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Title: ALUMINUM AND CHROMIUM LEACHING WORKSHOP WHITEPAPER

Abstract

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) billionsmore » 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.« less

Authors:
; ;
Publication Date:
Research Org.:
SRS
Sponsoring Org.:
USDOE
OSTI Identifier:
909349
Report Number(s):
WSRC-STI-2007-00168
TRN: US0703880
DOE Contract Number:
DE-AC09-96SR18500
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS; ALUMINIUM; CHEMISTRY; CHROMIUM; CONTAINERS; DISSOLUTION; KINETICS; LEACHING; LIFE CYCLE; LIQUID WASTES; OPERATING COST; PARTICLE PROPERTIES; RADIOISOTOPES; WASTE PROCESSING; WASTE STORAGE

Citation Formats

McCabe, D, Jeff Pike, J, and Bill Wilmarth, B. ALUMINUM AND CHROMIUM LEACHING WORKSHOP WHITEPAPER. United States: N. p., 2007. Web. doi:10.2172/909349.
McCabe, D, Jeff Pike, J, & Bill Wilmarth, B. ALUMINUM AND CHROMIUM LEACHING WORKSHOP WHITEPAPER. United States. doi:10.2172/909349.
McCabe, D, Jeff Pike, J, and Bill Wilmarth, B. Wed . "ALUMINUM AND CHROMIUM LEACHING WORKSHOP WHITEPAPER". United States. doi:10.2172/909349. https://www.osti.gov/servlets/purl/909349.
@article{osti_909349,
title = {ALUMINUM AND CHROMIUM LEACHING WORKSHOP WHITEPAPER},
author = {McCabe, D and Jeff Pike, J and Bill Wilmarth, B},
abstractNote = {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.},
doi = {10.2172/909349},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Wed Apr 25 00:00:00 EDT 2007},
month = {Wed Apr 25 00:00:00 EDT 2007}
}

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  • Abstract not provided.
  • The 1100 and 1200 C cyclic oxidation resistance of dense Ni-Cr-Al-Y - MgO, Ni-Cr-Al-Y - CaZrO/sub 3/, Ni-Cr-Al-Y - SrZrO/sub 3/, Ni-Cr-Al-Y - MgZrO/sub 3/ cermets and a 70 percent dense Ni-Cr-Al-Y developmental material was determined. The cermets contained 60 and 50 volume percent of Ni-Cr-Al-Y which formed a matrix with the oxide particles imbedded in it. The cermets containing MgO were superior to cermets based on zirconates and to the porous Ni-Cr-Al-Y material. Cyclic oxidation tests of four cermet systems are reported; variables include simple oxide content, element content, oxidation temperature, specific weight change, number of cycles, and X-raymore » diffraction pattern intensities: 2 figures and 3 tables include numeric data.« less
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  • The rate of oxidation is important to the long-term performance of reducing salt waste forms because the solubility of some contaminants, e.g., technetium, is a function of oxidation state. TcO 4 - in the salt solution is reduced to Tc(IV) and has been shown to react with ingredients in the waste form to precipitate low solubility sulfide and/or oxide phases [Shuh, et al., 1994, Shuh, et al., 2000, Shuh, et al., 2003]. Upon exposure to oxygen, the compounds containing Tc(IV) oxidize to the pertechnetate ion, Tc(VII)O 4 -, which is very soluble. Consequently the rate of technetium oxidation front advancementmore » into a monolith and the technetium leaching profile as a function of depth from an exposed surface are important to waste form performance and ground water concentration predictions. An approach for measuring contaminant oxidation rate (effective contaminant specific oxidation rate) based on leaching of select contaminants of concern is described in this report. In addition, the relationship between reduction capacity and contaminant oxidation is addressed. Chromate was used as a non-radioactive surrogate for pertechnetate in simulated waste form samples. Depth discrete subsamples were cut from material exposed to Savannah River Site (SRS) field cured conditions. The subsamples were prepared and analyzed for both reduction capacity and chromium leachability. Results from field-cured samples indicate that the depth at which leachable chromium was detected advanced further into the sample exposed for 302 days compared to the sample exposed to air for 118 days (at least 50 mm compared to at least 20 mm). Data for only two exposure time intervals is currently available. Data for additional exposure times are required to develop an equation for the oxidation front progression. Reduction capacity measurements (per the Angus-Glasser method, which is a measurement of the ability of a material to chemically reduce Ce(IV) to Ce(III) in solution) performed on depth discrete samples could not be correlated with the amount of chromium leached from the depth discrete subsamples or with the oxidation front inferred from soluble chromium (i.e., effective Cr oxidation front). Exposure to oxygen (air or oxygen dissolved in water) results in the release of chromium through oxidation of Cr(III) to highly soluble chromate, Cr(VI). Residual reduction capacity in the oxidized region of the test samples indicates that the remaining reduction capacity is not effective in re-reducing Cr(VI) in the presence of oxygen. Consequently, this method for determining reduction capacity may not be a good indicator of the effective contaminant oxidation rate in a relatively porous solid (40 to 60 volume percent porosity). The chromium extracted in depth discrete samples ranged from a maximum of about 5.8 % at about 5 mm (118 day exposure) to about 4 % at about 10 mm (302 day exposure). The use of reduction capacity as an indicator of long-term performance requires further investigation. The carbonation front was also estimated to have advanced to at least 28 mm in 302 days based on visual observation of gas evolution during acid addition during the reduction capacity measurements. Depth discrete sampling of materials exposed to realistic conditions in combination with short term leaching of crushed samples has potential for advancing the understanding of factors influencing performance and will support conceptual model development.« less