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At least 199 records · Page 11

Gandolinium poison solubility testing for the downstream impacts from accelerated basin de-inventory

The Accelerated Basin De-inventory (ABD) Program at the Savannah River Site (SRS) is designed to accelerate the de-inventory of L-Basin and accelerate the Spent Nuclear Fuel (SNF) Disposition mission. Spent fuel will be dissolved in H-Canyon without recovery of uranium. The dissolver solutions will be temporarily stored, pH-adjusted to excess hydroxide (which will facilitate precipitation of metal oxides/hydroxides), transferred to the Concentration, Storage, and Transfer Facility (CSTF), and subsequently immobilized in the Defense Waste Processing Facility (DWPF) during planned sludge batch campaigns. ABD accelerates basin closure, significantly reduces programmatic risk, and greatly reduces the lifecycle budget requirements for the site by eliminating the need for a SNF drying and packaging capability. The ABD approach represents a significant change to the clean-up approach for the SRS. However, the increased fissile loading in sludge batches, due to the dissolver solutions, requires investigation to ensure fissile limits are efficiently and safely managed; higher fissile loadings in the glass are projected to be two to three times higher than the current fissile concentration limit of 897 g/m 3 and will be addressed in a future report.

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Analysis of Tank 38H (HTF-38-21-95, -96) and Tank 43H (HTF-43-21-97, -98) Samples for Support of the Enrichment Control and Corrosion Control Programs

SRNL analyzed samples from Tank 38H and Tank 43H to support ECP and CCP. The results indicate the concentrations of most species in the Tank 38H surface sample increased from the previous surface sample. The Tank 38H sub-surface sample shows only minor changes in concentration for soluble species in the solution (e.g., Na, Al, Cs-137) relative to the previous sample, but a small decrease in concentrations for species typically associated with sludge solids (e.g., U, Pu, Fe, Si) likely because of a decrease in sludge solids from the previous sample. The large differences in the concentrations of major components between the Tank 38H surface and sub-surface samples indicate significant stratification of solution species within the tank.

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Evaluation of the Impact of Additional Manganese from the Recycle Collection Tank (RCT) Glycolate Destruction Process on Glass Properties

The Defense Waste Processing Facility (DWPF) is planning to implement glycolic acid as a reductant within the waste processing flowsheet. An assessment of the glycolic acid flowsheet has revealed the potential for thermolytic production of hydrogen in the Concentration, Storage and Transfer Facilities (CSTF) from glycolate entrained in the DWPF recycle stream. To mitigate this potential scenario, a glycolate destruction process utilizing sodium permanganate (NaMnO 4 ) is being developed for use in the DWPF Recycle Collection Tank (RCT). The RCT is fed by the Slurry Mix Evaporator Condensate Tank (SMECT) and the Off-Gas Condensate Tank (OGCT). The SMECT could receive glycolate via a foamover from the Sludge Receipt and Adjustment Tank (SRAT) or the Slurry Mix Evaporator (SME), and the OGCT could receive glycolate via carryover of sludge particles in the purge from the melter during surge conditions. The use of NaMnO 4 additions in the RCT will result in additional manganese (Mn) in the waste stream and needs to be evaluated.

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Accelerated Basin De-Inventory Maximum Fissile Estimate

The Accelerated Basin De-inventory (ABD) program increases processing of Spent Nuclear Fuel (SNF) in H-Canyon to accelerate the closure of L Basin. The dissolved SNF will be dispositioned to Sludge Batches that will be processing in the Defense Waste Processing Facility and converted to glass. The fissile glass loading directly impacts the amount of glass canisters made. This memorandum provides an estimated maximum quantity of total fissile expected to be transferred to a Sludge Batch to support increasing the fissile glass loading and thus reducing the number of canisters created across the lifetime of the ABD mission.

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Analysis of Tank 38h (HTF-38-23-19, -20) and Tank 43H (HTF-43-23-21, -22) Samples for Support of the Enrichment Control and Corrosion Control Programs

SRNL analyzed samples from Tank 38H and Tank 43H to support ECP and CCP. The results indicate the concentrations of most soluble species in the Tank 38H surface sample decreased significantly from the previous surface sample. The Tank 38H sub-surface sample shows changes in concentration for soluble species in the solution with some increasing and some decreasing. The current Thank 38H sub-surface sample contains visible sludge solids similar to the previous sample, i.e., less than 1%, based on visual appearance. The significant differences in the concentrations of major components between the Tank 38H surface and sub-surface samples indicate significant stratification of solution species between these two locations within the tank. Savannah River Mission Completion personnel indicate that ~ 150,000 gallons of Tank 22 supernate were received in Tank 38H since its last analysis during which time the 2H evaporator was not operated, so the observed stratification is expected. The Tank 43H surface and sub-surface samples are similar in composition to the previous samples. The similar solution compositions measured in the Tank 43H surface and sub-surface samples indicate a minimal stratification within the tank. The total uranium and plutonium in the current Tank 38H surface sample remains similar to the previous analysis. The Tank 38H sub-surface sample shows an increase in uranium and plutonium concentrations compared to the previous sample likely because of an increase in sludge solids in the current sample. The total uranium concentration in the Tank 43H surface sample is similar to the previous sample results while the plutonium in the Tank 43H sub-surface sample increased relative to the previous analysis. The sum of the major cations versus the sum of the major anions shows a difference of <10% for both samples from Tank 38H sub-surface sample (174 mg/L) increased compared with the previous sample. The Tank 38H surface sample silicon concentrations (27.5 mg/L) is one-half of the previous sample results. The Tank 43H surface sample silicon concentrations compared to the previous sample results indicate Si in the concentration range of 60 to 83 mg/L. Thus, these current samples analyzed from Tanks 38H and 43H show overall silicon concentrations ranging from 27.5 to 174 mg/L.

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Modelling the Liquid Waste Operation at the Savannah River Site

Modeling Successes Dounreay – Site Closure Optimization and Risk Reduction Re-structuring and streamlining a complex project plan to achieve site decommissioning in reduced time and at reduced cost, through automated task prioritization. Idaho AMWTP – Multi-stream Optimization Speeding up a complex facility with many process lines, by utilizing all of the process lines more efficiently and reducing overall plant downtime, by coordinating repairs and shutdowns. AWE –Waste Repackaging and Relocation Relocating schedule for waste material from an old storage facility to a new purpose-built one, safely, and in a timely fashion that removed the need to reassure the safety of the old facility. Sellafield – Effluent, Sludge and HAW Treatment Improving a wide range of chemical engineered processes including aqueous effluent treatment, chemically-reactive sludge management and waste vitrification processing. Strategic Petroleum Reserve – Cavern Management Linking chemistry models of petroleum prediction, through engineering cavern management to financial modeling of gasoline sales to benefit US government

Jung, Andrew W.↗

Improving Efficiency of DWPF Operations via Automating Process Calculations and Vitrifying High-Curie Feed- 24529

The Liquid Waste Organization (LWO) at the Savannah River Site (SRS) uses a “Power As One®” motto to process and dispose of radioactive waste. The Defense Waste and Processing Facility (DWPF) treats the high-level waste through a process of vitrification. The DWPF receives three incoming waste streams that are added to the Sludge Receipt and Adjustment Tank (SRAT): sludge, Monosodium Titanate/Sludge Solids (MST/SS), and Strip Effluent (SE). The liquid waste is mixed with pre-fabricated frit and treated with high temperatures in the melter prior to being poured into stainless steel canisters. The liquid cools to form solid glass within these canisters that are suitable for long-term storage and disposal. Savannah River Mission Completion (SRMC), the SRS liquid waste contractor for the U.S. Department of Energy, has implemented several facility improvements to further enhance the operations to support the Liquid Waste Operation (LWO) mission. Two of these operational enhancements include implementing the electronic Material Tracking Program Calculator (eMTPC)software and increasing the DWPF canister heat rate limit.

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Integration of Autothermal Oxidation into Hydrothermal Liquefaction

This report examines incorporating a mild oxidation process, in traditional Hydrothermal Liquefaction (HTL). The focus is on improving efficiency through heat recovery and autothermal operations. In WAO, pressurized and heated sludge, mixed with air, undergoes combustion reactions, generating CO 2 and other gases. A novel aspect is using reactor effluent heat to pre-heat incoming sludge, minimizing energy needs and enabling autothermal reactions at specific solids concentrations. The report discusses many advantages of this embodiment of the HTL process, which could eliminate heat exchangers by leveraging heat from oxidation. This approach simplifies operations.

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Impacts of Fast Critical Assembly Fuel Discards on Liquid Waste Processes

The Savannah River Nuclear Solutions (SRNS) Fast Critical Assembly (FCA) mission is reestablishing the electrolytic dissolver for processing of Pu and Pu-U materials clad in stainless steel (SS). H-Canyon is planning to dissolve and neutralize FCA fuel without recovering the special nuclear material (i.e., Pu) prior to discarding to the Concentration, Storage, and Transfer Facilities (CSTF) operated by the Savannah River Mission Completion (SRMC) Liquid Waste (LW) Organization. The FCA discards will be combined with sludge in the CSTF after Low Temperature Aluminum Dissolution (LTAD) if needed. The combined waste will be washed, concentrated, and vitrified at the Defense Waste Processing Facility (DWPF). The high level waste canisters produced will be temporarily stored in the Glass Waste Storage Buildings prior to transfer to a future federal repository. Decants from LTAD and sludge washing will be combined with DWPF recycle and dissolved salt cake to prepare salt batches for processing in the Salt Waste Processing Facility. The resulting decontaminated salt solution will be processed in the Saltstone Production Facility.

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Evaluation of the Potential for Precipitation of Solids during Storage of Non-Aluminum SNF Solutions

Non-aluminum clad spent nuclear fuels (NASNF) stored in the L-Area basin will be dissolved in H-Canyon using the 6.3D electrolytic dissolver. The solutions will be stored in either the hot or warm canyon until the preparation of a sludge batch for the Defense Waste Processing Facility. Spent nuclear fuel solutions could be stored for 1-2 years before transfer to the H-Area Tank Farm depending on the interval between sludge batches. The solution level in the storage tanks will be maintained; therefore, precipitation of solids due to evaporation is not an issue. However, the precipitation of solids from completely dissolved SNF due to solution instabilities has been observed during intermediate storage of solutions generating hydrated oxides.The presence of fissile material in these solids is generally associated with zirconium molybdate, which is known to act as a host lattice for Pu and can carry the actinides upon precipitation. The formation of zirconium molybdate solids which carry fissile material is a potential concern for the storage of NASNF solutions. To address this concern, the Savannah River National Laboratory performed a literature review to identify knowledge gaps which may require experimental work to determine if the formation of solids is a concern during storage of these solutions. Based on the literature review, the precipitation of zirconium molybdate solids from the Campaign 1 NASNF solutions during intermediatestorage is expected. This conclusion is supported by the identification of zirconium molybdate solids found on the H-Canyon 6.1D Dissolver MK-12 insert spacer. The formation of the zirconium molybdate solids is attributed to hydrolysis and radiolytic processes in the nitric acid solution. As the molybdate solids form, U and Pu can substitute for Zr in the crystal lattice resulting in co-precipitation. Generally, the Pu substitutes directly into the crystal lattice during precipitation while the U associated with the molybdate solids more likely absorbs from the solution. The U in the NASNF solutions is present as uranyl nitrate, a 2+ cation which will not substitute as easily into the molybdate crystal lattice for the Zr 4+ ion.

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Uranium Solubility and Supernate Enrichment Testing for Accelerated Basin De-Inventory Discards to Concentration, Storage, and Transfer Facilities

After future Accelerated Basin De-inventory (ABD) enriched uranium discards into sludge batches (SB), portions of supernate decants during SB preparation will be blended into salt batches (StB) and the resulting feeds must meet the nuclear safety requirements for the Salt Waste Processing Facility (SWPF). During previous SB10 sampling and testing, which involved H-Canyon material containing enriched uranium being mixed with Tank 51 sludge shortly after the H-Canyon stream was neutralized, it was identified that the uranium isotopic enrichment in the supernate deviated from the uranium isotopic enrichment in the slurry. The higher uranium isotopic enrichment in the supernate introduced the risk of challenging the feed requirements of SWPF. The ABD material added to SB11 was isotopically diluted with depleted uranium, mitigating any downstream impacts. However, H-Canyon desires to eliminate or minimize future depleted uranium additions in order to meet the mission schedule.

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New Tank Mapping Method Improves Waste Removal Process

Waste Tank Mapping Overview • Camera inspections are performed within available tank top risers and used to create waste tank maps – Several camera inspections are performed during waste removal transfers to verify the elevation of the visible salt/sludge mounds against the known elevation of the liquid surface • Tank mappings are used to evaluate the volume and distribution of saltcake or sludge that is present within the waste tank – Allows for refined operating strategies and process safety controls • New tank mapping process creates a standardized approach for accurately defining waste distribution within a waste tank while minimizing the required camera inspection footage – First utilized during the 2023 Tank 22 Sludge Removal Campaign

Mini, Melany [Savannah River Mission Completion (S↗

In-Tank Processing Using Low Temperature Aluminum Dissolution: Year 1 Progress Report

The Hanford Site stores approximately 56 million gallons of radioactive legacy defense waste in underground tanks. This study investigates the feasibility of utilizing in-tank low-temperature aluminum dissolution to favorably alter the transport properties of aluminum-rich southeast quadrant waste sludges, thereby de-risking sludge delivery for Direct Feed of High-Level Waste. Specifically, this study aims to assess the rate and extent of gibbsite dissolution under various conditions, including different particle sizes (~10 to 90 µm), NaOH concentrations (1 to 6 M), and the presence of specific analytes such as NO 2 - , NO 3 - , and other aluminum-rich waste background analytes, using simulated waste solids and liquids. Experimental tests were designed to highlight the impact of aluminum leaching on simulated waste transport properties, quantified by the just-suspended mixing speed (NJS), and were conducted under well-mixed, turbulent conditions, ensuring full suspension of gibbsite particles using an overhead mixer. The results suggest that the presence of NO 2 - and NO 3 - , in conjunction with leaching at relatively low free hydroxide contents, improved transport requirements (i.e., lowered NJS) for pure gibbsite slurries. These findings will inform the design of potential in-tank processing systems, optimizing aluminum dissolution for improved waste management in the Hanford Tank Farms.

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FY24 Task 5: Leachate Disposition

Directly feeding sludge solids to the high-level waste (HLW) Waste Treatment Plant represents an alternative flowsheet seeking to initiate sludge processing as soon as possible. Key processing functions previously captured during baseline pretreatment operations include leaching and washing prior to solids concentration. These operations should be considered in the potential direct feed flowsheets to maximize waste feed loading, minimize HLW volume, and mitigate corrosion challenges associated with vitrification of high phosphate and fluoride concentrations. Additionally, single-shell tank (SST) retrievals and waste transfers to double-shell tanks (DSTs) in a direct feed flowsheet would likely also benefit from some level of leaching, washing, and solids concentration in order to reduce DST space and mission duration. These operations could occur in a new facility or potentially in available DSTs. If washing and leaching are utilized, an effective disposition pathway for the wash water and leachate solutions are needed. Three target species that benefit significantly from leaching and washing are phosphate, fluoride and aluminum. Phosphate (PO 4 3- ) and fluoride (F - ) can contribute substantially to the amount of carrier fluid needed for dissolution, and the resulting volume of liquid generated. Disposition of this retrieval solution should be evaluated in order to prevent crystallization of these anions throughout system processing. Since there is a high probability that any retrieval solutions will be at or near their PO 4 3- and F - solubility limits, evaporation or blending with a high Na supernate (>3.5 M) is not recommended for the wash water streams without a method to remove precipitants prior to solution disposal. Additionally, aluminum present in the southeast quadrant of the Hanford site represents roughly 60% of the waste solids in the initial processing tanks. These aluminum solids are in the form of gibbsite (Al(OH) 3 ) and can pose significant challenges for processing due to the fast-settling times and high solids loading associated with these materials. Easily remediated by caustic addition to the solids, these wash solutions could be processed through crystalline silicotitanate (CST) ion exchange columns to prepare the supernate solutions for disposition. The current target for feed conditions to the Low Activity Waste (LAW) melter are waste streams that contain nominally 5-6 M Na. Fractions within the tanks contain upwards of 0.2 M phosphate and fluoride in solution at 3.5 M Na. Concentrating these solutions above 5 M Na would result in an exceedance of the solubility limits, and potential for uncontrolled precipitation of the phosphate and fluoride crystal material. The resulting crystalline salt material is typically sodium fluoride phosphate, also referred to as natrophosphate (Na 7 FPO 4 ·19H 2 O). Salt phases are of importance in tank waste due to their chemical reactivity, which can result in precipitation, dissolution, or transformation, impacting any downstream processes (Bolling et al. 2020, Russell, Snow, and Peterson 2010). Salt generation and precipitation could pose challenges by causing system plugging and melter corrosion if left in the supernate stream, or limit sodium molarity of the supernate that would be accepted without incident in waste operations. To understand the impact of this salt generation, the crystallization of natrophosphate in multiple simulant feed matrices was studied to understand the implications of various tank waste supernate chemistries. Three matrices were examined: high PO 4 3- /low F - , low PO 4 3- /high F - , and an average matrix. Subsequent testing was performed with the average matrix with the inclusion of CsNO 3 , and a final run with the average matrix including CsNO 3 and a 137 Cs spike for tracer purposes.

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FY24 Task 4: Studies of Phosphate and Fluoride Solubility for Dissolution of High Phosphate Tank Waste

Knowledge gaps have been identified in phosphate solubility in almost every single- and multi-component system, and particularly for aluminate in phosphate/hydroxide, where uncertainties in predicted values of aluminum solubility are greater than 50%. Solubility data of multicomponent, aqueous electrolytes containing sodium hydroxide, sodium fluoride, sodium phosphate, sodium nitrite, sodium nitrate, and dissolved gibbsite are also sparse. For example, for solutions of (i) sodium nitrate and sodium phosphate, data are only available at 30 and 50 °C, and for (ii) dissolved gibbsite in sodium hydroxide and sodium phosphate, only two data points are available at 20 and 40 °C. There is no data available on mixtures of sodium hydroxide, sodium phosphate, sodium fluoride, and dissolved gibbsite. These knowledge gaps were identified in a technical review of waste solubility data and the impact of dilution on solution stabilities and will be addressed in this work to predict aluminum hydroxide and sodium phosphate solubility in multicomponent electrolytes upon dilution, and upon variation of temperature. Results will provide the technical basis to develop accurate models for (i) gibbsite solubility and mass transfer of aluminum between solid and liquid forms following the sluicing of sludge and saltcake with water; and (ii) further blending of these suspensions with bismuth from bismuth phosphate waste, and zirconium and uranium left from the fuel decladding. This work will be essential to developing a disposition path for retrieval solutions from bismuth phosphate wastes. This effort would also support sludge washing to further reduce phosphate concentration if that process were to be added back to the flowsheet in the future.

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Automated Particle Analysis of Hanford Tank Wastes 241-AN-106, 241-AN-101, and 241-AW-105

This effort is involved in developing particle size and density distribution (PSDD) for the major phases within Hanford tank waste sludge. The object of this work has been to use automated particle analysis (APA) methods on the Scanning Electron Microscope (SEM) to provide PSDDs. The PSDD can be used to quantify the proportion of gibbsite particles likely to settle quickly and enable blending of wastes that may be prone to pipeline plugging such as the uranium phase, clarkeite with other wastes. The Hanford tank waste solids were analyzed with SEM combined with x-ray Energy Dispersive Spectroscopy (EDS) using APA. This method can allow thousands of individual particles to be characterized and so may provide a more representative view of the samples and information PSDDs. We characterized several as-received sludge samples and developed PSDD with APA. Sample preparation methods were found to impact the collected results, as it was more difficult to collect representative samples of the larger particles. Much of the material was also dried and cemented together that further impacted results.

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MHTLS Cross-flow Heat Exchanger Temperature Performance Data

The presentation and supporting information provide data on the performance of an engineering-scale cross-flow heat exchanger used in hydrothermal liquefaction (HTL). Temperature profiles are provide for the process of waste water treatment sludges and a food waste. The data can be used to model larger-scale heat exchangers used in HTL.

Bioenergy Technologies Tags Heat Exchanger HTL MHT↗

Sustainable Aviation Fuel from Hydrothermal Liquefaction of Wet Wastes

Hydrothermal liquefaction (HTL) uses heat and pressure to liquefy the organic matter in biomass/waste feedstocks to produce biocrude. When hydrotreated the biocrude is converted into transportation fuels including sustainable aviation fuel (SAF). Further, by liquifying the organic matter in wet wastes such as sewage sludge, manure, and food waste, HTL can prevent landfilling or other disposal methods such as anerobic digestion, or incineration. A significant roadblock to the development of a new route for SAF is the strict approval process, and the large volumes required (>400 L) for testing. Tier α and β testing can predict some of the properties required for ASTM testing with <400 mL samples. The current study is the first to investigate the potential for utilizing wet-waste HTL biocrude (WWHTLB) as an SAF feedstock. Herein, several WWHTLB samples were produced from food waste, sewage sludge, and fats, oils, and grease, and subsequently hydrotreated and distilled to produce SAF samples. The fuels (both undistilled and distilled samples) were analyzed via elemental and 2D-GC-MS. Herein, we report the Tier α and β analysis of an SAF sample derived originally from a WWHTLB. The results of this work indicate that the upgraded WWHTLB material exhibits key fuel properties, including carbon number distribution, distillation profile, surface tension, density, viscosity, heat of combustion, and flash point, which all fall within the required range for aviation fuel. WWHTLB has therefore been shown to be a promising candidate feedstock for the production of SAF.

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