Control of High-level Radioactive Waste-glass Melters
Control of High-level Radioactive Waste-glass Melters

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Published: 1990

Total Pages: 22

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The Defense Waste Processing Facility (DWPF) will immobilize Savannah River Site High Level Waste as a durable borosilicate glass for permanent disposal in a repository. The DWPF will be controlled based on glass composition. The following discussion is a preliminary analysis of the capability of the laboratory methods that can be used to control the glass composition, and the relationships between glass durability and glass properties important to glass melting. The glass durability and processing properties will be controlled by controlling the chemical composition of the glass. The glass composition will be controlled by control of the melter feed transferred from the Slurry Mix Evaporator (SME) to the Melter Feed Tank (MFT). During cold runs, tests will be conducted to demonstrate the chemical equivalence of glass sampled from the pour stream and glass removed from cooled canisters. In similar tests, the compositions of glass produced from slurries sampled from the SME and MFT will be compared to final product glass to determine the statistical relationships between melter feed and glass product. The total error is the combination of those associated with homogeneity in the SME or MFT, sampling, preparation of samples for analysis, instrument calibration, analysis, and the composition/property model. This study investigated the sensitivity of estimation of property data to the combination of variations from sampling through analysis. In this or a similar manner, the need for routine glass product sampling will be minimized, and glass product characteristics will be assured before the melter feed is committed to the melter.

Control of High-level Radioactive Waste-glass Melters. Part 4, Preliminary Analysis of DWPF Process Laboratory Capabilities
Control of High-level Radioactive Waste-glass Melters. Part 4, Preliminary Analysis of DWPF Process Laboratory Capabilities

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Publisher:

Published: 1990

Total Pages: 22

ISBN-13:

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The Defense Waste Processing Facility (DWPF) will immobilize Savannah River Site High Level Waste as a durable borosilicate glass for permanent disposal in a repository. The DWPF will be controlled based on glass composition. The following discussion is a preliminary analysis of the capability of the laboratory methods that can be used to control the glass composition, and the relationships between glass durability and glass properties important to glass melting. The glass durability and processing properties will be controlled by controlling the chemical composition of the glass. The glass composition will be controlled by control of the melter feed transferred from the Slurry Mix Evaporator (SME) to the Melter Feed Tank (MFT). During cold runs, tests will be conducted to demonstrate the chemical equivalence of glass sampled from the pour stream and glass removed from cooled canisters. In similar tests, the compositions of glass produced from slurries sampled from the SME and MFT will be compared to final product glass to determine the statistical relationships between melter feed and glass product. The total error is the combination of those associated with homogeneity in the SME or MFT, sampling, preparation of samples for analysis, instrument calibration, analysis, and the composition/property model. This study investigated the sensitivity of estimation of property data to the combination of variations from sampling through analysis. In this or a similar manner, the need for routine glass product sampling will be minimized, and glass product characteristics will be assured before the melter feed is committed to the melter.

Control of High Level Radioactive Waste-glass Melters. Part 5, Modelling of Complex Redox Effects
Control of High Level Radioactive Waste-glass Melters. Part 5, Modelling of Complex Redox Effects

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Published: 1991

Total Pages: 17

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Slurry Fed Melters (SFM) are being developed in the United States, Europe and Japan for the conversion of high-level radioactive waste to borosilicate glass for permanent disposal. The high transition metal, noble metal, nitrate, organic, and sulfate contents of these wastes lead to unique melter redox control requirements. Pilot waste-glass melter operations have indicated the possibility of nickel sulfide or noble-metal fission-product accumulation on melter floors, which can lead to distortion of electric heating patterns, and decrease melter life. Sulfide formation is prevented by control of the redox chemistry of the melter feed. The redox state of waste-glass melters is determined by balance between the reducing potential of organic compounds in the feed, and the oxidizing potential of gases above the melt, and nitrates and polyvalent elements in the waste. Semiquantitative models predicting limitations of organic content have been developed based on crucible testing. Computerized thermodynamic computations are being developed to predict the sequence and products of redox reactions and is assessing process variations. Continuous melter test results have been compared to improved computer staged-thermodynamic-models of redox behavior. Feed chemistry control to prevent sulfide and moderate noble metal accumulations are discussed. 17 refs., 3 figs.

Control of Radioactive Waste-glass Melters
Control of Radioactive Waste-glass Melters

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Published: 1990

Total Pages: 38

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Slurries of simulated high level radioactive waste and glass formers have been isothermally reacted and analyzed to identify the sequence of the major chemical reactions in waste vitrification, their effect on glass production rate, and the development of leach resistance. Melting rates of waste batches have been increased by the addition of reducing agents (formic acid, sucrose) and nitrates. The rate increases are attributable in part to exothermic reactions which occur at critical stages in the vitrification process. Nitrates must be balanced by adequate reducing agents to avoid the formation of persistent foam, which would destabilize the melting process. The effect of foaming on waste glass production rates is analyzed, and melt rate limitations defined for waste-glass melters, based upon measurable thermophysical properties. Minimum melter residence times required to homogenize glass and assure glass quality are much smaller than those used in current practice. Thus, melter size can be reduced without adversely affecting glass quality. Physical chemistry and localized heat transfer of the waste-glass melting process are examined, to refine the available models for predicting and assuring glass production rate. It is concluded that the size of replacement melters and future waste processing facilities can be significantly decreased if minimum heat transfer requirements for effective melting are met by mechanical agitation. A new class of waste glass melters has been designed, and proof of concept tests completed on simulated High Level Radioactive Waste slurry. Melt rates have exceeded 155 kg m−2 h−1 with slurry feeds (32 lb ft−2 h−1), and 229 kg kg m−2 h−1 with dry feed (47 lb ft−2 h−1). This is about 8 times the melt rate possible in conventional waste- glass melters of the same size. 39 refs., 5 figs., 9 tabs.

Control of High Level Radioactive Waste-glass Melters. Part 6, Noble Metal Catalyzed Formic Acid Decomposition, and Formic Acid
Control of High Level Radioactive Waste-glass Melters. Part 6, Noble Metal Catalyzed Formic Acid Decomposition, and Formic Acid

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Published: 1990

Total Pages: 25

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A necessary step in Defense Waste Processing Facility (DWPF) melter feed preparation for the immobilization of High Level Radioactive Waste (HLW) is reduction of Hg(II) to Hg(0), permitting steam stripping of the Hg. Denitrition and associated NOx evolution is a secondary effect of the use of formic acid as the mercury-reducing agent. Under certain conditions the presence of transition or noble metals can result in significant formic acid decomposition, with associated CO2 and H2 evolution. These processes can result in varying redox properties of melter feed, and varying sequential gaseous evolution of oxidants and hydrogen. Electrochemical methods for monitoring the competing processes are discussed. Laboratory scale techniques have been developed for simulating the large-scale reactions, investigating the relative effectiveness of the catalysts, and the effectiveness of catalytic poisons. The reversible nitrite poisoning of formic acid catalysts is discussed.

Numerical Simulation of High-level Radioactive Nuclear Waste Glass Production
Numerical Simulation of High-level Radioactive Nuclear Waste Glass Production

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Published: 1991

Total Pages: 10

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Vitrification of radioactive waste has become an international approach for converting highly radioactive wastes into a durable solid prior to placing them in a permanent disposal repository. The technology for the process is not new. The conversion melter is a direct descendant of all electric melters used for manufacturing of some commercial glass types. Therefore, the vitrification process of radioactive wastes inherits typical problems of all electric furnaces and creates some other specific problems such as noble metal sedimentation. The noble metals and nickel sulfides in the melter are heavier than molten glass and have a low solubility. In a reducing condition, these metals amalgamate and tend to settle on the melter floor. The metal deposit resulting from this settling has a potential to short circuit the melter. The objective of this paper is to identify the typical problems that have been encountered in the waste melter operations and to address how these problems can be tackled using state-of-the-art numerical simulation techniques. It is believed that the large amount of pilot-scale melter experience throughout the world, combined with the knowledge gained from state-of-the-art computer modeling techniques would give assurance that the existing and future radioactive wastes can be effectively converted into a durable glass material and safely placed in a permanent repository.

Characterization of High Level Nuclear Waste Glass Samples Following Extended Melter Idling
Characterization of High Level Nuclear Waste Glass Samples Following Extended Melter Idling

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Published: 2015

Total Pages:

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The Savannah River Site Defense Waste Processing Facility (DWPF) melter was recently idled with glass remaining in the melt pool and riser for approximately three months. This situation presented a unique opportunity to collect and analyze glass samples since outages of this duration are uncommon. The objective of this study was to obtain insight into the potential for crystal formation in the glass resulting from an extended idling period. The results will be used to support development of a crystal-tolerant approach for operation of the high level waste melter at the Hanford Tank Waste Treatment and Immobilization Plant (WTP). Two glass pour stream samples were collected from DWPF when the melter was restarted after idling for three months. The samples did not contain crystallization that was detectible by X-ray diffraction. Electron microscopy identified occasional spinel and noble metal crystals of no practical significance. Occasional platinum particles were observed by microscopy as an artifact of the sample collection method. Reduction/oxidation measurements showed that the pour stream glasses were fully oxidized, which was expected after the extended idling period. Chemical analysis of the pour stream glasses revealed slight differences in the concentrations of some oxides relative to analyses of the melter feed composition prior to the idling period. While these differences may be within the analytical error of the laboratories, the trends indicate that there may have been some amount of volatility associated with some of the glass components, and that there may have been interaction of the glass with the refractory components of the melter. These changes in composition, although small, can be attributed to the idling of the melter for an extended period. The changes in glass composition resulted in a 70-100 °C increase in the predicted spinel liquidus temperature (TL) for the pour stream glass samples relative to the analysis of the melter feed prior to the outage. This indicates that the potential for spinel crystallization increased as a result of idling for an extended period. However, the predicted TL of the pour stream glasses remained 150-200 °C below the mean melt pool temperature of about 1125 °C during the idling period. Given the change in predicted TL over the three month outage, the results indicate that it is important to have a thorough understanding of spinel crystallization within the melter for WTP to operate with a volume percent crystallization constraint. This knowledge will enable process control routines to be developed that avoid bulk crystallization in the melter and allow for recovery from off-normal events. The current WTP crystal-tolerant glass program will develop an improved understanding of spinel crystallization in the WTP melter to allow for operation at maximum waste loading in glass composition systems limited by predictions of spinel crystallization.