Nitrogen Trifluoride-Based Fluoride- Volatility Separations Process: Initial Studies

This document describes the results of our investigations on the potential use of nitrogen trifluoride as the fluorinating and oxidizing agent in fluoride volatility-based used nuclear fuel reprocessing. The conceptual process uses differences in reaction temperatures between nitrogen trifluoride and fuel constituents that produce volatile fluorides to achieve separations and recover valuable constituents. We provide results from our thermodynamic evaluations, thermo-analytical experiments, kinetic models, and provide a preliminary process flowsheet. The evaluations found that nitrogen trifluoride can effectively produce volatile fluorides at different temperatures dependent on the fuel constituent

The Status of Radiation Damage Experiments

Experiments have been on-going for about two years to determine the effects that radiation damage have on the physical and chemical properties of candidate titanate ceramics for the immobilization of plutonium. We summarize the results of these experiments in this document

Characterization, Leaching, and Filtration Testing for Tributyl Phosphate (TBP, Group 7) Actual Waste Sample Composites

.A testing program evaluating actual tank waste was developed in response to Task 4 from the M-12 External Flowsheet Review Team (EFRT) issue response plan. The bulk water-insoluble solid wastes that are anticipated to be delivered to the Waste Treatment and Immobilization Plant (WTP) were identified according to type such that the actual waste testing could be targeted to the relevant categories. Eight broad waste groupings were defined. Samples available from the 222S archive were identified and obtained for testing. The actual waste-testing program included homogenizing the samples by group, characterizing the solids and aqueous phases, and performing parametric leaching tests. The tributyl phosphate sludge (TBP, Group 7) is the subject of this report. The Group 7 waste was anticipated to be high in phosphorus as well as aluminum in the form of gibbsite. Both are believed to exist in sufficient quantities in the Group 7 waste to address leaching behavior. Thus, the focus of the Group 7 testing was on the removal of both P and Al. The waste-type definition, archived sample conditions, homogenization activities, characterization (physical, chemical, radioisotope, and crystal habit), and caustic leaching behavior as functions of time, temperature, and hydroxide concentration are discussed in this report. Testing was conducted according to TP-RPP-WTP-467

Nitrogen Trifluoride-Based Fluoride- Volatility Separations Process: Initial Studies

This document describes the results of our investigations on the potential use of nitrogen trifluoride as the fluorinating and oxidizing agent in fluoride volatility-based used nuclear fuel reprocessing. The conceptual process uses differences in reaction temperatures between nitrogen trifluoride and fuel constituents that produce volatile fluorides to achieve separations and recover valuable constituents. We provide results from our thermodynamic evaluations, thermo-analytical experiments, kinetic models, and provide a preliminary process flowsheet. The evaluations found that nitrogen trifluoride can effectively produce volatile fluorides at different temperatures dependent on the fuel constituent

Evaluation of Exothermic Reactions from Bulk-Vitrification Melter Feeds Containing Cellulose

PNNL has demonstrated that cellulose effectively reduces the amount of molten ionic salt during Bulk Vitrification of simulated Hanford Low Level Waste (LLW). To address concerns about the potential reactivity of cellulose-LLW, PNNL used thermogravimetric analysis, differential thermal analysis, and accelerating rate calorimetry to determine in these preliminary studies that these mixtures will support a self-sustaining reaction if heated to 110°C at adiabatic conditions. Additional testing is recommended

Characterization, Leaching, and Filtrations Testing of Ferrocyanide Tank sludge (Group 8) Actual Waste Composite

This is the final report in a series of eight reports defining characterization, leach, and filtration testing of a wide variety of Hanford tank waste sludges. The information generated from this series is intended to supplement the Waste Treatment and Immobilization Plant (WTP) project understanding of actual waste behaviors associated with tank waste sludge processing through the pretreatment portion of the WTP. The work described in this report presents information on a high-iron waste form, specifically the ferrocyanide tank waste sludge. Iron hydroxide has been shown to pose technical challenges during filtration processing; the ferrocyanide tank waste sludge represented a good source of the high-iron matrix to test the filtration processing

Thermal Stability Studies of Candidate Decontamination Agents for Hanford’s Plutonium Finishing Plant Plutonium-Contaminated Gloveboxes

This report provides the results of PNNL's and Fluor's studies of the thermal stabilities of potential wastes arising from decontamination of Hanford's Plutonium Finishing Plant's plutonium contaminated gloveboxes. The candidate wastes arising from the decontamination technologies ceric nitrate/nitric acid, RadPro, Glygel, and Aspigel

The Status of Radiation Damage Experiments

Experiments have been on-going for about two years to determine the effects that radiation damage have on the physical and chemical properties of candidate titanate ceramics for the immobilization of plutonium. We summarize the results of these experiments in this document

Laboratory Demonstration of the Pretreatment Process with Caustic and Oxidative Leaching Using Actual Hanford Tank Waste

This report describes the bench-scale pretreatment processing of actual tank waste materials through the entire baseline WTP pretreatment flowsheet in an effort to demonstrate the efficacy of the defined leaching processes on actual Hanford tank waste sludge and the potential impacts on downstream pretreatment processing. The test material was a combination of reduction oxidation (REDOX) tank waste composited materials containing aluminum primarily in the form of boehmite and dissolved S saltcake containing Cr(III)-rich entrained solids. The pretreatment processing steps tested included • caustic leaching for Al removal • solids crossflow filtration through the cell unit filter (CUF) • stepwise solids washing using decreasing concentrations of sodium hydroxide with filtration through the CUF • oxidative leaching using sodium permanganate for removing Cr • solids filtration with the CUF • follow-on solids washing and filtration through the CUF • ion exchange processing for Cs removal • evaporation processing of waste stream recycle for volume reduction • combination of the evaporated product with dissolved saltcake. The effectiveness of each process step was evaluated by following the mass balance of key components (such as Al, B, Cd, Cr, Pu, Ni, Mn, and Fe), demonstrating component (Al, Cr, Cs) removal, demonstrating filterability by evaluating filter flux rates under various processing conditions (transmembrane pressure, crossflow velocities, wt% undissolved solids, and PSD) and filter fouling, and identifying potential issues for WTP. The filterability was reported separately (Shimskey et al. 2008) and is not repeated herein

Filtration and Leach Testing for PUREX Cladding Sludge and REDOX Cladding Sludge Actual Waste Sample Composites

A testing program evaluating actual tank waste was developed in response to Task 4 from the M-12 External Flowsheet Review Team (EFRT) issue response plan (Barnes and Voke 2006). The test program was subdivided into logical increments. The bulk water-insoluble solid wastes that are anticipated to be delivered to the Hanford Waste Treatment and Immobilization Plant (WTP) were identified according to type such that the actual waste testing could be targeted to the relevant categories. Under test plan TP RPP WTP 467 (Fiskum et al. 2007), eight broad waste groupings were defined. Samples available from the 222S archive were identified and obtained for testing. Under this test plan, a waste testing program was implemented that included: • Homogenizing the archive samples by group as defined in the test plan. • Characterizing the homogenized sample groups. • Performing parametric leaching testing on each group for compounds of interest. • Performing bench-top filtration/leaching tests in the hot cell for each group to simulate filtration and leaching activities if they occurred in the UFP2 vessel of the WTP Pretreatment Facility. This report focuses on a filtration/leaching test performed using two of the eight waste composite samples. The sample groups examined in this report were the plutonium-uranium extraction (PUREX) cladding waste sludge (Group 3, or CWP) and reduction-oxidation (REDOX) cladding waste sludge (Group 4, or CWR). Both the Group 3 and 4 waste composites were anticipated to be high in gibbsite, thus requiring caustic leaching. WTP RPT 167 (Snow et al. 2008) describes the homogenization, characterization, and parametric leaching activities before benchtop filtration/leaching testing of these two waste groups. Characterization and initial parametric data in that report were used to plan a single filtration/leaching test using a blend of both wastes. The test focused on filtration testing of the waste and caustic leaching for aluminum, in the form of gibbsite, and its impact on filtration. The initial sample was diluted with a liquid simulant to simulate the receiving concentration of retrieved tank waste into the UFP2 vessel (< 10 wt% undissolved solids). Filtration testing was performed on the dilute waste sample and dewatered to a higher solids concentration. Filtration testing was then performed on the concentrated slurry. Afterwards, the slurry was caustic leached to remove aluminum present in the undissolved solid present in the waste. The leach was planned to simulate leaching conditions in the UFP2 vessel. During the leach, slurry supernate samples were collected to measure the dissolution rate of aluminum in the waste. After the slurry cooled down from the elevated leach temperature, the leach liquor was dewatered from the solids. The remaining slurry was rinsed and dewatered with caustic solutions to remove a majority of the dissolved aluminum from the leached slurry. The concentration of sodium hydroxide in the rinse solutions was high enough to maintain the solubility of the aluminum in the dewatered rinse solutions after dilution of the slurry supernate. Filtration tests were performed on the final slurry to compare to filtration performance before and after caustic leaching