15 Matching Results

Search Results

Advanced search parameters have been applied.

Studies with Ferrous Sulfamate and Alternate Reductants for 2nd Uranium Cycle

Description: A wide range of miniature mixer-settler tests were conducted to determine the source of iron and sulfur contamination in the uranium product stream (''1EU'') of H Canyon's 2nd Uranium Cycle. The problem was reproduced on the laboratory scale mixer-settlers by changing the feed location of ferrous sulfamate from stage D4 to stage D1. Other process variables effected no change. It was later determined that ferrous sulfamate (FS) solids had plugged the FS line to stage D4, causing FS to backup a ventline and enter the Canyon process at stage D1. Pluggage was almost certainly due to precipitation of FS solids during extended process downtime. During the search for the root cause, tests showed that FS solids were quite small (1-10 mm), and a portion of them could bypass the current Canyon prefilter (3-mm). Also, additional tests were done to find an alternate means of reducing and thereby removing plutonium and neptunium from the uranium product. These tests showed that FS was a more effective reductant than either ascorbic acid or a hydroxylamine nitrate (HAN) / dilute FS combination.
Date: January 15, 2003
Creator: Crowder, M.L.
Partner: UNT Libraries Government Documents Department

Evaporation of Pretreated Hanford Tank AW-101 Sample Mixed with Recycle

Description: This task was undertaken to provide validation data for the Treated Feed Evaporator flowsheet and operating conditions using Hanford Tank 241-AW-101 pretreated waste blended with simulated River Protection Project Waste Treatment Plant(RPP-WTP) waste recycles. This task provided the first opportunity to compare performance of blended actual treated waste to the performance of blended treated waste simulants and recycle simulants. Specific objectives were: (1) determining the effect of plant recycles; (2) developing solubility data, as well as chemical and physical property data; and (3) evaluating antifoam effectiveness. The treated AW-101 sample was produced from the composite effluent of Ion Exchange testing carried out at Savannah River Technical Center. The design basis operating conditions were validated. Blended solutions of pretreated Hanford Tank 241-AW-101 and simulated SBS A2 recycle boiled at expected RPP-WTP flowsheet conditions: 60 mm Hg and 50 degrees Celsius. As expected, boiling point increased with concentration. Specifically, the 35:65 blend of AW-101 to SBS A2 at 7.5 M sodium had boiling points of 53 degrees Celsius at 60 mm Hg and 59 degrees Celsius at 80 mm Hg. These were 6 to 7 degrees Celsius higher than those estimated by an OLI model. Precipitation of solids in the AW-101/SBS A2 matrix began between 8.7 M and 10.4 Msodium. No problematic or excessive solids were observed. Therefore, SBS recycles are not expected to have any adverse effect on the evaporation process in the RPP-WTP.
Date: March 1, 2004
Creator: Crowder, M.L.
Partner: UNT Libraries Government Documents Department

Solvent Quality Testing

Description: Typical plant solvent from H Canyon Tank 902 (used in 2nd Uranium Cycle) was obtained in early June 2001. To evaluate the solvent's quality, a wide range of tests was performed. This report covers analytical results, phase separation behavior, and extraction testing. Whenever possible, performance of plant solvent was compared to that of new solvent.
Date: September 30, 2002
Creator: Crowder, M.L.
Partner: UNT Libraries Government Documents Department


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 (HNO{sub 3}) 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 (PuO{sub 2}). 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 ...
Date: October 15, 2007
Creator: Rudisill, T.; Crowder, M. & Bronikowski, M.
Partner: UNT Libraries Government Documents Department


Description: H-Canyon and HB-Line are tasked with the production of PuO{sub 2} from a feed of plutonium metal. The PuO{sub 2} will provide feed material for the MOX Fuel Fabrication Facility. After dissolution of the Pu metal in H-Canyon, the solution will be transferred to HB-Line for purification by anion exchange. Subsequent unit operations include Pu(IV) oxalate precipitation, filtration and calcination to form PuO{sub 2}. This report details the results from SRNL anion exchange, precipitation, filtration, calcination, and characterization tests, as requested by HB-Line1 and described in the task plan. This study involved an 80-g batch of Pu and employed test conditions prototypical of HB-Line conditions, wherever feasible. In addition, this study integrated lessons learned from earlier anion exchange and precipitation and calcination studies. H-Area Engineering selected direct strike Pu(IV) oxalate precipitation to produce a more dense PuO{sub 2} product than expected from Pu(III) oxalate precipitation. One benefit of the Pu(IV) approach is that it eliminates the need for reduction by ascorbic acid. The proposed HB-Line precipitation process involves a digestion time of 5 minutes after the time (44 min) required for oxalic acid addition. These were the conditions during HB-line production of neptunium oxide (NpO{sub 2}). In addition, a series of small Pu(IV) oxalate precipitation tests with different digestion times were conducted to better understand the effect of digestion time on particle size, filtration efficiency and other factors. To test the recommended process conditions, researchers performed two nearly-identical larger-scale precipitation and calcination tests. The calcined batches of PuO{sub 2} were characterized for density, specific surface area (SSA), particle size, moisture content, and impurities. Because the 3013 Standard requires that the calcination (or stabilization) process eliminate organics, characterization of PuO{sub 2} batches monitored the presence of oxalate by thermogravimetric analysis-mass spectrometry (TGA-MS). To use the TGA-MS for carbon or oxalate content, ...
Date: August 22, 2012
Creator: Crowder, M. & Pierce, R.
Partner: UNT Libraries Government Documents Department


Description: Plutonium oxide (PuO{sub 2}) calcined at >900 C resists dissolution in nitric acid (HNO{sub 3})-potassium fluoride (KF) solutions, a common method for their dissolution. The Savannah River National Laboratory (SRNL) has developed an alternate method for large samples of PuO{sub 2}-bearing materials using sodium peroxide (Na{sub 2}O{sub 2}) fusion as a pretreatment. The products of the reaction between Na{sub 2}O{sub 2} and PuO{sub 2} have been reported in the literature. As part of the SRNL development effort, additional data about the reaction between Na{sub 2}O{sub 2} and PuO{sub 2} were required. Also needed were data concerning the reaction of Na{sub 2}O{sub 2} with other components that may be present in the feed materials. Sodium peroxide was reacted with aluminum metal (Al), beryllium metal (Be), graphite, potassium chloride (KCl), magnesium chloride (MgCl{sub 2}), and calcium chloride (CaCl{sub 2}). The paper reports and discusses the reaction products of these and related compounds with Na{sub 2}O{sub 2}.
Date: October 4, 2011
Creator: Pierce, R.; Missimer, D. & Crowder, M.
Partner: UNT Libraries Government Documents Department


Description: A straightforward method to evaluate the tritium content of Zircaloy-2 cladding hulls via oxidation of the hull and capture of the volatilized tritium in liquids has been demonstrated. Hull samples were heated in air inside a thermogravimetric analyzer (TGA). The TGA was rapidly heated to 1000 C to oxidize the hulls and release absorbed tritium. To capture tritium, the TGA off-gas was bubbled through a series of liquid traps. The concentrations of tritium in bubbler solutions indicated that tritiated water vapor was captured nearly quantitatively. The average tritium content measured in the hulls was 19% of the amount of tritium produced by the fuel, according to ORIGEN2 isotope generation and depletion calculations. Published experimental data show that Zircaloy-2 oxidation follows an Arrhenius model, and that an initial, nonlinear oxidation rate is followed by a faster, linear rate after 'breakaway' of the oxide film. This study demonstrates that the linear oxidation rate of Zircaloy samples at 974 C is faster than predicted by the extrapolation of data from lower temperatures.
Date: October 14, 2010
Creator: Crowder, M.; Laurinat, J. & Stillman, J.
Partner: UNT Libraries Government Documents Department


Description: H Canyon is considering a flowsheet change for Plutonium (Pu) Contaminated Scrap (PuCS) material. The proposed change is to route dissolved PuCS material directly to a uranium (U) storage tank. As a result, the PuCS solution will bypass Head End and First U Cycle, and will be purified by solvent extraction in Second U Cycle. The PuCS solution contains appreciable amounts of boron (B) and fluoride (F{sup -}), which are currently at trace levels in the U storage tank. Though unlikely, if the B concentration in the U storage tank were to reach 1.8 g B/g U, the entire contents of the U storage tank would likely require a second pass through Second U Cycle to provide sufficient decontamination to meet the Tennessee Valley Authority (TVA) Blend Grade Highly Enriched Uranium (HEU) specification for B, which is 30 {micro}g/g U. In addition, Second U Cycle is expected to provide sufficient decontamination of F{sup -} and Pu regardless of the amount of PuCS solution sent to the storage tank. Though aluminum (Al) is not present in the PuCS solution, B can be credited as a complexant of F{sup -}. Both stability constants from the literature and Savannah River National Laboratory (SRNL) corrosion studies were documented to demonstrate that B complexation of F{sup -} in nitric acid solutions is sufficient to prevent excessive corrosion. Though B and Al complex F{sup -} to a similar degree, neither completely eliminates the presence of free F{sup -} in solution. Therefore, a limited amount of corrosion is expected even with complexed F{sup -} solutions. Tanks maintained at ambient temperature are not expected to experience significant corrosion. However, the Low Activity Waste (LAW) evaporators may be subjected to a corrosion rate of about 25 mils per year (mpy) as they reach their highest F{sup -} concentrations. The ...
Date: October 22, 2007
Creator: Crowder, M.; Rudisill, T.; Laurinat, J. & Mickalonis, J.
Partner: UNT Libraries Government Documents Department


Description: To ensure safe storage, plutonium-bearing oxides are stabilized at 950 C for at least two hours in an oxidizing atmosphere. Stabilization conditions are expected to decompose organic impurities, convert metals to oxides, and result in moisture content below 0.5 wt%. During stabilization, the specific surface area is reduced, which minimizes readsorption of water onto the oxide surface. Plutonium oxides stabilized according to these criteria were sampled and analyzed to determine moisture content and surface area. In addition, samples were leached in water to identify water-soluble chloride impurity content. Results of these analyses for seven samples showed that the stabilization process produced low moisture materials (< 0.2 wt %) with low surface area ({le} 1 m{sup 2}/g). For relatively pure materials, the amount of water per unit surface area corresponded to 1.5 to 3.5 molecular layers of water. For materials with chloride content > 360 ppm, the calculated amount of water per unit surface area increased with chloride content, indicating hydration of hygroscopic salts present in the impure PuO{sub 2}-containing materials. The low moisture, low surface area materials in this study did not generate detectable hydrogen during storage of four or more years.
Date: September 28, 2009
Creator: Crowder, M.; Duffey, J.; Livingston, R.; Scogin, J.; Kessinger, G. & Almond, P.
Partner: UNT Libraries Government Documents Department


Description: The H-Canyon facility will be used to dissolve Pu metal for subsequent purification and conversion to plutonium dioxide (PuO{sub 2}) using Phase II of HB-Line. To support the new mission, SRNL conducted a series of experiments to produce calcined plutonium (Pu) oxide and measure the physical properties and water adsorption of that material. This data will help define the process operating conditions and material handling steps for HB-Line. An anion exchange column experiment produced 1.4 L of a purified 52.6 g/L Pu solution. Over the next nine weeks, seven Pu(IV) oxalate precipitations were performed using the same stock Pu solution, with precipitator feed acidities ranging from 0.77 M to 3.0 M nitric acid and digestion times ranging from 5 to 30 minutes. Analysis of precipitator filtrate solutions showed Pu losses below 1% for all precipitations. The four larger precipitation batches matched the target oxalic acid addition time of 44 minutes within 4 minutes. The three smaller precipitation batches focused on evaluation of digestion time and the oxalic acid addition step ranged from 25-34 minutes because of pump limitations in the low flow range. Following the precipitations, 22 calcinations were performed in the range of 610-690 C, with the largest number of samples calcined at either 650 or 635 C. Characterization of the resulting PuO{sub 2} batches showed specific surface areas in the range of 5-14 m{sup 2}/g, with 16 of the 22 samples in the range of 5-10 m2/g. For samples analyzed with typical handling (exposed to ambient air for 15-45 minutes with relative humidities of 20-55%), the moisture content as measured by Mass Spectrometry ranged from 0.15 to 0.45 wt % and the total mass loss at 1000 C, as measured by TGA, ranged from 0.21 to 0.58 wt %. For the samples calcined between 635 and 650 C, ...
Date: June 25, 2012
Creator: Crowder, M.; Pierce, R.; Scogin, J.; Daniel, G. & King, W.
Partner: UNT Libraries Government Documents Department


Description: Efforts are underway to qualify the Next-Generation Solvent for the Caustic Side Solvent Extraction (CSSX) process. Researchers at multiple national laboratories have been involved in this effort. As part of the effort to qualify the solvent extraction system at the Savannah River Site (SRS), SRNL performed a number of tests at various scales. First, SRNL completed a series of batch equilibrium, or Extraction-Scrub-Strip (ESS), tests. These tests used {approx}30 mL of Next-Generation Solvent and either actual SRS tank waste, or waste simulant solutions. The results from these cesium mass transfer tests were used to predict solvent behavior under a number of conditions. At a larger scale, SRNL assembled 12 stages of 2-cm (diameter) centrifugal contactors. This rack of contactors is structurally similar to one tested in 2001 during the demonstration of the baseline CSSX process. Assembly and mechanical testing found no issues. SRNL performed a nonradiological test using 35 L of cesium-spiked caustic waste simulant and 39 L of actual tank waste. Test results are discussed; particularly those related to the effectiveness of extraction.
Date: November 1, 2011
Creator: Pierce, R.; Peters, T.; Crowder, M. & Fink, S.
Partner: UNT Libraries Government Documents Department


Description: Researchers successfully demonstrated the chemistry and process equipment of the Caustic-Side Solvent Extraction (CSSX) flowsheet using MaxCalix for the decontamination of high level waste (HLW). The demonstration was completed using a 12-stage, 2-cm centrifugal contactor apparatus at the Savannah River National Laboratory (SRNL). This represents the first CSSX process demonstration of the MaxCalix solvent system with Savannah River Site (SRS) HLW. Two tests lasting 24 and 27 hours processed non-radioactive simulated Tank 49H waste and actual Tank 49H HLW, respectively. Conclusions from this work include the following. The CSSX process is capable of reducing {sup 137}Cs in high level radioactive waste by a factor of more than 40,000 using five extraction, two scrub, and five strip stages. Tests demonstrated extraction and strip section stage efficiencies of greater than 93% for the Tank 49H waste test and greater than 88% for the simulant waste test. During a test with HLW, researchers processed 39 liters of Tank 49H solution and the waste raffinate had an average decontamination factor (DF) of 6.78E+04, with a maximum of 1.08E+05. A simulant waste solution ({approx}34.5 liters) with an initial Cs concentration of 83.1 mg/L was processed and had an average DF greater than 5.9E+03, with a maximum DF of greater than 6.6E+03. The difference may be attributable to differences in contactor stage efficiencies. Test results showed the solvent can be stripped of cesium and recycled for {approx}25 solvent turnovers without the occurrence of any measurable solvent degradation or negative effects from minor components. Based on the performance of the 12-stage 2-cm apparatus with the Tank 49H HLW, the projected DF for MCU with seven extraction, two scrub, and seven strip stages operating at a nominal efficiency of 90% is {approx}388,000. At 95% stage efficiency, the DF in MCU would be {approx}3.2 million. Carryover of organic solvent ...
Date: September 27, 2011
Creator: Pierce, R.; Peters, T.; Crowder, M.; Caldwell, T.; Pak, D; Fink, S. et al.
Partner: UNT Libraries Government Documents Department


Description: Researchers successfully demonstrated the chemistry and process equipment of the Caustic-Side Solvent Extraction (CSSX) flowsheet using MaxCalix for the decontamination of high level waste (HLW). The demonstration was completed using a 12-stage, 2-cm centrifugal contactor apparatus at the Savannah River National Laboratory (SRNL). This represents the first CSSX process demonstration of the MaxCalix solvent system with Savannah River Site (SRS) HLW. Two tests lasting 24 and 27 hours processed non-radioactive simulated Tank 49H waste and actual Tank 49H HLW, respectively. A solvent extraction system for removal of cesium from alkaline solutions was developed utilizing a novel solvent invented at the Oak Ridge National Laboratory (ORNL). This solvent consists of a calix[4]arene-crown-6 extractant dissolved in an inert hydrocarbon matrix. A modifier is added to the solvent to enhance the extraction power of the calixarene and to prevent the formation of a third phase. An additional additive is used to improve stripping performance and to mitigate the effects of any surfactants present in the feed stream. The process that deploys this solvent system is known as Caustic Side Solvent Extraction (CSSX). The solvent system has been deployed at the Savannah River Site (SRS) in the Modular CSSX Unit (MCU) since 2008.
Date: November 29, 2011
Creator: Pierce, R.; Peters, T.; Crowder, M.; Pak, D.; Fink, S.; Blessing, R. et al.
Partner: UNT Libraries Government Documents Department


Description: The destructive examination (DE) of 3013 containers after storage is part of the Surveillance and Monitoring Program based on the Department of Energy's standard for long-term storage of Pu (DOE-STD-3013). The stored, Pu-bearing materials may contain alkali halide contamination that varies from trace amounts of salt to about 50 weight percent, with smaller fractions of other compounds and oxides. These materials were characterized prior to packaging, and surveillance characterizations are conducted to determine the behavior of the materials during long term storage. The surveillance characterization results are generally in agreement with the pre-surveillance data. The predominant phases identified by X-ray diffraction are in agreement with the expected phase assemblages of the as-received materials. The measured densities are in reasonable agreement with the expected densities of materials containing the fraction of salts and actinide oxide specified by the pre-surveillance data. The radiochemical results are generally in good agreement with the pre-surveillance data for mixtures containing 'weapons grade' Pu (nominally 94% {sup 239}Pu and 6% {sup 240}Pu); however, the ICP-MS results from the present investigation generally produce lower concentrations of Pu than the pre-surveillance analyses. For mixtures containing 'fuel grade' Pu (nominally 81-93% {sup 239}Pu and 7-19% {sup 240}Pu), the ICP-MS results from the present investigation appear to be in better agreement with the pre-surveillance data than the radiochemistry results.
Date: February 1, 2010
Creator: Kessinger, G.; Almond, P.; Bridges, N.; Bronikowski, M.; Crowder, M.; Duffey, J. et al.
Partner: UNT Libraries Government Documents Department