最新进展的基础上,重点介绍荧光光谱和拉曼光谱在配合物热力学数据测定及结构分析方面的应用,并展望多光谱联合研究方法在锕系/镧系元素配位化学研究中的应用前景。     

Separation of rare metal fission products in radioactive wastes in new directions of their utilization

An electrolytic extraction method has been studied to separate fission products (Ru, Rh, Pd, Tc, Se, Te, etc.) from the nuclear spent fuel. Yet they are rare metal fission products (RMFP), most are long-lived (LLFP; Pd, Tc, Se, Te). In the applied electrochemical separation process, Pd²⁺ cation itself would not only be easily deposited from various nitric acid solutions, but enhance also the deposition of RuNO³⁺ and ReO₄⁻ by acting as a catalyst (as Pd_adatom). Such Catalytic Electrolytic Extraction (CEE) method was found to be applicable in the case of TcO₄⁻ deposition. The quaternary-, Pd-Ru-Rh-Re, deposit Pt electrodes showed the highest cathodic current corresponding to the hydrogen evolution reaction, ca. twice superior to that of the Pt electrode in artificial sea water as well as in alkaline solution. Adsorption / desorption behavior of ¹⁰⁶Ru, etc. on the tertiary pyridine resin, being set as a pre-separation step to the CEE process, was newly confirmed by the reprocessing experiments with a highly irradiated fast reactor MOX fuel. The promising utilization of recovered RMFP will be a “FP-catalyst” for electrolytic hydrogen production, where they would be circulating material to bridge nuclear and hydrogen energy systems.     

Application of fluoride volatility method to the spent fuel reprocessing

ABSTRACT

An advanced reprocessing system has been developed to treat various SF (spent fuels): spent UO₂ and MOX (mixed oxide) fuels from LWR (light water reactor) and MOX fuel from FR (fast reactor). The system consists of SF fluorination to separate most U (uranium) as volatile UF₆, dissolution of solid residue containing Pu (plutonium), FP (fission products), MA (minor actinides) and partial U by nitric acid, and Pu+U separation from FP and MA by conventional solvent extraction. Gaseous UF₆ is purified by the thermal decomposition and the adsorption of volatile PuF₆ and adsorption of other impurities. This system is a hybrid process of fluoride volatility and solvent extraction and called FLUOREX. Fluorination of most U in the early stage of the reprocessing process is aimed at sharply reducing the amount of SF to be treated in the downstream aqueous steps and directly providing purified UF₆ for the enrichment process without conversion. The FLUOREX can flexibly adjust the Pu/U ratio, rapidly separate UF₆ and economically treat aqueous Pu+U. These features are especially suitable for the transition period fuel cycle from LWR to FR. This paper summarizes the feasibility confirmation results of FLUOREX.     

The evaluation of the pyrochemistry for the treatment of Gen IV nuclear fuels - Inert matrix chlorination studies in the gas phase or molten chloride salts

The structure of the fuels for the future Gen IV nuclear reactors will be totally different from those of PWR, especially for the GFR concept including a closed cycle. In these reactors, fissile materials (carbides or nitrides of actinides) should be surrounded by an inert matrix. In order to build a reprocessing process scheme, the behavior of the potential inert matrices (silicon carbide, titanium nitride, and zirconium carbide and nitride) was studied by hydro- and pyrometallurgy. This paper deals with the chlorination results at high temperature by pyrometallurgy. For the first time, the reactivity of the matrix towards chlorine gas was assessed in the gas phase. TiN, ZrN and ZrC are very reactive from 400 °C whereas it is necessary to be over 900 °C for SiC to be as fast. In molten chloride melts, the bubbling of chlorine gas is less efficient than in gas phase but it is possible to attack the matrices. Electrochemical methods were also used to dissolve the refractory materials, leading to promising results with TiN, ZrN and ZrC. The massive SiC samples used were not conductive enough to be studied and in this case specific SiC-coated carbon electrodes were used. The key point of these studies was to find a method to separate the matrix compounds from the fissile material in order to link the head to the core of the process (electrochemical separation or liquid-liquid reductive extraction in the case of a pyrochemical reprocessing).     

The closed on-site fuel cycle of the brest reactors

The BREST fast reactor with nitride fuel and lead coolant is being developed as a reactor of new generation, which has to meet a set of requirements placed upon innovative reactors, namely efficient use of fuel resources, nuclear, radiation and environmental safety, proliferation resistance, radwaste treatment and economic efficiency. Mixed uranium-plutonium mononitride fuel composition allows supporting in BREST reactor CBR≈1. It is not required to separate plutonium to produce “fresh” fuel. Coarse recovered fuel purification of fission products is allowed (residual content of FPs may be in the range of 10⁻² – 10⁻³ of their content in the irradiated fuel). High activity of the regenerated fuel caused by minor actinides is a radiation barrier against fuel thefts. The fuel cycle of the BREST-type reactors “burns” uranium-238, which must be added to the fuel during reprocessing. Plutonium is not extracted during reprocessing being a part of fuel composition, thus exhibiting an important nonproliferation feature.

The radiation equivalence between natural uranium consumed by the BREST NPP closed system and long-lived high-level radwaste is provided by actinides (U, Pu, Am) transmutation in the fuel and long-lived products (I, Tc) transmutation in the blanket. The high-level waste must be stored for approximately 200 years to reduce its activity by the factor of about 1000.

The design of the building and the entire set of the fuel cycle equipment has been completed for the demonstration BREST-OD-300 reactor, which includes all main features of the BREST-type reactor on-site closed fuel cycle.     

萃取分离法处理高放废液的进展

评述了近几年用萃取分离法从高放废液中去除超铀锕系元素的进展情况，着重介绍世界上已有的应用前景较好的ＴＲＵＥＸ流程（美）、ＤＩＡＭＥＸ流程（法）、ＤＩＤＰＡ流程（日）、ＣＴＨ流程（瑞典）和ＴＲＰＯ流程（中国）。     

干法后处理技术典型流程综述

虽然基于溶剂萃取的Purex流程在乏燃料后处理几十年的应用中取得的成功,使得水法后处理至今没有发展出可以取代这一流程的新萃取剂,但干法后处理却有了两种可供进一步发展的流程:氟化物挥发法和高温电化学法。氟化物挥发法存在的最大问题是热力学上PuF6必须在有大量F2过剩的条件下才稳定。高温电化学法适合于处理合金元件,以及氧化物和碳化物元件。首先,将核燃料熔解在熔盐中,然后,电解使铀钚在阴极上沉积,再对阴极上沉积出来的铀钚进行精制而得到铀钚产品。但该方法存在熔盐对MOX的熔解能力和对过程设备的腐蚀问题。     

高温气冷堆乏燃料后处理首端技术研究进展

高温气冷堆乏燃料采用后处理路线能充分利用核资源并减少需要最终地质处置的核废物量,有利于核能的可持续发展。传统的LWR乏燃料后处理首端过程不能用于处理高温气冷堆的乏燃料。高温气冷堆乏燃料元件及包覆层颗粒的破碎是首端处理技术的难点。破碎乏燃料元件及去除石墨的方法主要有机械碾碎法、燃烧法、脉冲电流法等;破碎及去除碳化硅的方法有传统机械碾碎法,以及正在发展中的熔融法、气流喷射粉碎法等,其中,气流喷射粉碎法具有较好的发展前景。目前,尚无一种理想的技术来解决高温气冷堆乏燃料后处理中的首端过程问题,需进一步开展高温气冷堆乏燃料后处理技术的研究。     

功能离子液体在镧锕系离子萃取分离中的研究进展北大核心CSCD

离子液体因其独特的物化性质已成为溶剂萃取领域中绿色环保、极具应用前景的稀释剂。除了对萃取剂和萃合物有良好溶解性之外,离子液体萃取体系通过离子交换机理的协同作用,往往还展现出更优的萃取性能。而功能离子液体通常是在离子液体结构基础上进行化学修饰,使其兼具离子液体和螯合基团的双重功能,在萃取过程中不仅能用作稀释剂,还具有萃取作用。近十余年来,功能离子液体在放化分离领域已引起广泛关注。本文首先对离子液体和功能离子液体进行了简介,重点讨论其结构上的关联与区别;再以功能为导向,综述了功能离子液体在铀酰离子、钍离子、镧系和次锕系金属离子萃取分离方面的国内外研究现状,并对功能离子液体在镧锕萃取分离领域的未来研究趋势进行了展望。