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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Radiolytic transformation of AHA under single-cycle conditions

Historically, the radiation robustness of extractant ligands and the impact of their radiolysis products have been used to evaluate the radiolytic feasibility of solvent system formulations for used nuclear fuel (UNF) reprocessing. However, other key additives (e.g., reducing and hold-back reagents) are employed by these solvent systems. These chemical species have typically been overlooked from a radiolytic perspective, and consequently little is known on how they impact process performance. Therefore, to holistically support the development of advanced, simplified, single-cycle flowsheets for UNF reprocessing, the radiation robustness of two key proposed additives – (i) the complexing reductant acetohydroxamic acid (AHA) and (ii) the hold-back reagent 1,2-cyclohexylenedinitrilotetraacetic acid (CDTA) – have been evaluated under envisioned process conditions using a combination of steady-state gamma and time-resolved pulsed electron irradiation techniques.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Purification of U from U-10Mo scrap generated during the fabrication of high performance research reactor fuel

A low enriched U-Mo alloy fuel is under development to replace highly enriched U fuels currently used in United States high performance research reactors. The alloy casting and fuel fabrication processes will generate scrap streams containing low enriched U (LEU) which must be recovered. Solvent extraction processes were designed using the Argonne Model for Universal Solvent Extraction (AMUSE) to purify solutions containing 20 and 50 g/L U. The feed for the solvent extraction processes was prepared from solutions generated from the dissolution of U-10Mo-Zr foils and U-10Mo-Zr-Al mini-plates. The U purification processes were demonstrated using two, 16-stage banks of miniature mixer-settlers. The solvent extraction experiments demonstrated that all design objectives for the U purification processes could be met. The U recovery in the product stream for each flowsheet was ≥99.9%. The flowsheet demonstrations also showed that the purity of the U Product will meet the requirements of the ASTM International C1462-21 specification for LEU metal enriched to less than 20% 235 U. In conclusion, the AMUSE modeling for both flowsheet demonstrations was validated by comparing predicted and measured concentrations of U, Mo, and Zr in the exit streams and stage samples at steady-state conditions in the mixer-settlers.

modified PUREX process↗
DOE OSTI2025

Developing Fluorescence-Based Sensors to Support Rare Earth Element Separation

Rare earth elements (REEs) are essential to most renewable energy technologies. Unfortunately, as we transition to sustainable energy production, the demand for REEs is rapidly growing well beyond current rates of production. As a result, novel means of efficient, scalable, and easily adaptable methods for processing primary and recycle feedstocks are needed. Development and integration of sensors for highly selective in-line monitoring can support more efficient design and testing of such novel separation processes, as well as more cost-effective deployment of those separation flowsheets. Work here will explore the application of fluorescence spectroscopy, a highly sensitive and selective technique, to quantify multiple lanthanides in complex mixtures including known interferents or quenching agents. Results include identification of the optimal excitation wavelength and the limit of detection of various rare earth elements as well as the performance of data-science-based quantification approaches in streams where “unknowns” are present. Overall, the data science tools in conjunction with optical sensor data were able to quantify analytes in the presence of other lanthanides which can be anticipated in the actual industrial stream. Here we include characterization of lanthanides in a microfluidic device similar to those used in new process development. This study demonstrates the capability of utilizing fluorescence spectroscopy to quantify analytes in a complicated solution matrix, suggesting this is a successful approach for in-line monitoring to optimize the separation efficiency in an industrial stream.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Multi-Sourced Collaboration for the Production and Refining of Rare Elements and Critical Metals (Final Technical Report)

The project objective was to develop a feasible and cost-effective method for recovering rare earth elements (REEs) and critical materials (CMs) from coal and coal byproducts, resulting in high-purity individually separated REEs and CMs. The targeted REEs included Y, Pr, Nd, Gd, Dy, and Sm, with a purity of over 99.5%, while the CMs included Co, Mn, Ga, Sr, Li, Ni, Zn, and Ge, with a purity of over 90%. The project aimed to design a prototype facility capable of producing 1-3 tonnes/day of high-purity REO mixes. The work was divided into four designated circuits: 1) REE extraction and concentration, 2) REE separation and purification, 3) RE metal production, and 4) CM production. To achieve these goals, the project involved 11 tasks, including technology reviews, research, process flow diagram development, mass balance estimation, and preliminary technical-economic analysis. The project team included researchers from the University of Kentucky, University of Alabama and Virginia Tech as well as process specialists from Argonne National Laboratory. MP Materials provided technical support regarding rare earth markets and processing while Alliance Coal performed resource assessment. The project included a market analysis for Nd/Pr, Tb, Dy, Gd, Y, Co, Mn, Li, Sr, Ga, Ni, Zn, and Ge. These analyses provided insights into the supply and demand trends as well as historic and future projections of market price relative to purity requirements for these elements. Two coal resources were selected for the project: the West Kentucky No. 13 (Baker) Seam and an undisclosed lignite resource in the Illinois coal basin. The estimated quantities of REEs in these resources were calculated based on production samples and drilling data. It was estimated that there is adequate supply for an operation producing one metric ton daily of higher purity mixed rare earth oxides (MREO) for approximately 20 years at a site located in western Kentucky. In Circuit 1, project data was obtained from a pilot heap leach and REE concentration facility. It was concluded that the existing circuit, which generated a MREO concentrate, two types of CM mixed products, and Li- and Sr-containing waters, would be suitable feed for circuits 2-4. Data from the first-of-its-kind coal coarse refuse heap leach pilot pad played a crucial role in estimating reliable elemental concentrations of the pregnant leaching solution (PLS). The average total REE concentration in the PLS was found to be 28.6 ppm. In Circuit 2, several concepts were explored including a novel process referred to as solvent-assisted chromatography (SAC). This concept involved a novel columnar reactor that incorporated multiple mixer/settlers, thereby enabling the operation of counter-flowing aqueous and organic phases. Unfortunately, due to project time constraints, a complete fundamental modeling analysis could not be completed to fully evaluate the technology. Molten salt electrowinning was considered as an alternative for circuit 3 following circuit 2 purification circuit utilizing the novel SAC process. A mass and energy balance of Nd reduction to metal in a fluoride containing molten salt electrolyte was conducted. Comparisons were made with the current state of Asian molten salt electrorefining, and potential improvements in siphoning rare earth metals (REM) from the reactor were presented. A cost estimate was performed for the production of 1 tonne per day, which yielded a total of $2.29 million for the nine electrowinning (EW) cells required. The selected option for circuits 2 and 3 was a plasma distillation process, which initially separates rare earth elements (REEs) from other elements. This is followed by selective electrowinning in various ionic liquids. The selection was made on the basis of thermodynamic modeling and experimental data previously published by a project partner. The combination offers an innovative approach to integrated refining and RE metal production. For Circuit 4, an extensive literature review was conducted for the processing of the CMs. The ultimate decision was to utilize a combined plasma and ionic liquid process as well to produce individual high-purity concentrates of Zn, Ni, Co, Mn, and Mg. A separate flowsheet for Li and Sr was recommended, which would yield carbonates of these elements. Due to the lack of suitable experimental data at this time, a process recommendation could not be provided but several methods have been proposed for consideration. Lastly, a techno-economic analysis (TEA) was conducted to assess the effectiveness of the proposed process for further investigation. The TEA results revealed a capital expense (CapEx) of $737 million and an annual operational expense (OpEx) of $220 million. Due to the selected elements, the hypothetical heap leach pad can produce 1 metric tonne per day of REO equivalent, but a conscious decision was made to only treat targeted REEs, resulting in the production of 0.4 metric tonne of REM. An estimated annual revenue of $90.87 million was projected based on standard market pricing information provided by the funding agency. During the TEA, ten different modules were evaluated for costing purposes. The precipitation circuit was identified as the largest single operational expense, followed by the Mg/Mn process due to the amount of treated metal. In terms of capital expenditures, the heap leach process incurred the highest cost, followed by the Mg/Mn process. The scalability of the plasma process is a crucial consideration since the reactors cannot be scaled beyond the largest demonstrated size due to their reliance on surface area of the slag and vapor phase. The purity estimate for the REEs are generally 98%±2% to produce a metal. The purity level being lower than the project objective was due to the lack of specific experimental data needed to tighten the tolerance of the estimates. Based on literature and previous experience, the CMs are estimated as follows; Ga (95%+, metal), Sr (95%+, carbonate), Li (95%+, carbonate), Ni (98%±2%, metal), Zn (95%+, metal sponge), Ge (95%+, metal), Co (98%±2%, metal), and Mn (98%±2%, metal).

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2021

Nuclear Fuels and Reprocessing Technologies: A U.S. Perspective

Reprocessing and/or waste management issues are of concern to the “back end” of the nuclear fuel cycle. Of course, there are a great many “nuclear fuel cycle” scenarios to consider; if not in practice, then at least in theory. The simplest conceptually is the “once through” fuel cycle in which the spent fuel is discarded. The more complex fuel cycle scenarios involve reprocessing spent nuclear fuels and a family of nuclear reactor technologies to accommodate burning and breeding for various military and commercial needs. Therefore, the selection of a specific “fuel cycle” is what ultimately imposes the engineering requirements of the reprocessing and waste management technologies. No one part is independent of the other parts in a fuel cycle flowsheet; all parts are fully integrated. This paper presents a summary of radiochemical processes, nuclear reactor technologies, nuclear fuel types, and the reprocessing technologies that serve the different nuclear fuel types. Comprehending how this series of topics are related to each other is a prerequisite to understanding the requirements of any reprocessing strategy. The summary materials presented here are selective, as opposed to comprehensive. More detailed information on any one subject can be found in the reference materials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Jacobian-based Model Diagnostics and Application to Equation Oriented Modeling of a Carbon Capture System

Equation-oriented (EO) modeling has the potential to enable the effective design and optimization of the operation of advanced energy systems. However, advanced modeling of energy systems results in a large number of variables and non-linear equations, and it can be difficult to search through these to identify the culprit(s) responsible for convergence issues. The Institute for the Design of Advanced Energy Systems Integrated Platform (IDAES-IP) contains a tool to identify poorly scaled constraints and variables by searching for rows and columns of the Jacobian matrix with small L2-norms so they can be rescaled. A further singular value decomposition can be per-formed to identify degenerate sets of equations and remaining scaling issues. This work presents an EO model of a flowsheet developed for post-combustion carbon capture using a monoethanolamine (MEA) solvent system as a case study. The IDAES diagnostics tools were successfully applied to this flowsheet to identify problems to improve model robustness and enable the optimization of process design and operating conditions of a carbon capture system.

Allan, Douglas↗
DOE OSTI2021

Pilot-Scale Testing of an Integrated Circuit for the Extraction of Rare Earth Minerals and Elements from Coal and Coal Byproducts Using Advanced Separation Technologies

The primary objective of this project was to develop and demonstrate an integrated pilot-scale circuitry for recovering high-value rare earth elements (REEs) from coal and coal byproducts. The target performance was to produce a mixed REE product with content of at least two percent by weight on a dry mass basis in a cost-effective and environmentally benign manner. During the first nine months of the project period (Phase 2 Budget Period 2), pilot plant construction was completed including all field site startup activities such as permitting, engineering design, procurement/bidding, unit fabrication, site construction, equipment installation, module assembly, safety training, and circuit shakedown. During the remaining 21 months of project period (Phase 2 Budget Period 3), detailed field-testing activities were performed including feedstock sample collection and preparation, exploratory testing, circuit modification, detailed parametric study, and performance optimization. A detailed techno-economic analysis was performed based on the pilot plant testing findings which provided various scenarios for REE production. The project successfully accomplished the proposed target performance by producing mixed rare earth oxide (REO) with greater than 90% purity by weight in a continuous pilot scale operation from two distinctly different coarse refuse materials (i.e., West Kentucky No. 13 and Fire Clay coal seams), and at least three secondary sources (i.e., heap leach process and naturally formed acid mine drainage system). Project partners included the University of Kentucky, Virginia Tech, West Virginia University, Alliance Coal, Blackhawk Mining, Mineral Refining Company, and Mineral Separation Technologies. The pilot scale test facility was constructed at a former mining complex owned by Alliance Natural Resource Partners (Alliance Coal). The site was rehabilitated to accommodate the equipment installation, construction and fabrication, electrical power requirement, water line management and containment. The process units constructed and installed included X-ray sorting unit, crushing and grinding unit, physical separation unit, acid leaching unit, solvent extraction unit, and wastewater management unit. A rare earth mineral concentration unit was constructed as a standalone unit for flexible operation. A detailed environmental assessment and control plan was carried out to identify and quantify any potential impacts of the pilot-scale processing circuitry on the human and eco-system health and well-being. Corresponding mitigation strategies and control measures were provided. A conceptual flowsheet was developed to effectively remove thorium and uranium from high purity rare earth oxide mix or any potential radionuclide enriched stream. The two distinct feedstock materials were secured from the Blackhawk Mining Complex in eastern Kentucky where the Fire Clay (Hazard No. 4) seam is processed. The West Kentucky No. 13 (Baker) coarse refuse material was collected from an active process stream at an Alliance coal preparation plant located in western Kentucky. Characterization analysis indicated that both of feed materials generated from the two sources contained >300 ppm of TREEs on a dry whole mass basis which met the requirements for a qualified feed stock. The two feedstocks were further upgraded using a dual x-ray sorter to prepare the feed material for hydrometallurgical circuit. Thermal treatment on feed material prior to leaching was found to: 1) improve the leaching recovery of REEs, 2) increase the leaching kinetics, and 3) allow the leaching reaction to occur at lower acidity. Roasting at 600°C was selected as the pre-treatment condition for both West Kentucky No. 13 and Fire Clay coarse refuse material. Over 40% of leaching recovery was achieved by roasting West Kentucky No. 13 material having a top particle size of 3 mm in the pilot scale operation using 1.2M sulfuric acid leaching at 75OC. Initial pilot scale testing involved continuous operation of the pilot plant for 94 hours. The leaching unit was operated at solid-to-liquid ratio of 1 to 10 (w/v) using 0.5M sulfuric acid solution at a temperature of 75°C. The continuous solvent extraction circuit utilized rougher and cleaner units with DEHPA and TBP as the extractants. An innovative stripping circuit was developed to accumulate the REE concentration in the stripping solution to a level above 600 ppm. A bleed stream from the recycled strip solution was treated using oxalic acid precipitation which produced a high grade rare earth oxalate. The oxalate product was roasted to remove the oxalate which produced a rare earth oxide product having a purity greater 90%. Due to high concentrations of contaminant ions in the pregnant leach solution (PLS), a modified flowsheet was developed that involved pre-concentration of the REEs using multiple stages of precipitation and redissolution. The advantage of this process was improved removal of contamination before the downstream purification process and a significant cost reduction relative to the circuit that utilized the solvent extraction process. The modified circuitry included processes involving leaching, multistage precipitation, redissolution, and oxalate precipitation followed by roasting of the oxalate product. The circuit produced a mixed REO that was 92.96% pure from the initial test. A detailed parametric test plan was carried out which involved varying key parameters including solids feed rate, acid flowrate, acid concentration, multistage precipitation pH, redissolution pH, oxalate precipitation dosage and pH. The response variables included REE recovery, contaminant recovery, REO product grade and overall chemical consumption. Test results indicated that the acid-to-solid ratio is the key parameter to leaching efficiency as performance deteriorated with an increase in solids concentration. The optimal pH determined for REE precipitation and redissolution was 6.5 and 2.5, respectively. Additional tests were conducted to further improve the flowsheet. Recirculating a portion of the PLS to the feed of the leach tanks improved the leaching performance by lowering the pH of the leaching system and reducing the contamination recovery by shortening the residence time. Moreover, the removal of Al prior to REE precipitation significantly reduced the oxalic acid consumption in the oxalate precipitation circuit. The modified circuit produced over 90% grade REO by weight from both West Kentucky No. 13 and Fire Clay coarse refuse material in pilot scale continuous test programs. A case analysis model was developed to project the REE and major contaminants concentration in each PLS stream based on the leaching condition, pH cut point, and oxalic acid dosage. A correlation was established using empirical and semi-empirical models. Using the models, chemical consumption required for each stage was predicted based on the projected performance of the hydrometallurgy circuit. After identifying the optimum conditions, validation tests were carried out for the treatment of both West Kentucky No. 13 and Fire Clay coarse refuse materials in the pilot plant. The actual circuit performance and chemical consumptions were very close to the model predictions. Other than the two coarse refuse sources, several secondary feedstocks were also tested in the pilot plant facility. A “heap leach” system was constructed using the coarse refuse material generated from cleaning the West Kentucky No. 13 seam coal. Using the two stage SX rougher and cleaner circuit, a concentrate with a grade >90% REO was produced while recovering >97% of the REEs from the heap leach PLS. Naturally generated acid mine drainage (AMD) from West Kentucky No.13 mine was processed using the multistage precipitation circuit in the pilot plant in a test conducted for a period of 32 hours. The final grade of the mix RE oxide produced from the AMD was 90.84% with an overall circuit recovery of 64%. The primary source of REE was the selective precipitation steps involving iron and aluminum rejection. The hydrophobic-hydrophilic separation (HHS) process was proven to effectively recover coal from fine waste materials. For REM recovery, the HHS process was able to produce concentrates at grades of approximately 1.8% REE on an ash basis; however, recovery values were typically low, <10%, under the optimal conditions determined in the laboratory-scale testing. Staged testing of the pilot-scale HHS process for coal recovery and semi-continuous laboratory testing for REM testing showed that a total concentration ratio of more than 15x was observed for the REM recovery process. A circuit simulation package was developed for REE extraction and purification using a spreadsheet-based platform (Microsoft Excel). The REESim circuit simulation package is configured to track the mass and volume flows of components passing through a series of unit operations specified and configured by the user. The mass rates can then be utilized by the user to determine important performance indicators such as product mass yields, concentrate purity levels, element-by-element recoveries, and so forth. The techno-economic analysis showed that the roasting and leaching operations were the most expensive capital items, each contributing approximately 30% to the total capital cost. One notable contributor to the high production costs was the low REE recovery observed in the pilot scale trials. The product basket price was shown to have a strong influence on the economic viability of the scenarios, with the scandium price being the most significant influencer. Operating cost was shown to be extremely sensitive to REE recovery, REE feed grade, and leaching acid consumption. An analysis of ten different scenarios for a 500 t/h commercial operation revealed that three were economically favorable, producing internal rates of return varying from 27.7% to 33.1% and payback periods of 4 to 5 years. The project successfully developed and demonstrated a process to recover REEs from coal and coal byproducts in a pilot-plant operation which consistently produced over 90% grade REO mix from varies types of feedstocks. Commercialization analysis showed that the technology readiness level successfully achieved TRL 6 at the end of the project and demonstrated the need and the potential for scaling the process to further advance the technologies toward the goal of providing a domestic supply of REEs at a commercial scale.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2022

Sludge Processing Options for early HLW Treatment at Hanford

The U.S. Department of Energy’s (DOE) Hanford Site has 177 underground storage tanks that contain wastes from past nuclear fuel reprocessing and waste-management operations. Over 20% of this waste is in the form of an insoluble sludge that will require solids concentration and washing prior to vitrification for long-term disposal. An assessment of potential flowsheet operations to support feed preparation activities prior to high level waste (HLW) vitrification has been conducted to better evaluate pretreatment processing options. Settling studies assessing the baseline approach of a settle-decant method were explored as well as a crossflow filtration system to be used alternatively for concentrating and washing HLW sludge. Significant variations in behavior of settling rates and sludge characteristics give reason to evaluate alternative pretreatment options for the HLW. Non-radioactive sludge containing iron oxide, boehmite, and gibbsite were evaluated via gravity settling and crossflow filtration to determine the behavior of these compounds in various tank waste matrices. Understanding the predictive capabilities of HLW solids settling as well as sludge concentration via crossflow filtration can help provide technical guidance during flowsheet planning.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Implementation of the Glycolate Destruction Process with Sodium Permanganate in the Defense Waste Processing Facility (DWPF) - 20141

The Savannah River Site (SRS) seeks to replace formic acid with glycolic acid as a chemical reductant in the Defense Waste Processing Facility (DWPF), where borosilicate glass is mixed with high-level radioactive waste, melted at high temperatures, then poured into stainless steel canisters for safe storage. Prior research and development have demonstrated the feasibility and advantages of the new nitric-glycolic acid flowsheet over the current nitric-formic acid flowsheet to chemically adjust the radioactive sludge slurry waste in the Sludge Receipt and Adjustment Tank (SRAT) prior to vitrification. Use of glycolic acid reduces hydrogen and ammonia generation during the reduction process, thus reducing flammability hazards and purge requirements in the DWPF processing vessels. In addition, glycolic acid will support the new Salt Waste Processing Facility (SWPF) by allowing for receipt of higher volumes of waste due to reduction of flammable gases, increased boil-up rates in the vessels, and easing the processing of future sludge batches containing high levels of mercury. However, during DWPF operations, trace amounts of glycolate are anticipated to be entrained in the recycle stream and sent to the Concentration, Storage, and Transfer Facilities (CSTF) via the Recycle Collection Tank (RCT). The RCT receives condensate from the Slurry Mix Evaporator Condensate Tank (SMECT) and Off-gas Condensate Tank (OGCT) that may contain unreacted glycolate. A literature review found the potential for hydrogen generation due to thermolysis of glycolate in caustic CSTF conditions. Savannah River National Laboratory (SRNL) conducted several tests on simulant and radioactive waste from various tanks at SRS and confirmed that glycolate added to waste at concentrations of approximately 1000 mg/L and higher generates hydrogen through thermolysis. There are potential operating scenarios in the future where glycolate concentration could exceed 1000 mg/L in the 2H Evaporator Drop Tank, the highest accumulation point for DWPF organics received via recycle. These findings presented a need to develop another process to mitigate the impact of glycolic acid to the CSTF. Several DWPF compatible options were evaluated for their ability to destroy glycolate in the DWPF recycle stream under various processing conditions, thereby mitigating its introduction to the CSTF. Downselection testing identified sodium permanganate as the most promising and simplest option to oxidize glycolate. It has been demonstrated to be effective in various RCT simulant compositions, operating temperatures, oxidant addition rates, solution pH, and initial glycolate concentrations. A feasibility study identified existing tanks within the facility that could be used for receiving and storing the commercially available sodium permanganate, as well as feeding it to the RCT for processing. The use of existing equipment as well as the ability to purchase the pre-mixed chemical reduces implementation and operational complexity. The downstream impacts of the sodium permanganate reaction were also evaluated and demonstrated to have minimal impact on other chemical species present in the RCT and CSTF, as well as on the materials of construction of the RCT and CSTF vessels and associated piping and instrumentation. Future work is in progress to validate the glycolate destruction process with testing in actual radioactive RCT waste before implementation in DWPF. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Recovery of valuable metals from electronic waste using a novel ammonia-based hydrometallurgical process

The growing quantity of waste electrical and electronic equipment (WEEE), also known as electronic waste (E-waste), has been an area of growing public concern. The abundance of valuable metals contained in waste printed circuit boards (WPCBs) has made it a promising secondary resource, especially for Cu and Au. Although the recovery of metals from WPCBs via hydrometallurgical routes has been studied extensively over the past 20 years, most of the research has been limited in the laboratory. In current hydrometallurgical processes, strong acids and expensive oxidizers are often used to ensure a high recovery of metals without considering the sustainability aspects of the environment and economics. To improve upon current hydrometallurgical offerings, the current study seeks to develop an energy-saving, environmentally friendly, economic and sustainable process to efficiently recover the valuable metals from real-world end-of-life WPCBs. The new contributions presented in this study are 1) design and evaluation of a comprehensive hydrometallurgical flowsheet; 2) employment of real end-of-life PCBs as feed materials in an investigation on Cu-NH3 leaching kinetics; 3) further application of kinetic model on a counter flow process simulation; and 4) evaluation of the influences by co-existing metals in Au-S2O3 leaching and recommendation for favorable leaching conditions.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2020

Dissolution of Fluoride Salts in Hanford Tank Waste

The Direct Feed High-Level Waste (DFHLW) strategy seeks to bypass the Hanford Waste Treatment and Immobilization Plant Pretreatment Facility while retaining some processing functions to maximize waste feed loading and minimize high-level waste (HLW) waste volume. The DFHLW flowsheet needs leaching, washing, and solids concentration operations either in new or existing tanks. The effectiveness and efficiency of sludge washing has a substantial impact on DST space, mission duration, and the evaporation and low-activity waste (LAW) treatment operations required by these large wash-water additions. One target species requiring washing is fluoride. The HLW glass composition limits for fluorine drive operations to dissolve fluoride-bearing salts into the LAW fraction and thereby maximize waste loading in HLW glass. The fluoride in many high-level wastes at Hanford is predominantly in the form of fluoride-salt precipitates: villiaumite (NaF), kogarkoite (Na 3 FSO 4 ), and natrophosphate (Na 7 F(PO 4 ) 2 ·19H 2 O). Fluoride produces melter off-gas that creates corrosion risk in the off-gas system piping, while the sulfate and phosphate in the fluoride double salts kogarkoite and natrophosphate can be detrimental to glass waste loading. Fluoride salts are sparingly soluble, with solubilities ranging from approximately 40 to 130 kg per kL of pure water, and the dissolution kinetics of the three fluoride salts are not well known. Unexpected delays in a tank dissolution process could be encountered as a result of the lack of information about dissolution rates. In addition, if the double salts show transient non-stoichiometric dissolution of fluoride versus phosphate or sulfate, unexpectedly high concentrations of one of these other constituents could be produced. Washington River Protection Solutions authorized Pacific Northwest National Laboratory to collect the available data for fluoride salt dissolution rate, provide a scoping estimate of dissolution time if possible, and identify gaps in the understanding and predictive capability for estimating dissolution time. Open literature and Hanford reports were reviewed to document, understand, and (where possible) evaluate limitations on fluoride salt equilibria and dissolution kinetics, including both mass transport and surface reaction rate. Scoping estimates of dissolution time were made for mass-transfer-controlled dissolution of spherical particles of fluoride salts suspended in liquid. This is not the only potential governing mechanism; dissolution could be substantially slower if the surface reaction rate (the rate of release of ions from the surface) is the controlling mechanism. When the minimum amount of water for complete dissolution is used and the slip velocity between the liquid and suspended particles is less than or equal to the terminal settling velocity, the estimated mass-transfer rates allow 0.1 mm particles of fluoride salt to dissolve in minutes at 25 °C in water containing no other dissolved salts. Much larger solids, such as the 6-mm chunks that have been seen in heels, could take a few hours to more than a week to dissolve. The actual dissolution times will depend strongly on the actual slip velocity, the extent of particle suspension, constraint by surface reaction rates, the ratio of solvent to solid, and the presence of common ions that shift the solubility equilibria to restrict dissolution of fluoride salts.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Feasibility of carbon foam-based sorbents for the abatement of gaseous mercury and iodine

The U.S. Department of Energy Hanford Site in Washington State is in the process of commissioning the Waste Treatment and Immobilization Plant to process a portion of the 54 million gallons of radioactive and chemical waste from cold war weapon production. Technologies for the capture of volatile species of concern are still being assessed, and new methods and materials are developed as operational and flowsheet mission risks are identified. One such area still being assessed is the abatement efficacy of the Carbon Adsorber units to retain gaseous mercury and 129 I released during processing. It is challenging to predict the mercury chemistry due to the variability of the feed, and different methods/materials are required for the capture of gaseous Hg 0 and Hg II compounds. In this study, the feasibility of using developmental carbon foam (CF) sorbents for the capture of iodine and mercury was assessed using static and dynamic flow testing and compared against a commercially available sorbent, BATII-37. Both CF and CF functionalized with bismuth particles (CF-Bi) chemisorbed iodine, and CF-Bi had similar mercury capture performance to BATII-37 in dynamic flow tests. While species loading concentrations were measurable, limitations in achieving a mass balance prevented a full evaluation of capture efficacy. Nonetheless, the results serve as an important first step in demonstrating the potential for simultaneous iodine and mercury capture.

Hanford site↗
DOE OSTI2023

Investigation of Potential Routes for Titanium and Mercury Concentrations within Salt Waste Processing Facility

Savannah River National Laboratory (SRNL) has been requested by Savannah River Mission Completion (SRMC)/ Salt Waste Processing Facility (SWPF) personnel to investigate the potential routes for titanium and mercury accumulations within the SWPF Flowsheet. The first part of this work examined how various forms of mercury can migrate through the solvent extraction system. This entailed single stage distribution tests, a multi-stage Extraction-Scrub-Strip (ESS) test, and a detailed speciation analysis of several salt batch feed samples.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Investigation of Mercury Compound Partitioning Through the Solvent Extraction System

Savannah River National Laboratory (SRNL) has been requested by Savannah River Mission Completion (SRMC)/ Salt Waste Processing Facility (SWPF) personnel to investigate the potential routes for titanium and mercury accumulations within the SWPF Flowsheet. This report documents work performed to examine how various forms of mercury can migrate through the multiple flowsheets of a solvent extraction system. This entailed 29 single stage distribution tests, a multi-stage Extraction-Scrub-Strip (ESS) test, and a detailed speciation analysis of several salt batch feed samples.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Simulant Development of Potential 200 West Area Waste Feeds

Preliminary planning for retrieval, qualification, and pretreatment of waste in Hanford’s 200 West Area (200W) has begun as part of the West Area Risk Management project. Experimental studies to technically mature pretreatment process operations will likely be needed because of the uniqueness of 200W waste. Pacific Northwest National Laboratory formulated five simulants to represent 200W-qualified feed based on the preliminary flowsheet provided by Washington River Protection Solutions, LLC. The simulant recipes were devised using applicable historical information as a reference point to support the use of the flowsheet waste vectors, which were combined into five distinct groups. These five groups formed the basis for the liquid composition targets that were adapted into recipes using charged-balanced salt species. The liquid phase recipes were batched in 1-L quantities and analyzed at Pacific Northwest National Laboratory. Once confirmed to be stable, the liquid solutions were tested for compatibility with candidate solid components. Specific solid components were recommended based on cross-examining the proposed solid phases in the flowsheet with relevant data from the literature. Mixtures of solid components were added to aliquots of the liquid batches and sub-sampled to measure particle size distribution. The measured distribution was compared to independently created benchmark distributions appropriate for each simulant. This process was iterated until a solid phase composition that resulted in a representative particle size distribution was found. After the final compositions were confirmed, a suite of chemical and physical characterization data was collected. This report describes the simulant basis, formulation methodology, laboratory measurements, and data collected for the recipes recommended to represent 200W waste feeds.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Iodine Speciation Basis and Gap Analysis for Hanford Tank Farm Inventory and during Processing

Pacific Northwest National Laboratory (PNNL) is providing baseline technical support to Washington River Protection Solutions (WRPS) for the One System River Protection Project (RPP) Integrated Flowsheet team. This report documents the evaluation of the technical bases available to support iodine speciation and distribution within Hanford wastes and subsequent waste streams generated during direct feed low-activity waste (DFLAW) pretreatment operations (specifically, waste retrievals and staging, and particle filtration and cesium decontamination using crystalline silicotitanate (CST) ion exchange [in the tank side cesium removal (TSCR) system]. The task performed a literature survey of information related to iodine species in environments analogous to Hanford tank waste and the subsequent waste streams to define a technical basis for the possible iodine speciation in Hanford waste. In doing so it can be determined how likely laboratory studies on iodine speciation in tank waste are to be universally relevant across the Hanford tanks. The task evaluated iodide and iodate as the primary species of interest with a focus on organo-iodine where appropriate.

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DOE OSTI2021

Proton Nuclear Magnetic Resonance (H NMR) of Glycolate in Real Waste: Developing and Testing Analytical Methods for the Savannah River Site Liquid Waste System

In preparation for implementing the NG acid flowsheet for the SRS LWS, analytical methods for determining glycolate at low concentration are desired to support system management and safety. Previous work documented that the IC method performed well for samples with low to moderate ionic strength. That work also included a scoping effort to determine if an alternate analytical strategy using H NMR would complement and extend the capabilities of the IC method. The H NMR scoping results indicated that the method had the potential to expand glycolate analysis in LWS samples to higher ionic strength tanks/solutions. The scope of this work is to develop innovative proton NMR techniques, including demonstrating ion exchange decontamination protocols needed for application of the technique to real waste samples. Part of radioactive waste processing at SRS uses formic acid to reduce oxidized (Hg 2+ ) to more volatile elemental Hg for steam striping, collecting, and disposal. Under acidic conditions found in the Chemical Processing Cell (CPC) at the Defense Waste Processing Facility (DWPF), formic acid has a much higher hydrogen generation rate than an alternative reductant, glycolic acid. Thus, an NG acid flowsheet has been developed utilizing glycolic acid with the benefit of easing the need for headspace monitoring requirements for hydrogen and ammonia at DWPF. Low concentrations of glycolate are conservatively assumed to be in the recycle stream, which will collect in the Recycle Collection Tank (RCT). The DWPF recycle stream collected in the RCT has a distinct pathway to the LWS waste tanks that feed the 2H and 3H Evaporator. This route involves transfer of the DWPF recycle to Tank 22 in the Concentration, Storage, and Transfer Facilities (CSTF) followed by transfer to the LWS tank farm/evaporators.

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