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Potential Research and Development Opportunities for Light Water Reactor Spent Nuclear Fuel at INL

This report documents the commercial spent nuclear fuel currently in storage at Idaho National Laboratory with a specific focus on the potential research and development (R&D) opportunities for this material. Commercial spent nuclear fuel is stored in dry casks on the INL site at the Idaho Nuclear Technology and Engineering Center (INTEC, formerly the Idaho Chemical Processing Plant or ICPP). This spent fuel was part of the DOE-industry cooperative dry cask demonstration project that began in 1983 and from historical fuel testing and treatment activities that had been performed at the Test Area North (TAN)-607 facility. Most of the fuel is “low burnup,” but given that it was removed from the respective reactors between 1970 and 1985, it was representative for its time. The majority of the fuel is of the 15×15 Westinghouse PWR variety, though additional fuel types (e.g., TN-BRP) and configurations are also stored. Potential R&D opportunities identified are (1) the REA-2023 cask, (2) the TN-BRP cask, and (3) the Castor V/21 cask. Fuel from the TN-24P may be an alternative to the intact assemblies in the Castor V/21. Specifically, the REA-2023 cask contains 9 rods that have been exposed to air since 2005. These rods have a detailed pre-loading characterization and thus any changes in corrosion or geometry can most likely be attributed to the storage environment. In addition, similar rods to the nine in REA-2023 reside in the Castor V/21 cask whose environment has been maintained with inert nitrogen. The Castor V/21 cask also contains intact PWR assemblies that could be used to perform limited confirmation of the pyroprocessing approach. An alternative to the use of the Castor assemblies for pyroprocessing is the consolidated fuel that is stored in the TN-24P, which would not require removal from the assembly grid since it has already been packaged in accessible two-piece shell strongback containers. The TN-BRP cask contains a number of Gd-doped, low burnup assemblies that could be of use to validate code packages used to justify burnup-up credit for boiling water reactors (BWRs). The INL dry casks are stored on the CPP-2707 pad at INTEC, adjacent to the CPP-603 Irradiated Fuel Storage Facility, which incorporates a dry hot cell that has the potential to receive a full scale commercial cask of the types identified. Several evaluations have been made regarding this task, including full scale mockup testing of the physical clearances required to remove and handle fuel assemblies and components. A proposed schedule of 14 months and cost of $5.3 million was the outcome of analysis performed by Fluor Idaho and is included as Appendix A & B. In addition to the spent fuel at INL, there is also a full-scale mockup assembly that was fabricated for the Protypical Consolidation Demonstration Project to validate fuel rod consolidation approaches. The assembly was fabricated by Westinghouse as a 15 x 15 PWR, using Zircaloy-4 tubing and steel end fittings in accordance with product specifications. The only departure from specification is the use of copper metal in lieu of uranium oxide pellets to achieve a weight that is within 10% of the standard.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Operation of Argonne's Liquid Salt-Liquid Metal Separation Testbed for U/TRU Product Processing

Argonne National Laboratory has constructed a liquid salt-liquid metal separation testbed for use in the development and advancement of cathode processing of U/TRU co‑deposits generated by pyroprocessing of used nuclear fuel. The U/TRU product recovered from the electrorefiner contains adhered and entrained salt that must be removed prior to consolidation of the U/TRU alloy for use in advanced reactor fuel fabrication. The bottom pour operation utilizes the low melting points of U/TRU co‑deposits and higher densities of molten metals compared to molten salts to separate and consolidate the U/TRU product. Argonne’s testbed is designed to support the development and optimization of bottom-pouring configurations for batch and semi-continuous operations, integration of process monitoring and control technologies, and determination of operational requirements for implementing in an industrial setting. Scoping tests were performed to demonstrate operational aspects of the testbed, including operation using single-pour spout and dual-pour spout configurations, effectiveness of salt containment and extent of salt vaporization, and the use of sensor probes to detect the location of the interface between the metal and salt phases during pouring. Recommendations for process optimization testing for further development of bottom pour processing to separate U/TRU alloys from adhered salt were made based on the results of scoping tests. Completing the recommended activities will increase the technical readiness level (TRL) of the liquid salt-liquid metal separation operation and consolidation of U/TRU alloys to support industrialization of pyroprocessing.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Experiments in anodic film effects during electrorefining of scrap U-10Mo fuels in support of modeling efforts

A monolithic uranium molybdenum alloy clad in zirconium has been proposed as a low enriched uranium (LEU) fuel option for research and test reactors, as part of the Reduced Enrichment for Research and Test Reactors program. Scrap from the fuel's manufacture will contain a significant portion of recoverable LEU. Pyroprocessing has been identified as an option to perform this recovery. A model of a pyroprocessing recovery procedure has been developed to assist in refining the LEU recovery process and designing the facility. Corrosion theory and a two mechanism transport model were implemented on a Mat-Lab platform to perform the modeling. In developing this model, improved anodic behavior prediction became necessary since a dense uranium-rich salt film was observed at the anode surface during electrorefining experiments. Experiments were conducted on uranium metal to determine the film's character and the conditions under which it forms. The electro-refiner salt used in all the experiments was eutectic LiCl/KCl containing UCl{sub 3}. The anodic film material was analyzed with ICP-OES to determine its composition. Both cyclic voltammetry and potentiodynamic scans were conducted at operating temperatures between 475 and 575 C. degrees to interrogate the electrochemical behavior of the uranium. The results show that an anodic film was produced on the uranium electrode. The film initially passivated the surface of the uranium on the working electrode. At high over potentials after a trans-passive region, the current observed was nearly equal to the current observed at the initial active level. Analytical results support the presence of K{sub 2}UCl{sub 6} at the uranium surface, within the error of the analytical method.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Multi-species Modeling of Molten-Salt Electrochemical Process

Spent nuclear fuel has been produced and stored in over 30 different countries which are operating commercial nuclear power plants. Molten-salt pyroprocessing has been developed for treating both oxide and metal spent nuclear fuels. This process separates long-lived actinide isotopes together as a group from fission products for burning the long-lived isotopes in fast reactors. Main processes of pyroprocessing such as oxide reduction, electrorefining, and electrowinning are based on a concept of electrolytic cell consuming energy to proceed electrochemical reactions. To scale-up the electrochemical processes, the design optimization of the key steps is required to reach high throughput that improves economic competitiveness and reduces an environmental impact. For the optimization, it is significant to compare different unit process designs and find optimum designs and operating conditions. However, this optimization process is very costly if we need to conduct experiments on every case with spent nuclear fuel. Instead, a validated simulation model can help to rapidly calculate and evaluate different case at significantly reduced costs. This paper presents recent development of multi-physics simulation of molten salt electrochemistry for partitioning spent nuclear fuel with limiting factors. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Shielding an Infrasound Sensor for INL’s Fuel Conditioning Facility

Idaho National Laboratory (INL) has been pyroprocessing spent fuel from the Experimental Breeder Reactor II (EBR-II). This process occurs in the Fuel Conditioning Facility (FCF) which houses the treatment of DOE-owned sodium-bonded metal fuel. The electrometallurgical methods used in FCF treat the spent fuel from EBR-II for recycling of the uranium. The radiation field present inside FCF throughout the pyroprocessing stages affects any electronic sensors and devices that may be used for research. An example of such device is a seismoacoustic sensor which detects sound and vibration waves from the equipment in the facility. Seismoacoustic sensors are of interest to research nonproliferation techniques.

46 - INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AN↗

Chemical Understanding of Actinide Separations

This work provides a broad overview of the separation processes used to isolate actinides and the experimentally and computationally determined chemical characteristics that define those separations. The redox chemistry of the actinides plays a pivotal role in both aqueous and pyrochemical processing separations. The near-overlapping energies of the 6d and 5f orbitals in the light actinides allow for facile adjustment of actinide oxidation states, which is used in many established separation methods. In contrast, the stable, generally 3+ oxidation states of the mid- and heavy actinides can make it difficult to separate them from the similarly lanthanides(III). In aqueous separations, the tendency of the actinides to form anionic and neutral aqueous complexes with a variety of complexants (especially soft donors) is used to achieve high separation factors between chemically similar elements in both solid–liquid separations and liquid–liquid extraction. This selectivity can be further tuned through the use of specialized organic or solid-phase ligands. Pyroprocessing separations utilize the unique redox behavior of the actinides to adjust their distribution between a molten salt electrolyte and either a solid electrode or molten metal phase. Atomic-level insights into the mechanisms underlying actinide separation processes, with the ultimate goal of predicting separation behavior, can be provided by electronic structure and statistical mechanical-based calculation methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spectroelectrochemistry of EuCl 3 in Four Molten Salt Eutectics; 3 LiCl−NaCl, 3 LiCl−2 KCl, LiCl−RbCl, and 3 LiCl−2 CsCl; at 873 K

Key electrochemical properties affecting pyroprocessing of nuclear fuel were examined in four eutectic melts using using Eu3+/2+ as a representative probe. We report the electrochemical and spectroelectrochemical behavior of EuCl3 in four molten salt eutectics (3 LiCl – NaCl, 3 LiCl – 2 KCl, LiCl – RbCl and 3 LiCl – 2 CsCl) at 873 K. Cyclic voltammetry was used to determine the redox potential for Eu3+/2+ and the applied potentials for spectroelectrochemistry. Single step chronoabsorptometry and thin-layer spectroelectrochemistry were used to obtain the number of electrons transferred, redox potentials and diffusion coefficients for Eu3+ in each eutectic melt. The redox potentials determined by thin-layer spectroelectrochemistry were extremely close to those obtained using cyclic voltammetry. The redox potential for Eu3+/2+ was most positive in the 3 LiCl - NaCl melt, showed a negative shift in the 3 LiCl - 2 KCl melt, and was the most negative in the LiCl - RbCl and 3 LiCl - 2 CsCl eutectics. The diffusion coefficient for Eu3+ followed this same trend; it was the largest in the 3 LiCl - NaCl melt and the smallest in the LiCl - RbCl and 3 LiCl - 2 CsCl melts. The basic one-electron reversible electron transfer for Eu3+/2+ was not changed by melt composition.

electrochemistry↗

Accurate determination of density, surface tension, and vessel depth using a triple bubbler system

Here, a triple bubbler sensor was developed for use in high temperature molten salt systems used in pyroprocessing to determine the density, surface tension, and depth of the molten salt. Preliminary bubbler testing was performed in aqueous solutions to calibrate and validate the bubbler sensor. Independently determined fluid property values and depths were compared to the calculated values and the percent differences were less than 0.16 %, 3.38 %, and 0.31 % for density, surface tension, and depth, respectively. In addition, uncertainties were within 0.04 %, 1.25 %, and 0.15 % for density, surface tension, and depth, respectively.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Analysis and modeling of the equilibrium behaviors of U and Pu in molten LiCl-KCl/Cd system at 500 °C

In the field of pyroprocessing of used nuclear fuels, liquid cadmium is applied in different ways to recover transuranics from molten salt, while effecting some degree of separations between transuranics and lanthanides. In this work, a model of the separation performance between uranium and plutonium across the phase boundary between molten salt and liquid cadmium is presented. The salt is the LiCl-KCl eutectic with solute concentrations of UCl 3 and PuCl 3 . The cadmium is the liquid cadmium phase field from the Cd-U-Pu ternary alloy system. Lastly, the model used to describe the behavior of uranium and plutonium in the salt/cadmium system is applied to describe the behavior of plutonium and lanthanide in the salt/cadmium system.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Thermal analysis of projected molten salt compositions during FFTF and EBR-II used nuclear fuel processing

This work studies the change in liquidus temperature of the salt used in the Mk-IV electrorefiner at the Idaho National Laboratory during processing campaigns of sodium-bonded driver fuels from Experimental Breeder Reactor II and the Fast Flux Test Facility reactor. Modeling and Simulation Tool for Electrochemical Recycling Systems (MASTERS), an INL proprietary pyroprocessing flowsheet simulation tool, was used to simulate the processing campaigns and determine the resulting composition changes of the Mark-IV electrorefiner salt. Surrogate salt samples simulating the Mk-IV electrorefiner salt during the fuel processing campaigns were prepared, and the thermal properties were measured via differential scanning calorimetry. Results from this study indicate that after processing approximately 2,150 kg of uranium metal from used fuel, the liquidus temperature of the molten salt exceeds 520°C, which is a significant increase from 352°C (the melting temperature of eutectic LiCl-KCl). It was also discovered that the liquidus temperature is strongly dependent on the amount of NaCl accumulating in the Mk-IV electrorefiner salt. Thus, the assessment of the liquidus temperature during the subsequent fuel processing campaigns can be simplified by considering the ternary LiCl-KCl-NaCl system only.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Electrochemical Salt Wasteform Development: A Review of Salt Treatment and Immobilization Options

Electrochemical reprocessing, also referred to as pyroprocessing, is a technique for recycling actinides from used nuclear fuel (UNF) to produce fuel for future reactors. Here, UNF is dissolved in a molten salt (e.g., LiCl-KCl eutectic) within an electrorefiner. After UNF dissolution, fission products are released into the electrolyte salt and converted to chlorides. This paper discusses wasteform options for processing the base electrolyte salt with the fission product salts as well as just the rare-earth fission products (as RECl 3 , REOCl, or REO x ) with the intent of finding optimal methods for reducing total waste salt volumes or partitioning the salt for alternate wasteform options. Furthermore, two of the more detailed partitioning options discussed herein include halide removal from the salt (dehalogenation), which accounts for more than half of the salt on a molar basis, and RE fission product removal for wasteforms with high-RE loadings. Wasteform properties are compared with emphasis on wasteform volume starting from a given amount of (1) total salt cations or (2) RE cations. Comparisons are also made of wasteform chemical durabilities, with the data available from like testing methods. A main conclusion from this work is the justification of subsequent salt processing after electrorefiner operations for achieving significant wasteform volume reduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Organic Acid-Assisted Thermal Dehalogenation of Halide Salt Nuclear Wastes: From Waste Salts to Borosilicate Glass

Only a handful of high-halide salt waste forms have been demonstrated for vitrification-based immobilization strategies for halide-salt nuclear waste streams (e.g., pyroprocessing wastes, molten salt reactor wastes) and they all have low waste loading potential and most have low chemical durabilities for high-alkali streams. An alternative approach to direct salt immobilization is salt partitioning prior to waste form fabrication and one option for partitioning is halide removal (called dehalogenation). Removing the halogen fraction through dehalogenation can significantly reduce the waste volume required for disposal in the primary waste form. Furthermore, when dehalogenation is performed using organic acids, the dehalogenation reagent can decompose during high-temperature vitrification, reducing waste loading limitations in the waste form. In the current work, different organic acids (i.e., oxalic, formic, acetic, oxamic, and citric) were evaluated for dehalogenation efficiency of a simple chloride salt simulant (7.19% LaCl 3 , 53.77% LiCl, and 39.04% KCl, by mole) and a more complex chloride salt simulant called ERV3 (electrorefiner version 3) at 150 °C–300 °C and using H + /Cl – molar ratios of 1:1, 2:1, and 3:1. Additionally, a borosilicate glass waste form called TARS (or the average of refined specifications) was formulated, produced, and characterized for dehalogenated ERV3.

Amorphous materials↗

Phosphate-Based Approaches for Dechlorination and Treatment of Salt Waste from Electrochemical Processing of Used Nuclear Fuel: A Perspective on Recent Work

Phosphate-based reagents are being considered by the U.S. Department of Energy (DOE) Office of Nuclear Energy to process halide salt-based nuclear wastes for stabilization prior to disposal. As evidenced by the Experimental Breeder Reactor-II (EBR-II) project, electrochemical processing (pyroprocessing) can be employed to recover uranium and other actinides for reintegration into the nuclear fuel cycle from metallic fuels. The resultant salt-based wastes generated from electrochemical processing of EBR-II fuel contains fission products within a LiCl–KCl eutectic salt that necessitate appropriate disposal. This paper provides an overview of recent efforts to support halide-based salt waste treatment for disposition, as well as a basis for comparison with other related efforts in salt waste treatment through salt partitioning initiatives. The U.S. DOE has selected a phosphate waste form reference material for further investigation and longer-term studies.

electrorefiner↗

Synergy in Materials: Leveraging Phosphosilicate Waste Forms for Electrochemical Salt Waste

Here, waste forms containing glassy and crystalline phosphate and silicate phases were produced to immobilize salt waste simulants from pyroprocessing and characterized by using Raman spectroscopy, Mössbauer spectroscopy, X-ray diffraction, scanning electron microscopy, heat capacity, and chemical durability measurements. In this work, a phosphosilicate waste form is presented to leverage the benefits of both borosilicate glasses and iron phosphate glasses. To improve waste loading, prior to immobilization, salt simulants were successfully dechlorinated using ammonium dihydrogen phosphate, mixed with a borosilicate frit (5–30 wt %) and Fe 2 O 3 , and vitrified. Additions of 2.5–15 wt % borosilicate glass (NBS3) improved normalized release rates for Cs relative to iron-phosphates without NBS3, resulting in chemical durabilities similar to high-level waste borosilicate glass reference materials. The release rates of the alkalis (i.e., Li, Na, K, Cs) were the lowest with the addition of 5 wt % NBS3. Although Sr was not specifically targeted in this study, evidence exists that it preferentially partitioned with Si to form an amorphous droplet phase within the iron phosphate glass matrix.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Application of a Triple Bubbler Sensor for Determining the Density, Surface Tension, and Depth in Molten Salts

Electrochemical (i.e. pyroprocessing) technology is being widely studied throughout the world as a potential alternative to aqueous reprocessing of spent nuclear fuel (SNF). Central to this process is the electrorefiner (ER), in which the useful uranium in the SNF is electrochemically transported through a molten salt electrolyte to a cathode for later recovery. As part of this process, uranium, plutonium, and other actinides accumulate in the ER salt over time. Material accountancy and safeguards of these special nuclear material buildups in near real-time is a significant challenge due to the elevated processing temperatures, remote operation within a hotcell, and high radiation fields. Analytical techniques outside of the hotcell can be used to provide the SNM concentrations of salt samples from the ER. However, determining the actual mass of these materials in the ER presents a significant challenge because the density and volume within the vessel is largely unknown. The Idaho National Laboratory (INL) has developed a triple bubbler sensor capable of determining the density, surface tension, and depth of a fluid in near real-time. Previous experiments in aqueous media has shown that the sensor is capable of determining the density, surface tension and depth with accuracies on the order of 0.2%. The goal of this current work is to test the sensor in several molten salt media to calibrate and validate the triple bubbler. Experiments have been performed in LiCl-KCl eutectic salt. Calibration factors were 1.0015 and 1.26 for density and surface tension, respectively. With the above calibration factors applied, the depth of the salt in the test vessel was determined to within 0.4%. These results indicate that the triple bubbler sensor has the potential to accurately (less than 1% uncertainty) determine the density, surface, tension, and depth of the ER salt in near real-time. The triple bubbler sensor designed at INL can significantly enhance the material accountancy, safeguards, and process monitoring of the electrochemical processing of SNF.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Novel Electrochemical Technique: Serial Open Circuit Potentiometry to Examine the Separability of Lanthanides in Molten Salts

The accumulation of lanthanide fission products in molten salts reduces the efficiency of pyroprocessing used nuclear fuel. Lanthanide fission products are notoriously difficult to separate due to their similar physical and electrical properties. We developed a novel electrochemical technique called serial open circuit potentiometry (SOCP) which allows us to delineate between metal deposition reactions with similar reduction potentials to great precision. SOCP has several advantages over traditional open circuit potentiometry including its ability to create 3D plots that describe all metal deposition reactions in a system. This information can be used to precisely determine equilibrium potentials of metal deposition reactions and quantify their error, determine nucleation potentials, and determine the nucleation and growth mechanism. In this work, we demonstrated the effectiveness of SOCP by studying molten salt mixtures containing CeCl3, GdCl3, and both CeCl3 and GdCl3 in LiCl-KCl eutectic.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗