10 research outputs found
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ALUMINUM AND CHROMIUM LEACHING WORKSHOP WHITEPAPER
A workshop was held on January 23-24, 2007 to discuss the status of processes to leach constituents from High Level Waste (HLW) sludges at the Hanford and Savannah River Sites. The objective of the workshop was to examine the needs and requirements for the HLW flowsheet for each site, discuss the status of knowledge of the leaching processes, communicate the research plans, and identify opportunities for synergy to address knowledge gaps. The purpose of leaching of non-radioactive constituents from the sludge waste is to reduce the burden of material that must be vitrified in the HLW melter systems, resulting in reduced HLW glass waste volume, reduced disposal costs, shorter process schedules, and higher facility throughput rates. The leaching process is estimated to reduce the operating life cycle of SRS by seven years and decrease the number of HLW canisters to be disposed in the Repository by 1000 [Gillam et al., 2006]. Comparably at Hanford, the aluminum and chromium leaching processes are estimated to reduce the operating life cycle of the Waste Treatment Plant by 20 years and decrease the number of canisters to the Repository by 15,000-30,000 [Gilbert, 2007]. These leaching processes will save the Department of Energy (DOE) billions of dollars in clean up and disposal costs. The primary constituents targeted for removal by leaching are aluminum and chromium. It is desirable to have some aluminum in glass to improve its durability; however, too much aluminum can increase the sludge viscosity, glass viscosity, and reduce overall process throughput. Chromium leaching is necessary to prevent formation of crystalline compounds in the glass, but is only needed at Hanford because of differences in the sludge waste chemistry at the two sites. Improving glass formulations to increase tolerance of aluminum and chromium is another approach to decrease HLW glass volume. It is likely that an optimum condition can be found by both performing leaching and improving formulations. Disposal of the resulting aluminum and chromium-rich streams are different at the two sites, with vitrification into Low Activity Waste (LAW) glass at Hanford, and solidification in Saltstone at SRS. Prior to disposal, the leachate solutions must be treated to remove radionuclides, resulting in increased operating costs and extended facility processing schedules. Interim storage of leachate can also add costs and delay tank closure. Recent projections at Hanford indicate that up to 40,000 metric tons of sodium would be needed to dissolve the aluminum and maintain it in solution, which nearly doubles the amount of sodium in the entire current waste tank inventory. This underscores the dramatic impact that the aluminum leaching can have on the entire system. A comprehensive view of leaching and the downstream impacts must therefore be considered prior to implementation. Many laboratory scale tests for aluminum and chromium dissolution have been run on Hanford wastes, with samples from 46 tanks tested. Three samples from SRS tanks have been tested, out of seven tanks containing high aluminum sludge. One full-scale aluminum dissolution was successfully performed on waste at SRS in 1982, but generated a very large quantity of liquid waste ({approx}3,000,000 gallons). No large-scale tests have been done on Hanford wastes. Although the data to date give a generally positive indication that aluminum dissolution will work, many issues remain, predominantly because of variable waste compositions and changes in process conditions, downstream processing, or storage limitations. Better approaches are needed to deal with the waste volumes and limitations on disposal methods. To develop a better approach requires a more extensive understanding of the kinetics of dissolution, as well as the factors that effect rates, effectiveness, and secondary species. Models of the dissolution rate that have been developed are useful, but suffer from limitations on applicable compositional ranges, mineral phases, and particle properties that are difficult to measure. The experimental bases for the models contain very few data points
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SODIUM ALUMINOSILICATE SOLIDS AFFINITY FOR CESIUM AND ACTINIDES
Washed sodium-aluminosilicate (NAS) solids at initial concentrations of 3.55 and 5.4 g/L sorb or uptake virtually no cesium over 288 hours, nor do any NAS solids generated during that time. These concentrations of solids are believed to conservatively bound current and near-term operations. Hence, the NAS solids should not have affected measurements of the cesium during the mass transfer tests and there is minimal risk of accumulating cesium during routine operations (and hence posing a gamma radiation exposure risk in maintenance). With respect to actinide uptake, it appears that NAS solids sorb minimal quantities of uranium - up to 58 mg U per kg NAS solid. The behavior with plutonium is less well understood. Additional study may be needed for radioactive operations relative to plutonium or other fissile component sorption or trapping by the solids. We recommend this testing be incorporated in the planned tests using samples from Tank 25F and Tank 49H to extend the duration to bound expected inventory time for solution
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SORPTION OF URANIUM, PLUTONIUM AND NEPTUNIUM ONTO SOLIDS PRESENT IN HIGH CAUSTIC NUCLEAR WASTE STORAGE TANKS
Solids such as granular activated carbon, hematite and sodium phosphates, if present as sludge components in nuclear waste storage tanks, have been found to be capable of precipitating/sorbing actinides like plutonium, neptunium and uranium from nuclear waste storage tank supernatant liqueur. Thus, the potential may exists for the accumulation of fissile materials in such nuclear waste storage tanks during lengthy nuclear waste storage and processing. To evaluate the nuclear criticality safety in a typical nuclear waste storage tank, a study was initiated to measure the affinity of granular activated carbon, hematite and anhydrous sodium phosphate to sorb plutonium, neptunium and uranium from alkaline salt solutions. Tests with simulated and actual nuclear waste solutions established the affinity of the solids for plutonium, neptunium and uranium upon contact of the solutions with each of the solids. The removal of plutonium and neptunium from the synthetic salt solution by nuclear waste storage tank solids may be due largely to the presence of the granular activated carbon and transition metal oxides in these storage tank solids or sludge. Granular activated carbon and hematite also showed measurable affinity for both plutonium and neptunium. Sodium phosphate, used here as a reference sorbent for uranium, as expected, exhibited high affinity for uranium and neptunium, but did not show any measurable affinity for plutonium
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USING WET AIR OXIDATION TECHNOLOGY TO DESTROY TETRAPHENYLBORATE
A bench-scale feasibility study on the use of a Wet Air Oxidation (WAO) process to destroy a slurry laden with tetraphenylborate (TPB) compounds has been undertaken. WAO is an aqueous phase process in which soluble and/or insoluble waste constituents are oxidized using oxygen or oxygen in air at elevated temperatures and pressures ranging from 150 C and 1 MPa to 320 C and 22 MPa. The products of the reaction are CO{sub 2}, H{sub 2}O, and low molecular weight oxygenated organics (e.g. acetate, oxalate). Test results indicate WAO is a feasible process for destroying TPB, its primary daughter products [triphenylborane (3PB), diphenylborinic acid (2PB), and phenylboronic acid (1PB)], phenol, and most of the biphenyl byproduct. The required conditions are a temperature of 300 C, a reaction time of 3 hours, 1:1 feed slurry dilution with 2M NaOH solution, the addition of CuSO{sub 4}.5H{sub 2}O solution (500 mg/L Cu) as catalyst, and the addition of 2000 mL/L of antifoam. However, for the destruction of TPB, its daughter compounds (3PB, 2PB, and 1PB), and phenol without consideration for biphenyl destruction, less severe conditions (280 C and 1-hour reaction time with similar remaining above conditions) are adequate
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ANALYSIS OF THE LEACHING EFFICIENCY OF INHIBITED WATER AND TANK 23H SIMULANT IN REMOVING RESIDUES ON TANK 48H WALLS
Solid residues on two sets of thermowell pipe samples from the D2 riser in SRS Tank 48H were characterized. The residue thickness was determined using the ASTM standard D 3483-05 and was found to be three order of magnitudes below the 1mm thickness estimated from an earlier video of the tank cooling coil inspection. The actual estimated thickness ranged from 4 to 20.4 microns. The mass per unit area ranged from 1 to 5.3 milligrams per square inch. The residues appear to consist primarily of potassium tetraphenylborate (39.8 wt% KTPB) and dried salt solution (33.5 wt% total of nitrates, nitrites and oxalate salts), although {approx}30% of the solid mass was not accounted for in the mass balance. No evidence of residue buildup was found inside the pipe, as expected. The residue leaching characteristics were measured by placing one pipe in inhibited water and one pipe in DWPF Recycle simulant. After soaking for less than 4 weeks, the inhibited water was 95.4% effective at removing the residue and the DWPF Recycle simulant was 93.5% effective. The surface appearance of the pipes after leaching tests appeared close to the clean shiny appearance of a new pipe. Total gamma counts of leachates averaged 48.1 dpm/ml, or an equivalent of 2.35E-11 Ci/gm Cs-137 (dry solids basis), which is much lower than the 1.4 E-03 Ci/gm expected for Tank 48 dry slurry solids
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SENSITIVITY ANALYSIS OF A TPB DEGRADATION RATE MODEL
A tetraphenylborate (TPB) degradation model for use in aggregating Tank 48 material in Tank 50 is developed in this report. The influential factors for this model are listed as the headings in the table below. A sensitivity study of the predictions of the model over intervals of values for the influential factors affecting the model was conducted. These intervals bound the levels of these factors expected during Tank 50 aggregations. The results from the sensitivity analysis were used to identify settings for the influential factors that yielded the largest predicted TPB degradation rate. Thus, these factor settings are considered as those that yield the ''worst-case'' scenario for TPB degradation rate for Tank 50 aggregation, and, as such they would define the test conditions that should be studied in a waste qualification program whose dual purpose would be the investigation of the introduction of Tank 48 material for aggregation in Tank 50 and the bounding of TPB degradation rates for such aggregations
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RECENT STUDIES OF URANIUM AND PLUTONIUM CHEMISTRY IN ALKALINE RADIOACTIVE WASTE SOLUTIONS
Solubility studies of uranium and plutonium in a caustic, radioactive Savannah River Site tank waste solution revealed the existence of uranium supersaturation in the as-received sample. Comparison of the results to predictions generated from previously published models for solubility in these waste types revealed that the U model poorly predicts solubility while Pu model predictions are quite consistent with experimental observations. Separate studies using simulated Savannah River Site evaporator feed solution revealed that the known formation of sodium aluminosilicate solids in waste evaporators can promote rapid precipitation of uranium from supersaturated solutions
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REACTIVITY OF RESORCINOL FORMALDEHYDE RESIN WITH NITRIC ACID
Solid-state infrared spectroscopy, differential scanning calorimetry, and elemental analysis have been used to evaluate the reactivity of resorcinol formaldehyde resin with nitric acid and characterize the solid product. Two distinct reactions were identified within the temperature range 25-55 C. The first reaction is primarily associated with resin nitration, while the second involves bulk oxidation and degradation of the polymer network leading to dissolution and off-gassing. Reaction was confirmed with nitric acid concentrations as low as 3 M at 25 C applied temperature and 0.625 M at 66 C. Although a nitrated resin product can be isolated under appropriate experimental conditions, calorimetry testing indicates no significant hazard associated with handling the dry material