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.     

Dissolution behavior of (U,Zr)O2-based simulated fuel debris in nitric acid

To explore the possibility of dissolving fuel debris into nitric acid as a potential pre-treatment for waste treatment in which the U and Pu are removed from the inventory, dissolution tests of U_1?xZr_xO₂ and (U,Pu)_1?xZr_xO₂ were carried out in 6 M HNO₃ at 353 K. At the end of the dissolution test (after 4 h), the ratio of dissolved uranium decreased with an increase in the Zr contents, x. While the dissolution of U-rich samples was congruent, a preferential leaching of U was observed with Zr-rich samples. Taking into account these different dissolution phenomena, the dissolution rate analysis was carried out using surface-area model to calculate the instantaneous dissolution rate (IDR). The IDR decreased from 10^?5 down to 10^?10 mol cm^?2 min^?1 as x increased from 0 to 0.95. From these findings, dissolution with HNO₃ is expected to be only applicable in U-rich part of fuel debris (x < 0.3) if the dissolution in 6 M HNO₃ at 353 K is assumed. Application of complexing acids, such as mixture of HNO₃ and HF, should be considered to increase the dissolution rate of the Zr-rich part.     

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.     

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.     

Feedback on neutron capture cross sections of 238Pu and 241Am from analyses of measured isotopic compositions of irradiated LWR fuels and MOX core physics experiments

The atomic fractions of ²³⁸Pu and ²⁴¹Am in MOX fuels recycled in light water reactors are 1% to 2% and not significant compared with those of major Pu isotopes. On the other hand, recent evaluated nuclear data libraries, such as JENDL-4.0 and JEFF-3.2, give noticeably different thermal and epithermal neutron capture cross sections for ²³⁸Pu and ²⁴¹Am. The thermal neutron capture cross sections of ²³⁸Pu and ²⁴¹Am in JEFF-3.2 are 31% and 9% larger than those of JENDL-4.0, respectively. This paper shows the effect of the differences in the neutron cross sections on analysis results of two different integral experiments. The first is the isotopic compositions of ²³⁸Pu on UO₂ and MOX fuels irradiated in BWR and PWR, and the second is the critical experiments of the water moderated cores fully loaded with MOX fuels. The former was analyzed by using the continuous energy Monte Carlo burnup calculation code MVP-BURN and the latter by the continuous energy Monte Carlo calculation code MVP. The comparisons between the calculated and measured results indicate that the most likely thermal and epithermal neutron capture cross sections of ²³⁸Pu and ²⁴¹Am should be around at the middle between those of JEFF-3.2 and JENDL-4.0.     

Analysis of Curium in Mixed Oxide Fuel Irradiated in the Experimental Fast Reactor JOYO for the Evaluation of Its Transmutation Behavior

Curium isotopes generated in the MOX fuel irradiated in the experimental fast reactor JOYO were analyzed by applying a sophisticated radiochemical technique. Curium was isolated from the irradiated MOX fuel by anion-ex- change chromatography using a mixed medium of nitric acid and methanol. The isotopic ratio of curium and its content were determined by thermal ionization mass spectroscopy and alpha-spectrometry, respectively. The curium content was less than 0.004 at% even at high burnup of 120GWd/t, which is much smaller than that of PWR-MOX at 60 GWd/t. On the basis of present analytical results, the transmutation behavior of curium isotopes in a fast reactor was discussed from various viewpoints. Transmutation rates of curium isotopes were estimated; the rate for ²⁴⁶Cm, which is known to be a key nuclide in the transmutation of curium, was larger than the previously reported value. It was concluded from these evaluations that the fast reactor was suitable for the incineration of curium.     

Effects of interaction between molten zircaloy and irradiated MOX fuel on the fission product release behavior

As a first step for obtaining experimental data on the effects of high-temperature chemical interaction on fission product release behavior, we focused on the dissolution of irradiated uranium plutonium mixed oxide (MOX) fuel by molten zircaloy (Zry) and carried out a heating test under the reducing atmosphere. Pieces of an irradiated MOX fuel pellet and cladding were subjected to the heating test at 2373 K for five minutes. The fractional release rate of cesium (specifically ¹³⁷Cs) was monitored during the test and its release behavior was evaluated. The observation of microstructures and measurements of elemental distribution in the heated specimen were also performed. We demonstrated experimentally that the fuel dissolution by molten Zry accelerated the release of Cs from the fuel pellets.     

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.     

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.     

An experimental investigation of accumulation and transmutation behavior of americium in the MOX fuel irradiated in a fast reactor

Americium isotopes generated in the MOX fuel irradiated in the experimental fast reactor JOYO were analyzed by applying a sophisticated radiochemical technique. Americium was isolated from the irradiated MOX fuel by a combined method of anion-exchange chromatography and oxidation of Am. The isotopic ratios of americium and its content were determined by thermal ionization mass spectroscopy and α-spectrometry, respectively. The americium isotopic ratio was similar for all the specimens, but was significantly different from that of PWR-MOX. On the basis of present analytical results, the accumulation and transmutation behavior of americium nuclides in a fast reactor is discussed from the viewpoints of neutron spectrum dependence and the isomeric ratio of the ²⁴¹Am capture reaction. The estimated isomeric ratio is about 87%, which is close to the latest evaluated value. A rapid estimation method of Am content by using the ²⁴⁰Pu to ²³⁹Pu ratio was adopted and proved to be valid for the spent fuel irradiated in the fast reactor.     

Estimation of the Grain Boundary Gas Inventory in MIMAS/AUC MOX Fuel and Consistency with REP-Na Test Results

In the frame of its research activities on fuel safety, the French “Institut de Radioprotection et de Sûreté Nucléaire” performed the REP-Na program in the CABRI reactor devoted to the study of Reactivity Initiated Accidents. Focused on high burn-up UO2 and MOX fuel behaviour, twelve tests (8 UO2 and 4 MOX) were realized from 1993 to 2000. In all these tests, the influence of grain boundary gas was evidenced and it appeared necessary to perform some estimation of its inventory in irradiated fuel. Such evaluations are presented for the MOX MIMAS/AUC fuel, based on two different approaches: “experimental” and “theoretical.” The fission gas amount located at the grain boundaries increases with burn-up in correlation with the production, but also with the initial Pu enrichment, as soon as the agglomerates have reached the full restructuring threshold for the High Burn-up Structure. The consistency with the REP-Na test results is checked, showing that a significant cladding deformation is needed, clearly higher than for UO2 fuel in order to release all the grain boundary gas in RIA. Furthermore, to the fission gas effect, adds the helium's occluded in the irradiated fuel whose amount increases with burn-up, Pu enrichment and ²⁴¹Pu and ²⁴¹Am initial content.     

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.     

Numerical Study on Effects of Fuel Mixture Fraction and Li-6 Enrichment on Neutronic Parameters of a Fusion–Fission Hybrid Reactor

This study presents the effects of mixture fractions of nuclear fuels (mixture of fissile–fertile fuels and mixture of two different fertile fuels) and ⁶Li enrichment on the neutronic parameters (the tritium breeding ratio, TBR, the fission rate, FR, the energy multiplication ratio, M, the fissile breeding rate, FBR, the neutron leakage out of blanket, L, and the peak-to-average fission power density ratio, Γ) of a deuterium–tritium (D–T) fusion neutron-driven hybrid blanket. Three different fertile fuels (²³²Th, ²³⁸U and ²⁴⁴Cm), and one fissile fuel (²³⁵U) were selected as the nuclear fuel. Two different coolants (pressurized helium and natural lithium) were used for the nuclear heat transfer out of the fuel zone (FZ). The Boltzmann transport equation was solved numerically for obtaining the neutronic parameters with the help of the neutron transport code XSDRNPM/SCALE4.4a. In addition, these calculations were performed by also using the MCNP4B code. The sub-limits of the mixture fractions and ⁶Li enrichment were determined for the tritium self-sufficiency. The considered hybrid reactor can be operated in a self-sufficiency mode in the cases with the fuel mixtures mixed with a fraction of equal to or greater than these sub-limits. Furthermore, the numerical results show that the fissile fuel breeding and fission potentials of the blankets with the helium coolant are higher than with the lithium coolant.     

Application of Multiband Method to Pin Cell Calculations

Abstract

In order to accurately calculate effective neutron cross sections in the resonance energy region, the multiband method has been applied to cell calculations. Cell calculations for UO² and MOX fuels of light water reactors have been performed and the results were compared with those of a continuous energy Monte Carlo code VIM and the conventional self-shielding method using the Dancoff factor.

The k∞values calculated by the multiband method agreed with those of the VIM calculations within 0.20% Δk for the UO² fuel cell and within 0.30% Δk for the MOX fuel cell, respectively, whereas the Dancoff factor method yielded about l.l%Δk errors for the two cells. The element- wise contribution to this error was investigated, and it was found that the effective microscopic cross sections, particularly those for the giant resonances of ²³⁸U, calculated by the multiband method were in good agreement with those of VIM. It was also found that interference effect between ²³⁸U and ²³⁵U resonances in the UO² fuel and that between ²³⁸U and ²³⁹Pu resonances in the MOX fuel made about 0.20%Δk contributions to k∞ in both fuel cells.     

ADAGIO technique: From UO2 fuels to MOX fuels

The amount of gas at the grain boundaries plays an important role in the fuel transient behaviour during accident conditions, such as a loss-of-coolant accident (LOCA) or a reactivity-initiated accident (RIA). Direct experimental determination of the grain boundary gas inventory has been performed for MOX fuel irradiated in an EDF pressurised water reactor (PWR) using the ADAGIO technique (ADAGIO is a French acronym meaning ‘Discriminatory Analysis of Accumulated Inter-granular and Occluded Gas’). The ADAGIO protocol applied to a MOX MIMAS fuel produced inter-granular gas fraction results that were consistent with those reached with other methods of evaluation i.e. electron probe microanalysis (EPMA). Furthermore, a new methodology for the numerical treatment of ⁸⁵Kr release kinetics which was developed for UO₂ was applied to MOX fuels. The corresponding results evidenced two types of release kinetics. These kinetics were attributed to the inter-granular bubbles of the UO₂ matrix and the bubbles located in the restructured zones, i.e. Pu agglomerates.     

A neutronic evaluation of the (Pu–U) and (Am–Pu–U) insertion in a typical fuel of Angra-I

The goal is to evaluate the neutronic behavior when (Pu–U) and (Am–Pu–U) mixed oxide are inserted in a typical cell of a Pressurized Water Reactor (PWR) such as Angra-I. Four types of fuels were studied: (1) MOX fuel enriched at 3.1% and V_m/V_f = 1.15; (2) MOX fuel enriched at 4.5% and V_m/V_f = 1.15; (3) MOX fuel enriched at 4.5% and V_m/V_f = 2.0 and (4) MOX fuel enriched at 4.5%, with 1% of Americium insertion in its composition (62.8% of Am²⁴¹, 0.1% of Am^242m and 37.1% of Am²⁴³) and with V_m/V_f = 2.0. The first case represents the standard state of Angra I, but with Pu. The second case is similar to the first but the enrichment is increased. To evaluate the Americium insertion, a study of the V_m/V_f was made and better results were obtained with V_m/V_f = 2.0 and to compare, this case was too evaluated to (Pu–U) in the third and fourth cases. The idea is to verify the possibility of using these fuels in Angra-I analyzing neutronic parameters such as infinite multiplication factor, hardening spectrum, Boron worth and reactivity temperature coefficients. The results show that it is possible to use all the studied fuels in Angra-I as well as to burn Am inserted in the MOX fuel by a considerable quantity during PWR operation. The WIMS-D5 code was used to perform a simplified neutronic and burnup simulations to evaluate this possibility.     

Neutronics and material attractiveness for PWR thorium systems using monte carlo techniques

Thorium (Th) oxide fuel offers a significant advantage over traditional low-enriched uranium and mixed uranium/plutonium oxide (MOX) fuel irradiated in a Light Water Reactor. The benefits of using thorium include the following: 1) unlike depleted uranium, thorium does not produce plutonium, 2) thorium is a more stable fuel material chemically than LEU and may withstand higher burnups, 3) the materials attractiveness of plutonium in Th/Pu fuel at high burnups is lower than in MOX at currently achievable burnups, and 4) thorium is three to four times more abundant than uranium. This paper quantifies the irradiation of thorium fuel in existing Light Water Reactors in terms of: 1) the percentage of plutonium destroyed, 2) reactivity safety parameters, and 3) material attractiveness of the final uranium and plutonium products. The Monte Carlo codes MCNP/X and the linkage code Monteburns were used for the calculations in this document, which is one of the first applications of full core Monte Carlo burnup calculations. Results of reactivity safety parameters are compared to deterministic solutions that are more traditionally used for full core computations.Thorium is fertile and leads to production of the fissile isotope ²³³U, but it must be mixed with enriched uranium or reactor-/weapons-grade plutonium initially to provide power until enough ²³³U builds in. One proposed fuel type, a thorium-plutonium mixture, is advantageous because it would destroy a significant fraction of existing plutonium while avoiding the creation of new plutonium. ²³³U has a lower delayed neutron fraction than ²³⁵U and acts kinetically similar to ²³⁹Pu built in from ²³⁸U. However, as with MOX fuel, some design changes may be required for our current LWR fleet to burn more than one-third a core of Th/Pu fuel and satisfy reactivity safety limits. The calculations performed in this research show that thorium/plutonium fuel can destroy up to 70% of the original plutonium per pass at 47 GWd/MTU, whereas only about 30% can be destroyed using MOX. Additionally, the materials attractiveness of the final plutonium product of irradiated plutonium/thorium fuel is significantly reduced if high burnups (∼94 GWD/MTU) of the fuel can be attained.     

Corrosion of irradiated MOX fuel in presence of dissolved H2

The corrosion behaviour of irradiated MOX fuel (47 GWd/tHM) has been studied in an autoclave experiment simulating repository conditions. Fuel fragments were corroded at room temperature in a 10 mM NaCl/2 mM NaHCO₃ solution in presence of dissolved H₂ for 2100 days. The results show that dissolved H₂ in concentration 1 mM and higher inhibits oxidation and dissolution of the fragments. Stable U and Pu concentrations were measured at 7 × 10⁻¹⁰ and 5 × 10⁻¹¹ M, respectively. Caesium was only released during the first two years of the experiment. The results indicate that the UO₂ matrix of a spent MOX fuel is the main contributor to the measured dissolution, while the corrosion of the high burn-up Pu-rich islands appears negligible.     

A Method for Determination of Plutonium in Blood by Anion Exchange

The anion exchange behavior of Pu(IV) and Pu(VI) were studied in solutions of both nitric acid and of ethanol-nitric acid mixture, and a method of determining plutonium content in blood was developed. About 10 ml of blood were wet-incinerated with concentrated nitric acid and evaporated to dryness. The residue was dissolved in 8 ml of 8 N nitric acid, and 12 ml of ethanol was added. The solution was passed through a resin column of Dowex 2, X8 (9 mm diam., 3.0cm long). After washing the column with ethanol-nitric acid mixed solution, plutonium was eluted with 10 ml of 1N nitric acid containing sulfur dioxide. The eluate was transferred to a cell for electrodeposition, which was carried out with 500 mA/cm² for 3 hr using a stainless steel disk as cathode.

The plutonium yield from the ion exchange was 85~91%, and the electrodeposition quantitative. The blank activity from the reagents, resin and disk was 10^?14Ci. With this method a 10-hr count with silicone semiconductor spectrometer, will permit determination of 5 × 10^?14 10^?13Ci of plutonium in 10 ml of blood.