Experimental study on elemental behaviors in fluorination of nuclear spent fuel with flame reactor

Our proposed spent nuclear fuel reprocessing technology named FLUOREX is a hybrid system based on reprocessing technologies of fluorination and solvent extraction for light water reactor fuel. In the current research, we experimentally clarified solid–gas transfer behaviours of the fluorides in the FLUOREX process and identified the volatile and non-volatile compounds in the fluorination. We carried out a fluorination experiment for simulated spent nuclear fuel and solid separation from the UF₆ gas stream. The distribution ratios of fission product elements in the experimental apparatus were evaluated. Molybdenum, Te, Nb, and Ru were volatilized by fluorination and they accompanied the UF₆ gas. However, 22.9% of the Ru and 3.4% of the Nb were retained as solids in the experimental apparatus, contrary to the fact that their partial pressures in the experiment were lower than their vapor pressures. Rubidium, Sr, Zr, Ce, and Nd were completely recovered as solid fluorides, and these results agreed with the prediction based on boiling points of their fluorides. Antimony was completely recovered as a solid; nevertheless, the boiling point of antimony pentafluoride was lower than the process temperature, and that was attributed to the formation of a non-volatile antimony oxyfluoride.     

Estimation of Spent Fuel Compositions from Light Water Reactors

The compositions and quantities of minor actinide (MA) and fission product (FP) in spent fuels will be diversified with the use of high discharged burnup fuels and MOX fuels in LWRs which will be a main part of power reactors in future.

In order to investigate above diversities, we have studied on the calculation method to be used in the estimation of spent fuel compositions and adopted the real irradiation calculation in which axial burnup and moderator distribution are considered in the burnup calculation.

On the basis of the calculations, compositions and burnup quantities of various LWR spent fuels (reactor type: PWR and BWR, discharged burnup: 33, 45 and 60 GWd/tHM, fuel type: U0₂ and MOX) are apparently estimated among various forms of fuels. As an example, it is shown that there are considerable discrepancy in MA burnup between PWR and BWR spent fuels.     

MOX Co-deposition Tests at RIAR for SF Reprocessing Optimization

The Oxide Electrowinning method has been studied as one of the candidate dry reprocessing concepts of the future fuel cycle systems. On the MOX co-deposition process, the main process of that method, some fundamental experiments have been performed to confirm its feasibility. In the experiments, several parameters were set to study the suitable electrolysis condition to obtain desired granule of MOX. The concentrations of uranium, plutonium, fission products(FP) simulators, and corrosion products(CP) simulators were adopted as the parameters. The blowing gas composition (O₂, Cl₂, Ar) during the electrolysis was also set as the variable condition. Through these experiments, it was clarified that the partial pressure of chlorine gas during electrolysis was important to obtain MOX granule with high Pu concentration (about 30%) without generating bottom precipitation in melt. Finally, adequacy of the process control method for MOX co-electrolysis was confirmed through the test using spent fast reactor(FR) fuel.     

Adsorption of Molybdenum Hexafluoride on Magnesium Difluoride for Uranium Purification in FLUOREX Reprocessing

The nuclear fuel reprocessing method FLUOREX is a hybrid system based on fluoride volatility and using solvent extraction. Spent nuclear fuel is fluorinated, and most of the uranium is recovered as UF₆ gas. UF₆ contains some volatile fission product (FP) fluorides, so we considered their elimination from UF₆ by adsorbing them on fluoride adsorbents. We experimentally examined the adsorption of MoF₆ on MgF₂ adsorbent; MoF₆ is present as a volatile FP fluoride in UF₆ produced by the fluorination of spent nuclear fuel. The adsorption isotherm of MoF₆ adsorption on MgF₂ was obtained at MoF₆ pressures from 10^?4 to 50 kPa. The saturated adsorption amount was 1:3 ± 0:4 mg/m² at MoF₆ pressures from 10^?4 to 1 kPa. At MoF₆ pressure of about 10^?3 kPa, the saturated adsorption amount had no dependence on adsorption temperatures from 398 to 463 K. We deduced that MoF₆ was adsorbed as a monomolecule layer on the MgF₂ surface at MoF₆ pressures from 10^?4 to 1 kPa, and the MoF₆ partial pressure in UF₆ could be decreased below 1 × 10^?4 kPa, which is the specific MoF₆ concentration for the reenrichment process.     

Fundamental Study of the Sulfide Reprocessing Process for Oxide Fuel (I) Study on the Pu,MA and FP Tracer-Doped U3O8

For the recovery of fuel materials from spent nuclear fuel, a novel reprocessing process based on the selective sulfurization of fission products (FP) has been proposed, where FP and minor actinides (MA) are first sulfurized by CS₂ gas, and then, dissolved by a dilute nitric acid solution. Consequently, the fuel elements are recovered as UO₂ and PuO₂. As a basic research of this new concept, the sulfurization and dissolution behaviors of U, Pu, Np, Am, Eu, Cs, and Sr were investigated by γ-ray and α spectrometries in this paper using ²³⁶Pu-, ²³⁷Np-, ²⁴¹Am-, ¹⁵²Eu-, ¹³⁷Cs-, and ⁸⁵Sr-doped U₃O₈ samples. The dependence of the dissolution ratio of each element on the sulfurization temperature was studied and reasonably explained by combining the information of the sulfide phase analysis and the chemical thermodynamics of the dissolution reaction. The sulfurization temperature ranging from 350 to 450°C seems to be promising for the separation of FP and MA from U and Pu, since a clear difference in the dissolution ratio between FP and U was derived by the sulfurization treatment in this temperature range.     

Burning of MOX fuels in LWRs; fuel history effects on thermal properties of hull and end piece wastes and the repository performance

The thermal impacts of hull and end piece wastes from the reprocessing of MOX spent fuels burned in LWRs on repository performance were investigated. The heat generation rates in MOX spent fuels and the resulting heat generation rates in hull and end piece wastes change depending on the history of MOX fuels. This history includes the burn-up of UO₂ spent fuels from which the Pu is obtained, the cooling period before reprocessing, the storage period of fresh MOX fuels before being loaded into an LWR, as well as the burn-up of the MOX fuels. The heat generation rates in hull and end piece wastes from the reprocessing of MOX spent fuels with any of those histories are significantly larger than those from UO₂ spent fuels with burn-ups of 45 GWd/THM. If a temperature below 80°C is specified for cement-based materials used in waste packages after disposal, the allowable number of canisters containing compacted hull and end pieces in a package for 45 and 70 GWd-MOX needs to be limited to a value of 0.4–1.6, which is significantly lower than 4.0 for 45 GWd-UO₂.     

Core concept of compound process fuel cycle

This paper presents fast reactor core concept and its feasibility as a part of newly proposed compound process fuel cycle in which spent fuels of light water reactor are multi-recycled without conventional reprocessing but with only pyrochemical processing, fuel re-fabrication and reloading to the fast reactor core. Results of the core survey analyses in order to find out the feasibility of this concept, taking example for BWR MOX spent fuel of 60 GWd/t burn-up, show that four times recycling of LWR spent fuel with the burn-up of more than 300 GWd/t can be achieved without increasing MA content. Such benefits will be expected in this concept as reduction of fuel cycle cost due to simplified reprocessing procedure, reduction of environmental impacts due to reduced high level waste, efficient utilization of nuclear fuel resources, enhancement of nuclear non-proliferation, and suppression of LWR spent fuel pile-up.     

Core characteristics of fast reactor cycle with simple dry pyrochemical processing

Fast reactor core concept and core nuclear characteristics are studied for the application of the simple dry pyrochemical processing for fast reactor mixed oxide spent fuels, that is, the Compound Process Fuel Cycle, large FR core with half of loaded fuels are recycled by the simple dry pyrochemical processing. Results of the core nuclear analyses show that it is possible to recycle FR spent fuel once and to have 1.01 of breeding ratio without radial blanket region. The comparison is made among three kinds of recycle fuels, LWR UO₂ spent fuel, LWR MOX spent fuel, and FR spent fuel. The recycle fuels reach an equilibrium state after recycles regardless of their starting heavy metal compositions, and the recycled FR fuel has the lowest radio-activity and the same level of heat generation among the recycle fuels. Therefore, the compound process fuel cycle has flexibility to recycle both LWR spent fuel and FR spent fuel. The concept has a possibility of enhancement of nuclear non-proliferation and process simplification of fuel cycle.     

Radiotoxicity hazard of U-free PuO2+ZrO2 and PuO2+ThO2 spent fuels in LWR

The radiotoxicity hazard of U-free Rock-like oxide: ROX (PuO₂+ZrO₂) and Thorium oxide: TOX (PuO₂+ThO₂) LWR spent fuels is investigated and radiotoxicity hazard of MOX spent fuel is considered as a reference case. The long-term ingestion radiotoxicity hazard of ROX spent fuel is one third and nearly one fourth of that of TOX and MOX spent fuels, respectively. This is because the discharged Pu and long lived Np in ROX fuel is less than that of TOX and MOX fuels. In TOX fuel, discharged Pu and MA are lower than that of MOX fuel but the long-term radiotoxicity hazard of spent fuel is nearly the same as MOX spent fuel. At the cooling 10⁵ years, the radiotoxicity hazard of TOX spent fuel is approximately ten and three times higher than that of ROX and MOX spent fuels, respectively due to higher toxic contribution of ²²⁹Th in TOX spent fuel.     

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.     

Releases of Cesium and Poorly Volatile Elements from UO2 and MOX Fuels under Severe Accident Conditions

Radionuclide release from fuel under severe accident conditions has been investigated in the VEGA program at the Japan Atomic Energy Agency. In this program, three types of fuel, two UO₂ fuels irradiated at PWR and BWR and a MOX fuel irradiated at the ATR Fugen, were heated up to about 3130K in helium atmosphere at 0.1 MPa. Comparison of experimental data and evaluation with computer code analyses showed that Cs release is essentially identical among the three fuels. The Cs release from fuel may differ below about 1770K due to a difference in migration to grain boundaries during irradiation. The difference was not also observed for releases of poorly volatile elements, namely, U, Pu, Sr and Mo between UO₂ and MOX fuels. The release rate of Pu became slightly higher than that of U at 3130 K. The release rate of Sr increased at 3130 K, while that of Mo was quite low at temperatures above 2310 K.     

Parametric Survey for Benefit of Partitioning and Transmutation Technology in Terms of High-level Radioactive Waste Disposal

Benefit of implementing Partitioning and Transmutation (P&T) technology was parametrically surveyed in terms of high-level radioactive waste (HLW) disposal by discussing possible reduction of the geological repository area. First, the amount and characteristics of HLWs caused from UO₂ and MOX spent fuels of light-water reactors (LWR) were evaluated for various reprocessing schemes and cooling periods. The emplacement area in the repository site required for the disposal of these HLWs was then estimated with considering the temperature constrain in the repository. The results showed that, by recycling minor actinides (MA), the emplacement area could be reduced by 17–29% in the case of UO₂-LWR and by 63–85% in the case of MOX-LWR in comparison with the conventional PUREX reprocessing. This significant impact in MOX fuel was caused by the recycle of 241Am which was a long-term heat source. Further 70–80% reduction of the emplacement area in comparison with the MA-recovery case could be expected by partitioning the fission products (FP) into several groups for both fuel types. To achieve this benefit of P&T, however, it is necessary to confirm the engineering feasibility of these unconventional disposal concepts.     

Development of hybrid reprocessing technology based on solvent extraction and pyro-chemical electrolysis

Toshiba has been proposing a new fuel cycle concept for the transition period from Light Water Reactors (LWRs) to Fast Reactors (FRs). This concept involves a more valuable process for LWR spent-fuel reprocessing than the conventional process and improved proliferation resistance. We have been developing a new technology, the Toshiba Hybrid Reprocessing Process, based on solvent extraction and pyro-chemical electrolysis, for spent fuel reprocessing for the transition period from LWRs to FRs. The Toshiba Hybrid Reprocessing Process combines the solvent extraction process of the LWR spent fuel in nitric acid with the recovery of high-purity uranium (U) and the pyro-chemical process in molten salts for recovery of impure plutonium with minor actinides (Pu + MA). High-purity U is used for LWR fuel, and impure Pu + MA is used for metallic FR fuel. Valence control by the electrolysis and solvent extraction tests using LWR spent fuel and oxalate precipitation tests were carried out to confirm the feasibility of the Toshiba Hybrid Reprocessing Process. A consecutive processing equipment for the solvent extraction process and a bench-scale apparatus for the pyro-chemical process were manufactured. The consecutive processing equipment consists of a flow type electrolytic cell and a centrifugal extractor. The test revealed that U of 99.99% of purity was recovered. The bench-scale apparatus consists of a reactor for oxalate precipitation, a solid-liquid separator in which nitric acid with fission products and precipitation are separated, and a drying equipment in which the precipitation is dry. Precipitation test with neodymium (Nd) which is simulated as Pu + MA in nitric acid was carried out. It was confirmed that precipitation ratio of Nd was more than 99.9% and that moisture ratio of the precipitation was less than 10%. The results suggested that U recovery of LWR spent fuel was 99.99% with the consecutive processing equipment and Pu + MA recovery was more than 99.9% with the bench-scale apparatus. The Toshiba Hybrid Reprocessing Process could recover high-purity U used for LWR fuel, and impure Pu + MA used for metallic FR fuel.     

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).     

高温气冷堆和轻水堆超铀元素管理特性研究

乏燃料中长寿命锕系元素对环境造成长期潜在危害,本文研究球床高温气冷堆不同燃料循环中超铀元素的产生和焚烧特性。在250 MW球床模块式高温气冷堆示范电站HTR-PM铀钚循环的乏燃料中提取铀和钚作为核燃料,设计了PuO₂和MOX燃料元件,将新设计的燃料元件重新装入与HTR-PM相同结构和尺寸的堆芯,分别形成纯钚燃料循环和MOX燃料循环。采用高温气冷堆物理设计程序VSOP,研究了高温气冷堆一次通过燃料循环和不同闭式燃料循环的超铀元素焚烧特性,并与轻水堆燃料循环结果进行比较和分析。结果表明：高温气冷堆一次通过燃料循环超铀元素生成率约为轻水堆的1/2;高温气冷堆闭式燃料循环能有效嬗变超铀元素。     

Analysis of measured isotopic compositions by CASMO5 coupled with a JENDL-4.0 base library for irradiated fuel of light water reactors

Measured isotopic compositions of UO₂ and MOX fuel samples taken from irradiated light water reactor fuel assemblies were analyzed by CASMO5 coupled with a JENDL-4.0 base library to assess the uncertainties in the calculated isotopic compositions on heavy and fission product nuclides. The burnup calculations for the analysis were performed based on a single-assembly model taking into account the detail fuel assembly specifications and irradiation histories. For the MOX fuel samples, a multiple-assembly model was also adopted taking into account the effect of the surrounding UO₂ fuel assemblies. The average and standard deviation of the biases (C/E ? 1's (here C and E are calculated and measured results, respectively)) were calculated for each nuclide separately on the PWR and BWR UO₂ fuel samples. The averaged biases for ²³⁵U, ²³⁶U, ²³⁹Pu, ²⁴⁰Pu, ²⁴¹Pu and ²⁴²Pu were 2.7%, ?0.9%, 0.3%, 0.7%, ?2.4% and ?1.7% for PWR UO₂ samples, and 6.7%, ?1.5%, 2.5%, ?0.6%, 0.4% and ?0.1% for BWR UO₂ samples, respectively. The biases with the single-assembly model on the MOX fuel samples showed large positive values of ²³⁹Pu, and application of the multiple-assembly model reduced the biases as reported in our previous studies.     

Waste disposal aspects of the long term cooling characteristics of irradiated nuclear fuels

A study has been made of the long term cooling characteristics of nuclear fuels irradiated in commercial reactor designs of interest within the U.K. In the case of thermal reactors, Magnox, AGR, SGHWR, LWR and HTR systems fuelled with either natural or enriched uranium are considered, together with a fast reactor fuelled with plutonium derived either from the Magnox or the AGR programmes. Alternative uses for Magnox plutonium are considered by simulating a plutonium fuelled HTR thermal system and the development of a $\text{Th}{}^{233}\text{U}$ fuel cycle has been anticipated for both a fast reactor and an HTR.For each system the activities as a function of cooling time are considered on the assumption of U/Pu recovery from the fuel during reprocessing within a year of discharge from the reactor and for the alternative case of no U/Pu extraction. The reprocessing waste products associated with the various fuel cycles have then been compared both on the basis of decay heating and radiological hazard per GW(e) yr. Finally, recycling of transplutonium elements is also considered with a view to reducing the long term heating commitment from the higher actinides.     

Analysis of measured isotopic compositions of high-burnup PWR MOX and UO2 fuels in the MALIBU program

The measured isotopic compositions of fuel samples taken from high-burnup spent PWR MOX and UO₂ assemblies in the MALIBU program has been analyzed by lattice physics codes. The measured isotopes were U, Np, Pu, Am, and Cm isotopes and about 30 major fission product nuclides. The codes used in the present study were a continuous-energy Monte Carlo burnup calculation code (MVP-BURN) and a deterministic burnup calculation code (SRAC) based on the collision probability method. A two-dimensional multi-assembly geometrical model (2 × 2 model) was mainly adopted in the analysis in order to include the fuel assemblies adjoining the relevant fuel assembly, from which the samples were taken. For the MOX sample, the 2 × 2 model significantly reduces the deviations of the calculated results from the measurements compared with a single assembly model. The calculation results of MVP-BURN in the 2 × 2 model reproduce the measurements of U, Np, and Pu isotopes within 5% for the MOX sample of 67 GWd/t. The deviations of their calculated results of U, Np, and Pu isotopes from the measurements are less than 7% for the UO₂ sample of 72 GWd/t.     

Thermal conductivity degradation analyses of LWR MOX fuel by the quasi-two phase material model

The temperature measurements of mixed oxide (MOX) and UO₂ fuels during irradiation suggested that the thermal conductivity degradation rate of the MOX fuel with burnup should be slower than that of the UO₂ fuel. In order to explain the difference of the degradation rates, the quasi-two phase material model is proposed to assess the thermal conductivity degradation of the MIMAS MOX fuel, which takes into account the Pu agglomerate distributions in the MOX fuel matrix as fabricated. As a result, the quasi-two phase model calculation shows the gradual increase of the difference with burnup and may expect more than 10% higher thermal conductivity values around 75 GWd/t. While these results are not fully suitable for thermal conductivity degradation models implemented by some industrial fuel manufacturers, they are consistent with the results from the irradiation tests and indicate that the inhomogeneity of Pu content in the MOX fuel can be one of the major reasons for the moderation of the thermal conductivity degradation of the MOX fuel.     

Recycling of uranium from spent RBMK fuel in the nuclear fuel cycle

It is shown that there is promise in using the uranium product obtained by reprocessing spent nuclear fuel from RBMK reactors as a non-initial fuel source for thermal reactors. A technical path for spent nuclear fuel from RBMK reactors is proposed: radiochemical reprocessing and obtaining oxides of recycled uranium. Oxides of the category RBMK-poor are packed and then stored in a near-surface storage facility; oxides of the category RBMK-rich are fluoridated, and UF₆ is fed into separation production for additional enrichment to the required content of ²³⁵U. Additional advantages of recycled RBMK uranium as a source of non-initial ²³⁵U are the low content of ²³²U and the relatively low activity of spent fuel, which simplifies its reprocessing.