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Used nuclear fuel separations process simulation and testing

Recent efforts in separations process simulation at Argonne have expanded from the traditional focus on solvent extraction flowsheet design in order to capture process dynamics and to simulate other components, processing and systems of a used nuclear fuel reprocessing plant. For example, the Argonne Model for Universal Solvent Extraction (AMUSE) code has been enhanced to make it both more portable and more readily extensible. Moving away from a spreadsheet environment makes the addition of new species and processes simpler for the expert user, which should enable more rapid implementation of chemical models that simulate evolving processes. The dyAMUSE (dynamic AMUSE) version allows the simulation of transient behavior across an extractor. Electrochemical separations have now been modeled using spreadsheet codes that simulate the electrochemical recycle of fast reactor fuel. The user can follow the evolution of the salt, products, and waste compositions in the electro-refiner, cathode processors, and drawdown as a function of fuel batches treated. To further expand capabilities in integrating multiple unit operations, a platform for linking mathematical models representing the different operations that comprise a reprocessing facility was adapted to enable systems-level analysis and optimization of facility functions. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Segmented Gamma Scanner for Small Containers of Uranium Processing Waste- 12295

The Segmented Gamma Scanner (SGS) is commonly utilized in the assay of 55-gallon drums containing radioactive waste. Successfully deployed calibration methods include measurement of vertical line source standards in representative matrices and mathematical efficiency calibrations. The SGS technique can also be utilized to assay smaller containers, such as those used for criticality safety in uranium processing facilities. For such an application, a Can SGS System is aptly suited for the identification and quantification of radionuclides present in fuel processing wastes. Additionally, since the significant presence of uranium lumping can confound even a simple 'pass/fail' measurement regimen, the high-resolution gamma spectroscopy allows for the use of lump-detection techniques. In this application a lump correction is not required, but the application of a differential peak approach is used to simply identify the presence of U-235 lumps. The Can SGS is similar to current drum SGSs, but differs in the methodology for vertical segmentation. In the current drum SGS, the drum is placed on a rotator at a fixed vertical position while the detector, collimator, and transmission source are moved vertically to effect vertical segmentation. For the Can SGS, segmentation is more efficiently done by raising and lowering the rotator platform upon which the small container is positioned. This also reduces the complexity of the system mechanism. The application of the Can SGS introduces new challenges to traditional calibration and verification approaches. In this paper, we revisit SGS calibration methodology in the context of smaller waste containers, and as applied to fuel processing wastes. Specifically, we discuss solutions to the challenges introduced by requiring source standards to fit within the confines of the small containers and the unavailability of high-enriched uranium source standards. We also discuss the implementation of a previously used technique for identifying the presence of uranium lumping. The SGS technique is a well-accepted NDA technique applicable to containers of almost any size. It assumes a homogenous matrix and activity distribution throughout the entire container; an assumption that is at odds with the detection of lumps within the assay item typical of uranium-processing waste. This fact, in addition to the difficultly in constructing small reference standards of uranium-bearing materials, required the methodology used for performing an efficiency curve calibration to be altered. The solution discussed in this paper is demonstrated to provide good results for both the segment activity and full container activity when measuring heterogeneous source distributions. The application of this approach will need to be based on process knowledge of the assay items, as biases can be introduced if used with homogenous, or nearly homogenous, activity distributions. The bias will need to be quantified for each combination of container geometry and SGS scanning settings. One recommended approach for using the heterogeneous calibration discussed here is to assay each item using a homogenous calibration initially. Review of the segment activities compared to the full container activity will signal the presence of a non-uniform activity distribution as the segment activity will be grossly disproportionate to the full container activity. Upon seeing this result, the assay should either be reanalyzed or repeated using the heterogeneous calibration. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Prairie Island Nuclear Station Spent Filter Processing for Direct Disposal - 12333

This paper will discuss WMG's filter processing experience within the commercial nuclear power industry, specifically recent experience processing high activity spent filters generated by Xcel Energy's Prairie Island Nuclear Station (Prairie Island), located in Welch, MN. WMG processed for disposal eighty-four 55-gallon drums filled with varying types of high activity spent filters. The scope of work involved characterization, packaging plan development, transport to the WMG's Off-Site Processing location, shredding the filter contents of each drum, cement solidifying the shredded filter material, and finally shipping the solidified container of shredded filter material to Clive, Utah where the container was presented to EnergySolutions Disposal site for disposal in their Containerised Waste Facility. This sequence of events presented in this paper took place a total of nine (9) times over a period of four weeks. All 1294 filters were successfully solidified into nine (9) -WMG 142 steel liners, and each was successfully disposed of as Class A Waste at EnergySolutions Disposal Site in Clive, Utah. Prairie Island's waste material was unique in that all its filters were packaged in 55-gallon drums; and since the station packaged its filters in drums it was much easier to develop packaging plans for such a large volume of legacy filters. For this author, having over 20-years of waste management experiences, storing and shipping waste material in 55-gallon drums is not immediately thought of as a highly efficient method of managing its waste material. However, Prairie Island's use of 55-gallon drums to store and package its filters provided a significant advantage. Drums could be mixed and matched to provide the most efficient processing method while still meeting the Waste Class A limits required for disposal. (author)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The ELIPSE Process: An Underwater Plasma Technology for Liquid Treatment - 16026

Radioactive liquid organic wastes are very various and produced in different quantities. Some of them are treated through specific processes when others are still waiting from outlet to be destroyed and stabilized. Their different composition (chlorinated, phosphate, sulfated, fluorinated, ...) make their treatment difficult in a same technology. The ELIPSE process has been design to propose an innovative solution leading to a global treatment of what is usually called 'orphan liquids'. This brand new technology involved a non-transferred plasma torch working under a water column ensuring the cooling, the filtration and the scrubbing of the gases coming from the combustion of the liquids. Furthermore, the water that ensures the global cooling of the system leads to low or to avoid the corrosion in a compact process. Only the nozzle of the torch may be affected by the corrosion and may become a wearing part of the system of treatment. After giving a detailed description of the ELIPSE process, the present paper will focus on the results obtained for the treatment of such different liquids as tributyl phosphate, perfluorinated oil and trichloroethylene. In addition to obtaining destruction efficiency upper than 99%, the corrosion seems to have been significantly limited. These features lead to the first conclusion that the ELIPSE process could be a solution for the future to the problem of the hazardous liquid treatment, nuclear or not. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Thermal Process Technology for Nuclear Applications - 20379

ANSTO's Synroc technology has been developed to provide a safe, secure matrix for the immobilization and final disposal of radioactive waste. Synroc technology will be used to manage radioactive wastes from the production of the radioisotope Molybdenum-99 (Mo-99). This paper shall outline various stages of the process development with specific reference to the thermal treatment technology of calcination. Calcination is a key step in the Synroc process [1-2].The rotary thermal processing system includes: an advanced heating element design for increased robustness and ease of remote operation and maintenance, an enhanced modular design of components for ease of remote maintenance in a hot cell and in compliance with hot cell radioactive environment requirements for safety, reliability and maintainability. In addition to thermal treatment of waste from nuclear medicine production, this technology provides solutions for a variety of nuclear materials processing applications including sintering UO{sub 2} pellets for reactor fuel rods, oxidation of UO{sub 2} pellets, swarf, and powder to U{sub 3}O{sub 8}, de-nitration of Uranyl nitrate and hydrofluorination of UO{sub 2} pellets. The paper will also discuss thermal processing solutions for a range of nuclear applications. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Overview of Upcoming Process Improvement Efforts at the Saltstone Facilities at the Savannah River Site - 20474

The Saltstone Facilities at the Savannah River Site (SRS) process and dispose of low activity salt solution waste generated by other liquid waste facilities. Today in the Liquid Waste System (LWS), approximately 125 million liters of salt waste remain to be processed. The Saltstone Production Facility (SPF) receives the decontaminated salt waste, which is mixed with dry feeds consisting of cement, fly ash and slag to produce the saltstone. The mixed slurry is pumped to the Saltstone Disposal Units (SDUs) for safe disposal in the Saltstone Disposal Facility (SDF). To support continuous Salt Waste Processing Facility (SWPF) operations at annual processing volumes many times higher than present, significant modifications are required to ensure that the SPF has the capacity to support the throughput of salt waste. These changes include several infrastructure upgrades that are being worked through the Enhanced Low Activity Waste Disposal (ELAWD) project. In addition to infrastructure upgrades, Savannah River Remediation (SRR), the Savannah River Site's Liquid Waste Contractor for the U.S. Department of Energy, has identified a flowsheet improvement opportunity of implementing a cement-free saltstone formulation to eliminate cement from the current three component formulation. This two-component formulation would simplify the procurement, transport, off-loading, and storage of the premix materials, and increase the storage capacity for the individual components. This flowsheet, when implemented, will reduce operational risk and improve throughput necessary to achieve disposal rates necessary for SWPF operations. Research has been completed to confirm the feasibility of this formulation, with the new cement-free flowsheet expected to be implemented in the next few years. Improvements have also been identified downstream of the SPF to increase SDU utilization. Specifically, a concentrated effort has taken place to raise the fill height in SDU 6 to the full disposal height, 13 meters, to maximize the usage of each SDU in support of the liquid waste disposal mission. This improvement has been made through additional thermal modeling and improved process understanding to create a SDU flammability model and control strategy more representative of facility operations. This work will allow for the completion of construction and operational readiness for SDU 7 while filling SDU 6 to ensure there is no lapse in available space once SWPF starts up. A summary of these improvements as they relate to increased throughput will be provided along with associated status. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A New Understanding of Decarbonizing Industrial Process Heat

Analysis conducted over the last few years has improved our understanding of how industrial process heat is used in the United States. These improvements are important for characterizing the possibilities for industrial decarbonization. However, this analysis has largely been conducted from technical perspective and has remained disconnected from the social processes that underlie how industrial firms may adopt and implement technologies to decarbonize their process heating operations. This presentation introduces the concept of generic and configurational technology systems, and outlines the how the incorporation of user requirements and local contexts are essential for successful implementation of configurational systems. Insights drawn from semi-structured interviews with representatives of industrial firms are used to support the hypothesis that industrial process heat technologies are configurational. The potential implications for strategies to decarbonize process heat are then discussed.

adoption↗

Co-Processing Fast Pyrolysis Bio-Oils and Hydrothermal Liquefaction Biocrudes in Fluid Catalytic Cracking and Hydroprocessing in Refineries

Co-processing of biogenic feedstocks within the existing petroleum infrastructure represents an opportunity to incorporate large volumes of bio-carbon into transportation fuels. However, upgrading intermediate liquids from biomass and waste to final products efficiently and economically, while minimizing impacts to existing refinery infrastructure, remains a notable barrier to commercialization. The co-processing project, Bio-oil Co-processing with Refinery Streams, aimed to generate foundational knowledge for processing renewable intermediates in petroleum refineries and offer co-processing strategies, as well as develop new methods for biogenic carbon tracking and measurement.

bio-oil↗

Development of Leaching Processes for the Recovery of Rare Earth Elements from Acid Mine Drainage Precipitates

Acid mine drainage (AMD) has been a challenge for mine operators to address and has had significant environmental impacts when there is a failure to address it. Fortunately, there is a regulation in the US that requires the treatment of AMD before water can be discharged into the environment. AMD is generated when sulfide minerals are exposed to water and air from mining. The acidic water then leaches metals from the surrounding rock, creating the potential for environmental contamination of this acidic water containing dissolved metals. AMD can contain high concentrations of metals like iron, aluminum, and manganese and also have been shown to contain trace concentrations of critical minerals, including rare earth elements (REEs). This environmental waste stream is now being researched as a potential source for REEs. There is a patented process for processing and extracting REEs from AMD which produces rare earth oxide preconcentrate (REOP) from AMD treatment precipitates and a final stage mixed rare earth oxide (MREO) product. This body of research examines a selective leaching process for each of these products and determines the activation energy associated with the leaching processes. Acid leaching with HCl was examined to selectively leach REEs from REOP while contaminant metals remained in the solid residue. The maximum leaching recovery of the REEs from the REOP was approximately 90% and an activation energy of 6.4 kJ/mol at pH 3.0. Ammonium chloride leaching was examined to selectively remove contaminant metals from a MREO product. The ammonium chloride process successfully leached major contaminant metals in excess of 85% recovery and had a maximum activation energy of 40.0 kJ/mol.

01 COAL, LIGNITE, AND PEAT↗

Benefits and challenges of vibroacoustic process monitoring to support operators in nuclear research facilities

According to the International Atomic Energy Agency in 2024, global nuclear energy capacity is projected to increase by 2.5 times by 2050 in their high-case scenario. Research on the laboratory scale of innovative processes within nuclear facilities is ongoing to improve nuclear fuel cycle capabilities. Vibroacoustic process monitoring of these techniques has potential to inform operators regarding process specific metrics, predictive maintenance, and anomalous event detection. Additionally, this type of monitoring has the potential to aid in nuclear safeguards. Challenges regarding vibroacoustic monitoring in these environments include high temperature, high radiation, limited access, and shielded equipment limiting sensor type and placement. Microphones, accelerometers, and temperature sensors were deployed both inside and near these environments during operation to determine environment driven limitations, sound attenuation of containment enclosures, process specific metrics, and future potential of vibroacoustic monitoring in these environments. Overall, this work highlights the benefits and limitations of vibroacoustic process monitoring in nuclear research facilities.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Optimal Methanol Production via Sorption-Enhanced Reaction Process

To counter the equilibrium limitations in traditional methanol production from synthesis gas, a periodic and sorption-enhanced methanol synthesis process (SE-MeOH) with in situ removal of water byproduct is designed and optimized. A generalized reaction–adsorption modeling and simulation framework is coupled with a simulation-based constrained gray-box optimizer to obtain the optimal cycle configuration, design parameters, process specifications, and operating conditions. The best-case results indicate that SE-MeOH processes can break the barrier of the current limit of industrial methanol yield and improve it by 55–87% with a slight compromise (9–46%) on CH 3 OH production capacity. This trade-off is a result of periodic operation which is required for sorption enhancement. The techno-economic optimization of a base industrial reactor also leads to more than 7% improvement in methanol yield with only 2% decrease in production capacity while keeping the cost of syngas-to-methanol production competitive. The SE-MeOH system is further optimized through varying the feed specifications and number of reactor tubes. Furthermore, the results suggest that the synthesis gas composition, flow rate, and number of tubes are the major factors in determining methanol process performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simultaneous Process and Heat Exchanger Network Synthesis Using a Discrete Temperature Grid

We present mixed-integer linear programming models for utility targeting and heat exchanger network synthesis that account for variable stream temperatures and flow rates as well as unclassified streams and thus can be combined with process synthesis optimization models. By projecting temperature information onto a fixed discrete temperature grid, the model remains linear even under variable temperatures and flow rates, leading to a more tractable optimization model. The proposed model is well suited to address problems in the area of process intensification where the close interaction between different phenomena naturally leads to process synthesis problems with unclassified process streams. Several extensions are presented, including nonisothermal mixing as well as phase changes. Moreover, we show how a nonuniform grid can be adopted to reduce the complexity of the model for medium and large-size problems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Defense Waste Processing Facility (DWPF) Durability-Composition Models and the Applicability of the Associated Reduction of Constraints (ROC) Criteria for High TiO 2 Containing Glasses

Radioactive high-level waste (HLW) at the Savannah River Site (SRS) has successfully been vitrified into borosilicate glass in the DWPF since 1996. Vitrification requires stringent product/process (P/P) constraints since the glass cannot be reworked once it has been poured into ten foot tall by two foot diameter canisters. A unique “feed forward” statistical process control (SPC) was developed for this control rather than relying on statistical quality control (SQC). In SPC, the feed composition to the DWPF melter is controlled prior to vitrification. In SQC, the glass product would be sampled after it is vitrified. Individual glass property-composition models form the basis for the “feed forward” SPC. The models transform constraints on the melt and glass properties into constraints on the feed composition going to the melter in order to determine, at the 95% confidence level, that the feed will be processable and that the durability of the resulting waste form will be acceptable to a geologic repository. The DWPF SPC system is known as the Product Composition Control System (PCCS). One of the process models within PCCS is known as the Thermodynamic Hydration Energy Reaction MOdel (THERMO™). The DWPF will soon be receiving increased concentrations of TiO 2 -, Na 2 O-, and Cs 2 O-enriched wastes from the Salt Waste Processing Facility (SWPF). The SWPF has been built to pretreat the high-curie fraction of the salt waste to be removed from the HLW tanks in the F- and H-Area Tank Farms at the SRS. In order to validate the existing TiO 2 term in THERMO™ beyond 2.0 wt% in the DWPF, new durability data were developed over the target range of 2.00 to 6.00 wt% TiO 2 and evaluated against the 1995 durability model. The durability was measured by the 7-day Product Consistency Test. This study documents the adequacy of the existing THERMO™ terms. It is recommended that the modified THERMO™ durability models and the modified property acceptable region limits for the durability constraints be incorporated in the next revision of the technical bases for PCCS and then implemented into PCCS. It is also recommended that an reduction of constraints of 4 wt% Al 2 O 3 be implemented with no restrictions on the amount of alkali in the glass for TiO 2 values ≥2 wt%. The ultimate limit on the amount of TiO 2 that can be accommodated from SWPF will be determined by the three PCCS models, the waste composition of a given sludge batch, the waste loading of the sludge batch, and the frit used for vitrification.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Comparison of effects of cold‐region soil/snow processes and the uncertainties from model forcing data on permafrost physical characteristics

Abstract We used a land surface model to (1) evaluate the influence of recent improvements in modeling cold‐region soil/snow physics on near‐surface permafrost physical characteristics (within 0–3 m soil column) in the northern high latitudes (NHL) and (2) compare them with uncertainties from climate and land‐cover data sets. Specifically, four soil/snow processes are investigated: deep soil energetics, soil organic carbon (SOC) effects on soil properties, wind compaction of snow, and depth hoar formation. In the model, together they increased the contemporary NHL permafrost area by 9.2 × 10 6 km 2 (from 2.9 to 12.3—without and with these processes, respectively) and reduced historical degradation rates. In comparison, permafrost area using different climate data sets (with annual air temperature difference of ∼0.5°C) differed by up to 2.3 × 10 6 km 2 , with minimal contribution of up to 0.7 × 10 6 km 2 from substantial land‐cover differences. Individually, the strongest role in permafrost increase was from deep soil energetics, followed by contributions from SOC and wind compaction, while depth hoar decreased permafrost. The respective contribution on 0–3 m permafrost stability also followed a similar pattern. However, soil temperature and moisture within vegetation root zone (∼0–1 m), which strongly influence soil biogeochemistry, were only affected by the latter three processes. The ecosystem energy and water fluxes were impacted the least due to these soil/snow processes. While it is evident that simulated permafrost physical characteristics benefit from detailed treatment of cold‐region biogeophysical processes, we argue that these should also lead to integrated improvements in modeling of biogeochemistry.

58 GEOSCIENCES↗

Improving the representation of hydrologic processes in Earth System Models

Many of the scientific and societal challenges in understanding and preparing for global environmental change rest upon our ability to understand and predict the water cycle change at large river basin, continent, and global scales. However, current large-scale models, such as the land components of Earth System Models (ESMs), do not yet represent the terrestrial water cycle in a fully integrated manner or resolve the finer-scale processes that can dominate large-scale water budgets. This paper reviews the current representation of hydrologic processes in ESMs and identifies the key opportunities for improvement. This review suggests that (1) the development of ESMs has not kept pace with modeling advances in hydrology, both through neglecting key processes (e.g., groundwater) and neglecting key aspects of spatial variability and hydrologic connectivity; and (2) many modeling advances in hydrology can readily be incorporated into ESMs and substantially improve predictions of the water cycle. Accelerating modeling advances in ESMs requires comprehensive hydrologic benchmarking activities, in order to systematically evaluate competing modeling alternatives, understand model weaknesses, and prioritize model development needs. This demands stronger collaboration, both through greater engagement of hydrologists in ESM development and through more detailed evaluation of ESM processes in research watersheds. Advances in the representation of hydrologic process in ESMs can substantially improve energy, carbon and nutrient cycle prediction capabilities through the fundamental role the water cycle plays in regulating these cycles.

54 ENVIRONMENTAL SCIENCES↗

Versatile Sequential Casting Processing for Highly Efficient and Stable Binary Organic Photovoltaics

Forming an ideal bulk heterojunction (BHJ) morphology is a critical issue governing the photon to electron process in organic solar cells (OSCs). Complementary to the widely-used blend casting (BC) method for BHJ construction, sequential casting (SC) can also enable similar or even better morphology and device performance for OSCs. Here, BC and SC methods on three representative donor:acceptor (D:A) blends are utilized, that is, PM6:PC 71 BM, PM6:IT-4F and PM6:L8-BO. Higher power conversion efficiencies (PCEs) in all cases by taking advantage of beneficial morphology from SC processing are achieved, and a champion PCE of 18.86% (certified as 18.44%) based on the PM6:L8-BO blend is reached, representing the record value among binary OSCs. The observations on phase separation and vertical distribution inspire the proposal of the swelling–intercalation phase-separation model to interpret the morphology evolution during SC processing. Further, the vertical phase segregation is found to deliver an improvement of device performance via affecting the charge transport and collection processes, as evidenced by the D:A-ratio-dependent photovoltaic properties. Besides, OSCs based on SC processing show advantages on device photostability and upscale fabrication. Finally, this work demonstrates the versatility and efficacy of the SC method for BHJ-based OSCs.

14 SOLAR ENERGY↗

Observational process data analytics using causal inference

Voluminous process data are available with the paradigm shift toward smart manufacturing. However, most historical data are observational, containing noncausal correlations due to confounders and mediators. Estimating causal effects from observational data remains a bottleneck in leveraging them for active applications such as optimization and control. Further, this work aims to introduce a causal modeling framework for analyzing observational process data and extracting quantitative causal information. We demonstrate a real-world application in steel manufacturing where causal inference is used to analyze observational production data and improve the steelmaking process. Additionally, we propose a novel formulation for identifying critical process parameters from observational data, where causal inference is combined with variance-based methods to estimate corresponding risks of interventions to the manufacturing system. The proposed methods are compared with statistical ones to illustrate that causally interpreting statistical correlation leads to problematic results, while the provided workflow generates satisfactory strategies for process improvement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of melting processes on the structure and precipitation of a heavy rainstorm in Beijing

Abstract Beijing and its surrounding areas experienced a torrential rainstorm from July 21 to 22, 2012. Previous studies have shown that melting was the main rainwater source in this process. In this paper, melting conversion processes were set to zero (NPMLT test) to analyze the effect of microphysical processes on the structure and precipitation of the convective system. The results showed that without the melting processes, the wind shear at the 700 hPa level decreased, and the wind field in Beijing and its surrounding areas changed. The cold front system moved faster, and the rainfall amount only reached the low rain level, much lower than that during the actual rainstorm. The hydrometeors sources had apparently changed. Though the latent heat release was large and little latent heat absorption occurred in the NPMLT test, the net latent heat did not affect the development of the convective system, and the precipitation was low. Therefore, microphysical processes greatly influence precipitation and convective system.

Guo, Chunwei↗