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.     

A new concept for the nuclear fuel recycle system: Application of the fluoride volatility reprocessing

Hybrid Recycle System (HRS) is proposed as an advanced recycle system. The HRS consists of improved fluoride volatility reprocessing and vibration packing MOX fuel fabrication processing. For the former, a part of U is volatilized as hexafluoride with diluted F₂ gas, and then residual U and Pu are volatilized with concentrated F₂ gas. Plutonium content of the mixed fluoride gas can be adjusted as desired by controlling the U fluorination reaction in the first step. The U is highly decontaminated and the mixture gas of UF₆ and PuF₆ is not purified. The fluoride mixture is reacted with H₂O and H₂ and directly converted to the mixed oxide grain for the vibration packing. The HRS can reduce the costs of reprocessing and fuel fabrication, the amounts of radioactive wastes and the probability of Pu proliferation.     

Actinide reformer concept

The partitioning and transmutation technology is effective to reduce the environmental impact from disposition of high-level radioactive wastes and improve the efficiency of geological disposal. However, Am and Cm and their daughter nuclides are difficult to handle in the fuel cycle because of their high decay heat and radioactivity. These nuclides also give the chemical instability which harms the soundness of fuel pellet properties.

We propose a new system concept “actinide reformer”, which reforms Am and Cm into Pu by neutron capture reactions and decay. Am and Cm are separated from the PUREX reprocessing process and converted to chloride molten-salt fuel. Using liquid-type fuel, above mentioned defects can be compensated. Actinide reformer is an accelerator-driven system which is composed of a 10 MW-class cyclotron, a tungsten target and a subcritical core. Spent molten-salt fuel is reprocessed as an on-line fuel exchange manner to extract fission products and recover Pu to send back to a power generation cycle. The decay heat and neutron emission from the fuel with recovered Pu are smaller than those of MOX fuel with 5% of minor actinide addition. It expects no significant engineering difficulties and cost increase for construction of MOX fuel based reprocessing/fabrication plant and power reactors.     

铀钚萃取洗涤-共反萃工艺的离心萃取器台架实验研究

由于快堆MOX乏燃料放射性强,需要缩短停留时间以降低溶剂辐解,本工作以离心萃取器为萃取设备,在短停留时间下进行了快堆MOX乏燃料后处理铀钚萃取洗涤-共反萃工艺研究。研究结果显示,该工艺在单级停留时间约20s时具有良好的铀钚收率,萃取洗涤过程中铀和钚收率均大于99.99%,共反萃过程中铀和钚收率分别为99.99%和99.94%;同时能有效防止第三相的形成,避免钚的聚合沉淀。     

Determination of fissile fraction in MOX (mixed U + Pu oxides) fuels for different burnup values

When spent Light Water Reactor fuels are processed by the standard Purex method of reprocessing, plutonium (Pu) and uranium (U) in spent fuel are obtained as pure and separate streams. The recovered Pu has a fissile content (consisting of ²³⁹Pu and ²⁴¹Pu) greater than 60% typically (although it mainly depends on discharge burnup of spent fuel). The recovered Pu can be recycled as mixed-oxide (MOX) fuel after being blended with a fertile U makeup in a MOX fabrication plant. The burnup that can be obtained from MOX fuel depends on: (1) isotopic composition of Pu, which is closely related to the discharge burnup of spent fuel from which Pu is recovered; (2) the type of fertile U makeup material used (depleted U, natural U, or recovered U); and (3) fraction of makeup material in the mix (blending ratio), which in turn determines the total fissile fraction of MOX. Using the Non-linear Reactivity Model and the code MONTEBURNS, a step-by-step procedure for computing the total fissile content of MOX is introduced. As was intended, the resulting expression is simple enough for quick/hand calculations of total fissile content of MOX required to reach a desired burnup for a given discharge burnup of spent fuel and for a specified fertile U makeup. In any case, due to non-fissile (parasitic) content of recovered Pu, a greater fissile fraction in MOX than that in fresh U is required to obtain the same burnup as can be obtained by the fresh U fuel.     

Determination of Li-6/Li-7 Isotopic Ratio by Means of Thermogravimetric Analysis for Lithium Sulphate Monohydrate

Plutonium concentrations and burnup at Pu spots were calculated in U-Pu mixed oxide (MOX) fuel pellets for light water reactors with the neutron transport and burnup calculation code VIMBURN. The calculation models were suggested for Pu spots and U matrices in a heterogeneous MOX fuel pellet. The calculated Pu concentrations and burnup at Pu spots were compared with the PIEs data in a MOX pellet (38.8 MWd/kgHM). The calculated Pu concentrations agreed by 5–18% with the measured ones, and the calculated burnup did by less than 10% with the estimated one with the measured Nd concentrations. Commercial PWR types of MOX fuels were also analyzed with the calculation code and the models. Burnup at Pu spot increased as the distance was greater from the radial center of a MOX fuel pellet. Burnup at Pu spots in the peripheral region became 3–5 times higher than pellet average burnup of 40 MWd/kgHM. The diameters (20–100 μm) of Pu spots were not found a significant factor for burnup at Pu spots. In the outer half volume region (outer than r/r _o=0.7) of a MOX fuel pellet, burnup at Pu spots exceeded 70MWd/kgHM (the threshold burnup of microstructure change in UO₂ fuel pellet) at pellet average burnup of 1430 MWd/kgHM.     

Development of a Process for Co-Conversion of Pu-U Nitrate Mixed Solutions to Mixed Oxide Powder Using Microwave Heating Method

For the complete nuclear fuel cycle, the development of a process for the co-conversion of Pu-U nitrate mixed solutions to mixed oxide powder has been performed along the line of non-proliferation policy of nuclear materials. A new co-conversion process using a microwave heating method has been developed and successfully demonstrated with good results using the test unit with a capacity of 2 kg MOX/d. Through the experiments and engineering test operations, several important data have been obtained concerning the feasibility of the test unit, powder characteristics and homogeneity of the product, and impurity pickups during denitration process. The results of these experimental operations show that the co-conversion process using a microwave heating method has many excellent advantages, such as good powder characteristics of the product, good homogeneity of Pu-U oxide, simplicity of the process, minimum liquid waste, no possibility of changing the Pu/U ratio and stable operability of the plant. Since August 1979, plutonium nitrate solution transported from the Tokai Reprocessing Plant has been converted to mixed oxide powder which has the Pu/U ratio = 1. The products have been processed to the ATR “FUGEN” reloading fuel. Based on the successful development of the co-conversion process, the microwave heating direct denitration facility with a 10 kg MOX/d capacity has been constructed adjacent to the reprocessing plant. This facility will come into hot operation by the fall of this year. For future development of the microwave heating method, a continuous direct denitration, a vitrification of high active liquid waste and a solidification of the plutonium-contaminated waste are investigated in Power Reactor and Nuclear Fuel Development Corp.     

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.     

Interpretation of actinide transmutation in thermal and fast reactors

The commonly used transmutation rate of minor actinides in nuclear reactors is decomposed into four components, overall fission rate, Pu production rate, MA production rate, and element production rate. The physical meanings of these factors are described. The transmutation rates of minor actinides in two types of highly-moderated PWRs, a MOX fueled Na cooled fast reactor, and a metal fueled Pb cooled fast reactor are interpreted using the four components. The metal fueled Pb cooled fast reactor can incinerate minor actinides most (79kg/GWth/year), and this amount is about 4 times larger than the thermal reactors. The thermal reactors have large relative overall fission rates for ²⁴¹Am and have a potential for the incineration of ²⁴¹Am.     

Utilization of rock-like oxide fuel in the phase-out scenario

Utilization of rock-like oxide (ROX) fuel in light water reactors for plutonium (Pu) burning was studied by nuclear material balance (NMB) analysis for a case of Japanese phase-out scenario under investigation after the Fukushima accident. For the analysis, the NMB code was developed with features of accurate burn-up calculation, flexible combination of reactors and fuels, and an ability to estimate waste and repository. Three scenario groups of once-through Pu burning in mixed oxide (MOX) fuel and in ROX fuel were analyzed. Using two full-MOX or full-ROX reactors the Pu amount is reduced to about one-half and the isotopic vector of Pu deteriorated for being used as a nuclear weapon, especially in terms of spontaneous fission neutron generation. Effects of ROX reactors are more significant than MOX reactors in terms of both reduction in the Pu amount and deterioration of the isotopic vector. Repository footprint and potential radiotoxicity are not reduced by the MOX and ROX reactors because the heat and toxicity of MOX and ROX spent fuels are considerably high.     

氨基羟基脲应用于钚净化浓缩循环

进行了氨基羟基脲(HSC)的硝酸水溶液对30%(体积分数,下同)磷酸三丁酯(TBP)/煤油中高浓度四价钚(Pu(Ⅳ))的还原反萃行为研究,并采用试管串级实验对HSC在钚净化浓缩循环中反萃段工艺进行了验证。结果表明:HSC能有效地实现有机相中高浓Pu(Ⅳ)的反萃;采用13级逆流反萃试管串级实验(还原反萃段10级,补充萃取段3级),对PUREX流程钚净化浓缩反萃段工艺进行了验证,在相比(2BF∶2BX∶2BS)为1∶0.25∶0.15的条件下,Pu的收率为99.99%;钚中去铀的分离因子SF(U/Pu)=3.7×10⁵。HSC作为还原反萃剂,可以实现30%TBP/煤油中高浓度Pu(Ⅳ)的有效反萃,在钚净化浓缩循环工艺中有良好的应用前景。     

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.     

Design of a gadolinia bearing mixed-oxide fuel assembly for pressurized water reactors

A study on neutronics design of a gadolinia (Gd₂O₃) bearing mixed-oxide (MOX) fuel assembly (MOX-UO₂ (Gd₂O₃) assembly) was performed for the purpose of suppressing the use of fresh lumped burnable poison rods (BPRs). The MOX-UO₂ (Gd₂O₃) assembly investigated consists of MOX and UO₂ (Gd₂O₃) fuel rods, which have already been verified through both fabrication and irradiation experiences. In all, 16 UO₂ (10 wt% Gd₂O₃) fuel rods are located at every corner and the peripheral region of the MOX-UO₂ (Gd₂O₃) assembly in order to reduce the power peaking of MOX fuel rods due to the thermal neutron inflow, and to reduce the reactivity penalty at the end of cycle (EOC). Since fresh BPRs are not expected to be inserted and UO₂ (Gd₂O₃) fuel rods are located at every corner of the assembly, the number of splits in plutonium (Pu) content can be only two, which is less than three splits required for a standard MOX assembly. Core characteristics of an equilibrium core loaded with MOX-UO₂ (Gd₂O₃) assemblies are evaluated and it is verified that adoption of the MOX-UO₂ (Gd₂O₃) assembly is effective to avoid the use of fresh BPRs with securing both the core safety and cycle length. The simplication of the splits in Pu content is also supposed to be beneficial, since it has the possibility of reduce MOX fuel fabrication costs.     

Some aspects of risk reduction strategy by multiple recycling in fast burner reactors of the plutonium and minor actinide inventories

This paper shows the impact of recycling light water reactor (LWR) mixed oxide (MOX) fuel in a fast burner reactor on the plutonium (Pu) and minor actinide (MA) inventories and on the related radioactivities. Reprocessing of the targets for multiple recycling will become increasingly difficult as the burnup increases. Multiple recycling of Pu + MA in fast reactors is a feasible option which has to be studied very carefully: the Pu (except the isotopes Pu-238 and Pu-240), Am and Np levels decrease as a function of the recycle number, while the Cm-244 level accumulates and gradually transforms into Cm-245. Long cooling times (10 + 2 years) are necessary with aqueous processing. The paper discusses the problems associated with multiple reprocessing of highly active fuel types and particularly the impact of Pu-238, Am-241 and Cm-244 on the fuel cycle operations. The calculations were performed with the zero-dimensional ORIGEN-2 code. The validity of the results depends on that of the code and its cross-section library. The time span to reduce the initial inventory of Pu + MA by a factor of 10 amounts to 255 years when average burnups are limited to 150 GW · d t⁻¹ (tonne).     

基于MPMS计算模型的PUREX 1B流程模拟研究

为模拟铀钚氧化还原萃取（PUREX）的U/Pu分离流程（简称1B流程）,以多级混合澄清槽为萃取设备,以化学反应体系和经验萃取体系为基础,基于MPMS计算模型框架建立了以NH₃OH+-N₂H₄（HAN-HYD）作为还原萃取剂的1B流程数学模型。通过对比文献数据,验证了模型的有效性。应用该数学模型探究了某低流速高酸洗涤液在特定参数条件下的1B流程中发挥的效应,结果表明该低流速高酸洗涤液的引入会降低U/Pu回收率。为进一步评估不同条件下低流速高酸洗涤液对1B流程分离效率和回收效率的影响,通过改变模型中低流速高酸洗涤液的工艺参数获得不同的U/Pu分离效果。计算结果表明,在不引入低流速高酸洗涤液的条件下,1B流程能获得最优的U/Pu分离效率。该数学模型将为基于多级混合澄清槽的1B流程工艺评估和预测等提供有益帮助。      

Potential reprocessing improvements in the Advanced Fuel Recycle System

From the aspects of economical competitiveness, proliferation resistance, and minimizing waste problems, PNC has proposed an improved recycle concept for the FBR fuel cycle, termed Advanced Fuel Recycle System. Reprocessing in this system is based on the well-known PUREX flowsheet and features a “single cycle Pu/U co-extraction flowsheet” with lower decontamination factor (DF) than that in the conventional process. This feature is practical because of the FBR's low neutronic sensitivity to impurities.

Such a simplified extraction process without purification cycles should substantially reduce not only the number of process components but also the quantities of liquid to be treated in other related processes, so it will lead to the proportional reduction in waste processing, waste itself, and all other related equipments and facilities. This should improve overall economics. One method being examined to further reduce the liquid throughputs and simplify the process is to apply the crystallization technique to dissolver solution.

Overall, with this proposed concept, proliferation resistance will be significantly improved because plutonium is always recovered as a mixture with the uranium and DF of the plutonium product is low.

Reprocessing and fabrication processes are integrated into one fuel cycle plant in this system further contributing to these improvements.     

Design of an overmoderated fuel and a full MOX core for plutonium consumption in boiling water reactors

The use of uranium–plutonium mixed oxide fuel (MOX) in light water reactors (LWR) is nowadays a current practice in several countries. Generally 1/3 of the reactor core is loaded with MOX fuel assemblies and the other 2/3 with uranium assemblies. Nevertheless the plutonium utilization could be more effective if the full core could be loaded with MOX fuel. In this paper the design of a boiling water reactor (BWR) core fully loaded with an overmoderated MOX fuel design is investigated. The design of overmoderated BWR MOX fuel assemblies based on a 10×10 lattice are developed, these designs improve the neutron spectrum and the plutonium consumption rate, compared with standard MOX assemblies. In order to increase the moderator to fuel ratio two approaches are followed: in the first approach, 8 or 12 fuel rods are replaced by water rods in the 10×10 lattice; in the second approach, an 11×11 lattice with 24 water rods is designed with an active fuel length very close to the standard MOX assembly. The results of the depletion behavior and the main steady state core parameters are presented. The feasibility of a full core loaded with the 11×11 overmoderated MOX fuel assembly is verified. This design take advantage of the softer spectrum comparable to the 10×10 lattice with 12 water rods but with thermal limits comparable to the standard MOX fuel assembly.     

New concept of designing Pu and MA containing fuel for fast reactors

New type of metal base fuel element is suggested for fast reactors. Basic approach to fuel element development - separated operations of fabricating uranium meat fuel element and introducing into it Pu or MA dioxides powder, that results in minimizing dust forming operations in fuel element fabrication. According to new fuel element design a framework fuel element having a porous uranium alloy meat is filled with standard PuO₂ powder of <50 μm fractions prepared by pyrochemical or other methods. In this way a high uranium content fuel meat metallurgically bonded to cladding forms a heat conducting framework, pores of which contain PuO₂ powder. Framework fuel element having porous meat is fabricated by capillary impregnation method with the use of Zr eutectic matrix alloys, which provides metallurgical bond between fuel and cladding and protects it from interaction. As compared to MOX fuel the new one features high thermal conductivity, higher uranium content, hence, high conversion ratio does not interact with fuel cladding and is more environmentally clean. Its principle advantage is a simple production process that is easily realized remotely, feasibility of involving high background Pu and MA isotopes into closed nuclear fuel cycle at the minimal influence on environment.     

The prospect of mox fuel based PbBi cooled small nuclear power reactors

Safety performance of MOX fuel based PbBi cooled small fast power reactors has been analyzed and discussed. Though the thermal conductivity of MOX fuel is not large relative to that of nitride or metal fuel, but by proper combination of relatively small power density and relatively large natural circulation it can compensate fuel temperature decrease with coolant temperature increase smartly during unprotected loss of flow accident. Under such condition, accident analysis discussed in this paper show that under unprotected total loss of flow (ULOF) accident the reactor can survive inherently using combination of reactivity feedback. For unprotected rod run out transient over power (UTOP) accident the MOX reactor can overcome external reactivity by smaller power increase compared to that of nitride fueled reactors case. In this case doppler feedback plays much more important role compared to radial expansion component. So the MOX fueled small power reactors discussed here can survive both UTOP and ULOF accident with still enough temperature margin.     

Neutronic performance comparation of MOX, nitride and metallic fuel based 25–100 MWe Pb–Bi cooled long life fast reactors without on-site refuelling

In this paper the performance of 25–100 MWe Pb–Bi cooled long life fast reactors based on three type of fuels: MOX, Nitride and Metal are compared and discussed. In general MOX fuel (UO₂–PuO₂) has lower atomic density compared to the nitride or metal fuel, but MOX fuel has some advantages such as higher Doppler coefficient, high melting point and availability. Nitride fuel has advantages such as high density, high thermal conductivity, and high melting point, but need N-15 to avoid C-14 problems.

The results show that nitride fuel as well as MOX fuel can be used to develop 25–100 MWe (75–300 MWth) Pb–Bi cooled long life reactors without on-site fuelling. The results show that nitride fuels have more superior neutronic characteristics compared to that of MOX fuel due to higher density. However, in the large power level both fuels can be easily applied. In lower power level the MOX fuel need higher fuel volume fraction to reach the comparable target of nitride fuelled cores.