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Author: Publisher: ISBN: Category : Languages : en Pages :
Book Description
The H-Canyon facility will be used to dissolve Pu metal for subsequent purification and conversion to plutonium dioxide (PuO2) using Phase II of HB-Line. To support the new mission, the development of a Pu metal dissolution flowsheet which utilizes concentrated (8-10 M) nitric acid (HNO3) solutions containing potassium fluoride (KF) is required. Dissolution of Pu metal in concentrated HNO3 is desired to eliminate the need to adjust the solution acidity prior to purification by anion exchange. The preferred flowsheet would use 8-10 M HNO3, 0.015-0.07 M KF, and 0.5-1.0 g/L Gd to dissolve the Pu up to 6.75 g/L. An alternate flowsheet would use 8-10 M HNO3, 0.1-0.2 M KF, and 1-2 g/L B to dissolve the Pu. The targeted average Pu metal dissolution rate is 20 mg/min-cm2, which is sufficient to dissolve a 'standard' 2250-g Pu metal button in 24 h. Plutonium metal dissolution rate measurements showed that if Gd is used as the nuclear poison, the optimum dissolution conditions occur in 10 M HNO3, 0.04-0.05 M KF, and 0.5-1.0 g/L Gd at 112 to 116 C (boiling). These conditions will result in an estimated Pu metal dissolution rate of ≈11-15 mg/min-cm2 and will result in dissolution times of 36-48 h for standard buttons. The recommended minimum and maximum KF concentrations are 0.03 M and 0.07 M, respectively. The maximum KF concentration is dictated by a potential room-temperature Pu-Gd-F precipitation issue at low Pu concentrations. The purpose of the experimental work described in this report was two-fold. Initially a series of screening experiments was performed to measure the dissolution rate of Pu metal as functions of the HNO3, KF, and Gd or B concentrations. The objective of the screening tests was to propose optimized conditions for subsequent flowsheet demonstration tests. Based on the rate measurements, this study found that optimal dissolution conditions in solutions containing 0.5-1.0 g/L Gd occurred in 8-10 M HNO3 with 0.04-0.05 M KF at 112 to 116 C (boiling). The testing also showed that solutions containing 8-10 M HNO3, 0.1-0.2 M KF, and 1-2 g/L B achieved acceptable dissolution rates in the same temperature range. To confirm that conditions identified by the dissolution rate measurements for solutions containing Gd or B can be used to dissolve Pu metal up to 6.75 g/L in the presence of Fe, demonstration experiments were performed using concentrations in the optimal ranges. In two of the demonstration experiments using Gd and in one experiment using B, the offgas generation during the dissolution was measured and samples were analyzed for H2. The experimental methods used to perform the dissolution rate measurements and flowsheet demonstrations and a discussion of the results are presented.
Author: Publisher: ISBN: Category : Languages : en Pages :
Book Description
The H-Canyon facility will be used to dissolve Pu metal for subsequent purification and conversion to plutonium dioxide (PuO2) using Phase II of HB-Line. To support the new mission, the development of a Pu metal dissolution flowsheet which utilizes concentrated (8-10 M) nitric acid (HNO3) solutions containing potassium fluoride (KF) is required. Dissolution of Pu metal in concentrated HNO3 is desired to eliminate the need to adjust the solution acidity prior to purification by anion exchange. The preferred flowsheet would use 8-10 M HNO3, 0.015-0.07 M KF, and 0.5-1.0 g/L Gd to dissolve the Pu up to 6.75 g/L. An alternate flowsheet would use 8-10 M HNO3, 0.1-0.2 M KF, and 1-2 g/L B to dissolve the Pu. The targeted average Pu metal dissolution rate is 20 mg/min-cm2, which is sufficient to dissolve a 'standard' 2250-g Pu metal button in 24 h. Plutonium metal dissolution rate measurements showed that if Gd is used as the nuclear poison, the optimum dissolution conditions occur in 10 M HNO3, 0.04-0.05 M KF, and 0.5-1.0 g/L Gd at 112 to 116 C (boiling). These conditions will result in an estimated Pu metal dissolution rate of ≈11-15 mg/min-cm2 and will result in dissolution times of 36-48 h for standard buttons. The recommended minimum and maximum KF concentrations are 0.03 M and 0.07 M, respectively. The maximum KF concentration is dictated by a potential room-temperature Pu-Gd-F precipitation issue at low Pu concentrations. The purpose of the experimental work described in this report was two-fold. Initially a series of screening experiments was performed to measure the dissolution rate of Pu metal as functions of the HNO3, KF, and Gd or B concentrations. The objective of the screening tests was to propose optimized conditions for subsequent flowsheet demonstration tests. Based on the rate measurements, this study found that optimal dissolution conditions in solutions containing 0.5-1.0 g/L Gd occurred in 8-10 M HNO3 with 0.04-0.05 M KF at 112 to 116 C (boiling). The testing also showed that solutions containing 8-10 M HNO3, 0.1-0.2 M KF, and 1-2 g/L B achieved acceptable dissolution rates in the same temperature range. To confirm that conditions identified by the dissolution rate measurements for solutions containing Gd or B can be used to dissolve Pu metal up to 6.75 g/L in the presence of Fe, demonstration experiments were performed using concentrations in the optimal ranges. In two of the demonstration experiments using Gd and in one experiment using B, the offgas generation during the dissolution was measured and samples were analyzed for H2. The experimental methods used to perform the dissolution rate measurements and flowsheet demonstrations and a discussion of the results are presented.
Author: William J. Jenkins Publisher: ISBN: Category : Plutonium Languages : en Pages : 12
Book Description
Plutonium metal was found to dissolve readily in sulfamic acid and in mixtures of sulfamic and nitric acid. This method of dissolution is convenient in a plant process for the recovery of off-standard metal.
Author: Publisher: ISBN: Category : Languages : en Pages :
Book Description
The deinventory and deactivation of the Savannah River Site's (SRS's) FB-Line facility required the disposition of approximately 2000 items from the facility's vaults. Plutonium (Pu) scraps and residues which do not meet criteria for conversion to a mixed oxide fuel will be dissolved and the solution stored for subsequent disposition. Some of the items scheduled for dissolution are composite materials containing Pu and tantalum (Ta) metals. The preferred approach for handling this material is to dissolve the Pu metal, rinse the Ta metal with water to remove residual acid, and burn the Ta metal. The use of a 4 M nitric acid (HNO3) solution containing 0.2 M potassium fluoride (KF) was initially recommended for the dissolution of approximately 500 g of Pu metal. However, prior to the use of the flowsheet in the SRS facility, a new processing plan was proposed in which the feed to the dissolver could contain up to 1250 g of Pu metal. To evaluate the use of a larger batch size and subsequent issues associated with the precipitation of plutonium-containing solids from the dissolving solution, scaled experiments were performed using Pu metal and samples of the composite material. In the initial experiment, incomplete dissolution of a Pu metal sample demonstrated that a 1250 g batch size was not feasible in the HB-Line dissolver. Approximately 45% of the Pu was solubilized in 4 h. The remaining Pu metal was converted to plutonium oxide (PuO2). Based on this work, the dissolution of 500 g of Pu metal using a 4-6 h cycle time was recommended for the HB-Line facility. Three dissolution experiments were subsequently performed using samples of the Pu/Ta composite material to demonstrate conditions which reduced the risk of precipitating a double fluoride salt containing Pu and K from the dissolving solution. In these experiments, the KF concentration was reduced from 0.2 M to either 0.15 or 0.175 M. With the use of 4 M HNO3 and a reduction in the KF concentration to 0.175 M, the dissolution of 300 g of Pu metal is expected to be essentially complete in 6 h. The dissolution of larger batch sizes would result in the formation of PuO2 solids. Incomplete dissolution of the PuO2 formed from the metal is not a solubility limitation, but can be attributed to a combination of reduced acidity and complexation of fluoride which slows the dissolution kinetics and effectively limits the mass of Pu dissolved.
Author: E. S. Maxwell Publisher: ISBN: Category : Plutonium Languages : en Pages : 8
Book Description
On prolonged heating in dilute nitric acid (0.5M to 6.8M) a considerable amount of Pu(+4) is oxidized to Pu(+8). Precipitation of the plus three plutonium oxalate is complete in fifteen minutes. Oxidation of Pu(+4) to Pu(+8) by bromine is quantitative at 105 deg C after 1/2 hour; at 50 deg C the rate of oxidation is slow, but measurable. At room temperature the rate is too slow to measure. A method of converting PuC13 to Pu(NO3)4 is given. A solubility of NaPuO2Ac3 increases with temperature the value at 25 deg C being 19.5 g/iiter and that at 95 deg C, 37.5 g/liter. Supersaturation was observed on slow cooling of a saturated solution. p2.
Author: Publisher: ISBN: Category : Languages : en Pages :
Book Description
The dissolution of plutonium dioxide in nitirc acid (HNO3) at high hydrofluoric acid (HF) concentrations has been investigated. Dissolution rate curves were obtained using 12M HNO3 and HF at concentrations varying from 0.05 to 1.0 molar. The dissolution rate increased with HF concentration up to 0.2M and then decreased at higher concentrations. There was very little plutonium dissolved at 0.7 and 1.0M HF because of the formation of insoluble PuF4. Various oxidizing agents were added to 12M HNO3-1M HF dissolvent to oxidize Pu(IV) to Pu(VI) and prevent the formation of PuF4. Ceric (Ce(IV)) and silver (Ag(II)) ions were the most effective in dissolving PuO2. Although these two oxidants greatly increased the dissolution rate, the rates were not as rapid as those obtained with 12M HNO3-0.2M HF.
Author: Publisher: ISBN: Category : Languages : en Pages :
Book Description
A two-step process for dissolving plutonium metal, which two steps can be carried out sequentially or simultaneously. Plutonium metal is exposed to a first mixture containing approximately 1.0M-1.67M sulfamic acid and 0.0025M-0.1M fluoride, the mixture having been heated to a temperature between 45.degree. C. and 70.degree. C. The mixture will dissolve a first portion of the plutonium metal but leave a portion of the plutonium in an oxide residue. Then, a mineral acid and additional fluoride are added to dissolve the residue. Alteratively, nitric acid in a concentration between approximately 0.05M and 0.067M is added to the first mixture to dissolve the residue as it is produced. Hydrogen released during the dissolution process is diluted with nitrogen.
Author: Publisher: ISBN: Category : Languages : en Pages : 5
Book Description
Thermal stability tests were conducted with a nitric acid (HNO3)/hydroxylammonium nitrate (HAN)/potassium fluoride (KF) solution. The solution has great potential for use in plutonium dissolution because of the small quantity of hydrogen and other offgases produced. Tests were carried out in a Reactive Systems Screening Tool (RSST). The RSST is a calorimeter equipped with temperature and pressure probes as well as a heater that can heat a liquid sample at a programmed rate. In most cases, the calorimeter was pressurized with nitrogen to reduce evaporation of the liquid sample during heating. For the proposed solution, an autocatalytic reaction occurred between 113 and 131 degrees Celsius with 300 psig or 50 psig nitrogen inside the RSST vapor space. At ambient pressure, the solution boiled at about 110 degrees Celsius. After extensive boiling, the concentrations of HNO3 and HAN increased and the autocatalytic reaction occurred. Tests were also conducted with 1000 ppm Fe present in the solution. The range of the autocatalytic reaction initiation temperature was reduced to 105-120.5 degrees Celsius. With iron at ambient pressure, boiling still occurred above 100 degrees Celsius prior to the autocatalytic reaction, which occurred at 108-109 degrees Celsius. These results demonstrated the stability of the proposed HAN flowsheet, for which the planned dissolving temperature is 50-60 degrees Celsius. Additional tests were carried out with more concentrated solutions to further characterize the autocatalytic reaction initiation temperature. Increasing the nitric acid concentration to 3M decreased the reaction initiation temperature to 102-103 degrees Celsius. Increasing the HAN concentration increased the temperature rise of the reaction from 10-30 degrees Celsius to greater than 40 degrees Celsius. Increasing both reactants-to 3M nitric acid and 0.9M HAN-yielded a reaction initiation temperature of 91 degrees Celsius (with or without iron), the lowest observed in this study. This study was the first part of a larger flowsheet development / demonstration program for the plutonium metal dissolving process. The results of the study may be useful for similar flowsheets.
Author: E.R. Merz Publisher: Springer Science & Business Media ISBN: 9780792338413 Category : Science Languages : en Pages : 360
Book Description
This NATO Advanced Research Workshop on Disposal of Weapons Plutonium is a follow-up event to two preceding workshops, each dealing with a special subject within the overall disarmament issue: "Disposition of Weapon Plutonium", sponsored by the NATO Science Committee. The first workshop of this series was held at the Royal Institute of International Affairs in London on 24-25 January 1994, entitled "Managing the Plutonium Surplus, Applications, and Options". Its over all goal was to clarify the current situation with respect to pluto nium characteristics and availability, the technical options for use or disposal, and their main technical, environmental, and economic constraints. In the immediate term, plutonium recovered from dismantled nuclear warheads will have to be stored securely, and under international safeguards if possible. In the intermediate term, the principal alter natives for disposition of this plutonium are: irradiation in mixed oxide (MOX) fuel assemblies in existing commercial light-water reac tors or in specially adapted light-water reactors capable of operation with full cores of MOX fuel .and irradiation in future fast reactors. Another option is to blend plutonium with high-level waste as it is vitrified for final disposal in a geologic repository. In both cases, the high radioactivity of the resulting products provides "self shielding" and prevents separation of plutonium without already developed and available sophisticated technology. The so-called "spent fuel standard" as an effective protection barrier is - quired in either case.
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Author: United Kingdom Atomic Energy Authority
Author: William J. Jenkins
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Author: E. S. Maxwell
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Author: E. L. Whittaker
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Author: E.R. Merz