高温熔盐中氧化物乏燃料的电化学还原研究进展

干法后处理流程可应用于快堆乏燃料后处理。由美国开发的熔盐电解精炼流程是目前最具应用前景的干法后处理流程之一。为了将电解精炼流程应用于氧化物乏燃料后处理,需要将氧化物乏燃料转化为金属。目前电化学还原是应用最广的氧化物乏燃料还原方法,但是该过程仍然存在亟待解决的关键科学与技术问题。本文针对氧化物乏燃料电化学还原研究进展进行综合阐述,主要包括过程简介、研究现状及电化学还原机理等几个方面。     

俄罗斯氧化物乏燃料电沉积流程研究进展

高温熔盐干法后处理以熔盐作为电解质,通过电解精炼和电沉积回收核燃料中的铀和钚。目前,俄罗斯、美国、日本、韩国和欧盟等国均在积极发展乏燃料高温熔盐干法后处理技术的研究,其中俄罗斯的金属氧化物核燃料电沉积流程是经典的流程之一。本文对俄罗斯原子反应堆研究所(Research Institute of Atomic Reactors, RIAR)发展的氧化物乏燃料高温熔盐电沉积干法后处理的发展现状、流程及特点进行了综述。     

俄罗斯氧化物乏燃料电沉积流程研究进展

高温熔盐干法后处理以熔盐作为电解质，通过电解精炼和电沉积回收核燃料中的铀和钚。目前，俄罗斯、美国、日本、韩国和欧盟等国均在积极发展乏燃料高温熔盐干法后处理技术的研究，其中俄罗斯的金属氧化物核燃料电沉积流程是经典的流程之一。本文对俄罗斯原子反应堆研究所（Research Institute of Atomic Reactors,RIAR）发展的氧化物乏燃料高温熔盐电沉积干法后处理的发展现状、流程及特点进行了综述。     

干法后处理流程中电解精炼设备研发进展北大核心CSCD

高燃耗快堆乏燃料具有高钚含量、强放射性、高释热率等特点。基于溶剂萃取原理的水法后处理工艺存在溶剂易辐解等问题,宜对高燃耗快堆乏燃料采用干法后处理工艺进行处理。熔盐电解干法工艺采用耐辐照的无机盐为介质,通过电化学方法分离回收锕系元素,是最具应用前景的干法后处理技术。在熔盐电解干法工艺流程中,承担锕系元素分离任务的电解精炼单元是核心环节。本文调研了乏燃料干法后处理过程中电解精炼设备的研发进展,分析了电解精炼设备关键技术和发展趋势,为我国快堆乏燃料电解精炼设备的研发提供了参考。     

氯化锂熔盐中八氧化三铀电解还原基础研究

将氧化物乏燃料直接电解还原为粗金属的过程是目前以电解还原-电解精炼为特征的主流干法后处理流程的重要步骤。二氧化铀（UO₂）是乏燃料的最主要成分,将致密的UO₂芯块转化为八氧化三铀（U₃O₈）粉末后,再进行电化学还原能有效提高还原速率。因此,以U₃O₈为研究对象,开展其在氯化锂（LiCl）熔盐中的电解还原机理研究,对后处理干法流程的开发具有重要的现实意义。本文在650 ℃的LiCl熔盐中,采用循环伏安法和恒电位电解法,研究U₃O₈的电解还原行为;对电解后的样品,运用XRD、SEM等手段分析其组成和形貌,并推测相应的还原机理。     

乏燃料干法后处理中的熔盐减压蒸馏技术

本文扼要介绍了熔盐减压蒸馏技术在美国橡树岭国家实验室用于熔盐反应堆氟化物熔盐回收,以及近年来美、韩、日和法等国用于水堆/快堆乏燃料中熔盐电解阴极产物纯化的概况,分析减压蒸馏技术在这两个领域应用中面临的挑战,提出可能的发展策略。进一步强调指出,蒸馏分离技术需要与放射化学相结合,形成化学反应-蒸馏/减压蒸馏的新模式,以应对钍基熔盐反应堆乏燃料干法后处理的严峻挑战。     

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。     

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。     

LiF对LiCl-KCl熔盐中钆电解精炼的影响

正熔盐电解精炼干法后处理技术受到越来越多核能国家的关注,以较高的去污系数从乏燃料中回收铀钚已成为研究热点。根据之前的研究发现,LiF加入LiCl-KCl熔盐前后对钆、铽的还原电位有影响,以此为理论基础,进行了LiF加入LiCl-KCl熔盐前后对钆、铽电解精炼的影响。图1为LiF加入前后的电解曲线,加入LiF后进行钆、铽电解精炼时两种熔盐体系所得到的阴极产物示于图2。表1列出不同金属样品中的元素含     

干法后处理熔盐电解精炼过程数学模型研究

熔盐电解精炼是乏燃料干法后处理的核心工艺单元,通过数学模型探索高温熔盐电解精炼过程的化学与电化学变化,可为电解精炼工艺优化和设备设计提供参考依据。本文基于电化学热力学及物质传递公式建立了乏燃料熔盐电解精炼过程的数学模型,以铀钚锆三元合金燃料为研究对象,计算了燃料中关键元素的电极电势、分电流及物料分布随时间的变化。采用向后差分法对物料分布变化方程进行离散,通过文献实验数据对建立的数学模型进行了准确性验证。结果表明,模拟计算所得阴极沉积铀产品与实验数据的相对误差为2.80%,所建数学模型具有较好的拟合性。同时采用所建模型模拟计算了电流强度对乏燃料电解精炼过程的影响,结果表明电解速率与电流强度呈正比,不改变钚铀锆的溶解和沉积顺序。     

Preliminary conceptual design of a geological disposal system for high-level wastes from the pyroprocessing of PWR spent fuels

The inventories of spent fuels are linearly dependent on the production of electricity generated by nuclear energy. Pyroprocessing of PWR spent fuels is one of promising technologies which can reduce the volume of spent fuels remarkably. The properties of high-level wastes from the pyroprocessing are totally different from those of spent fuels. A geological disposal system is proposed for the high-level wastes from pyroprocessing of spent fuels. The amount and characteristics of high-level wastes are analyzed based on the material balance of pyroprocessing. Around 665 kg of monazite ceramic wastes are expected from the pyroprocessing of 10 MtU of PWR spent fuels. Decay heat from monazite ceramic wastes is calculated using the ORIGEN-ARP program. Disposal modules consisting of storage cans, overpacks, and a deposition hole or a disposal tunnel are proposed. Four kinds of deposition methods are proposed. Thermal design is carried out with ABAQUS program and geological data obtained from the KAERI Underground Research Tunnel. Through the thermal analysis, the spacing between the disposal modules is determined for the peak temperature in buffer not to exceed 100 °C. Thermal analysis shows that the optimum spacing between the vertical deposition holes with 4 overpacks is 8 m when the disposal tunnel spacing is 40 m and optimum spacing of 2 m for horizontal disposal tunnel with 25 m tunnel spacing. Also, the spacing reduces to 6 m for vertical deposition when the double-layered buffer is used, which reduces the disposal area to one-sixty fifth (1/65th) compared with the direct disposal of spent fuels. Finally, the effect of cooling time on the disposal area is illustrated.     

Synergistic hydrogen production by nuclear-heated steam reforming of fossil fuels

Processes and technologies to produce hydrogen synergistically by the nuclear-heated steam reforming reaction of fossil fuels are reviewed. Formulas of chemical reactions, required heats for reactions, saving of fuel consumption, reduction of carbon dioxide emission, and possible processes are investigated for such fossil fuels as natural gas, petroleum and coal.

In this investigation, examined are the steam reforming processes using the “membrane reformer” and adopting the recirculation of reaction products in a closed loop configuration. The recirculation-type membrane reformer process is considered to be the most advantageous among various synergistic hydrogen production processes. Typical merits of this process are; nuclear heat supply at medium temperature around 550°C, compact plant size and membrane area for hydrogen production, efficient conversion of a feed fossil fuel, appreciable reduction of carbon dioxide emission, high purity hydrogen without any additional process, and ease of separating carbon dioxide for future sequestration requirements.

The synergistic hydrogen production using fossil fuels and nuclear energy can be an effective solution in this century for the world which has to use fossil fuels to some extent, according to various estimates of global energy supply, while reducing carbon dioxide emission.     

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。     

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.     

Nuclear energy and waste management - pyroprocess for system symbiosis

The actinide management has become a key issue in nuclear energy. Recovering and fissioning transuranium elements reduce the long-term proliferation risks and the environmental burden. The better way of waste management will be made by system symbiosis: a combination of light-water reactor and fast reactor and/or accelerator-driven transmutation system should be sought. The new recycling technology should be able to achieve good economy with smaller plants, which can process fuels from different types of reactors on a common technical basis. Ease in handling the higher heat load of transuranium nuclides is also important. Pyroprocesses with the use of molten salts are regarded as the strong candidate for such recycling technology. In JAEA, the first laboratory for the high-temperature chemistry of Am and Cm has been established. The fundamental data will be combined with the computer code for predicting the molten-salts electrolytic processes.     

Comments on americium volatilization during fuel fabrication for fast reactors

The physical processes relevant to the fabrication of metallic nuclear fuels are analyzed, with attention to recycling of fuels containing U, Pu, and minor volatile actinides for use in fast reactors. This analysis is relevant to the development of a process model that can be used for the numerical simulation and prediction of the spatial distribution of composition in the fuel, an important factor in fuel performance.     

Flow sheet calculations in Thorex method for reprocessing Th-based spent fuels

A model for flow sheet calculations of solvent extraction processes in reprocessing of Th-based spent fuels is proposed and two computer programs, one for extraction section and the other for scrubbing section calculations, are developed. Recoveries and decontamination factors are calculated for a standard Thorex method used for reprocessing Th-based spent fuels. Results compare well with those in literature and the model provides a simple means to study the Thorex method.     

Nuclear carbonization and gasification of biomass for effective removal of atmospheric CO2

By the process of carbonization of biomass a portion of carbon element in biomass is stabilized as solid carbon, and the remaining portion of carbon, which is the volatile product from carbonization, is converted by the subsequent gasification and conversion process to carbon-neutral synthetic fuels, which can replace the fossil derived fuels currently used.In these processes, nuclear energy can effectively be utilized for supplying energy, thus avoiding the CO₂ emission from any biomass or fossil combustion. By utilizing nuclear energy, most of the carbons in biomass are converted to either stabilized solid carbon or carbon-neutral fuels.Thus, significant amount of CO₂ can efficiently be removed from the atmosphere by processing a part of annual growth of biomass, which leads to the decrease of atmospheric CO₂ concentration.     

Plutonium redistribution in fast reactor mixed oxide fuel pins

Some redistribution effects of uranium and plutonium, caused by thermal diffusion and evaporation-condensation processes in mixed oxide fuels, are discussed by means of autoradiographs of sections of fuel pins irradiated in the fast flux of the RAPSODIE reactor. The change in the stoichiometric state as a function of burnup and the radial distribution of oxygen are described and their influence on the redistribution processes is discussed. A model and suitable data are given to calculate redistribution effects on the basis of thermal diffusion in fast reactor fuels. In fuel pins with power ratings of 500 W/cm and 600 W/cm the enrichment of plutonium around the central cavity produces an increase in the central temperature of about 100°C and 250° C, respectively.     

Nuclear energy for transportation: Paths through electricity, hydrogen and liquid fuels

The transportation sector consumes about a quarter of final energy in Japan and worldwide, and presently most of the energy is supplied by petroleum. For global environment and resources, it is important to seek possibilities of replacing a substantial part of the transportation energy by nuclear energy.

For supplying nuclear energy to the transportation sector, investigated are the paths through such ‘energy carriers’ as electricity, hydrogen and synthetic liquid fuels, to the means of transportation such as automobiles. These energy carriers can be produced from nuclear energy, by itself or synergistically with other primary energies like fossil fuels or biomass.

In this paper, possibilities and impacts of these energy carriers to power transportation means are reviewed, and measures and tasks to supply these energy carriers from nuclear energy are examined.

In converting the primary energies into the energy carriers, the synergistic process may be more advantageous than the individual process. Some of the exploratory processes to produce synthetic liquid fuels from fossil fuels and nuclear energy are presented.