COMBINED RETENTION OF MOLYBDENUM AND SULFUR IN SIMULATED HIGH LEVEL WASTE GLASS.

COMBINED RETENTION OF MOLYBDENUM AND SULFUR IN SIMULATED HIGH LEVEL WASTE GLASS.

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Published: 2009

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This study was undertaken to investigate the effect of elevated sulfate and molybdenum concentrations in nuclear waste glasses. A matrix of 24 glasses was developed and the glasses were tested for acceptability based on visual observations, canister centerline-cooled heat treatments, and chemical composition analysis. Results from the chemical analysis of the rinse water from each sample were used to confirm the presence of SO2−4 and MoO3 on the surface of glasses as well as other components which might form water soluble compounds with the excess sulfur and molybdenum. A simple, linear model was developed to show acceptable concentrations of SO42− and MoO3 in an example waste glass composition. This model was constructed for scoping studies only and is not ready for implementation in support of actual waste vitrification. Several other factors must be considered in determining the limits of sulfate and molybdenum concentrations in the waste vitrification process, including but not limited to, impacts on refractory and melter component corrosion, effects on the melter off-gas system, and impacts on the chemical durability and crystallization of the glass product.


RETENTION OF SULFATE IN HIGH LEVEL RADIOACTIVE WASTE GLASS.

RETENTION OF SULFATE IN HIGH LEVEL RADIOACTIVE WASTE GLASS.

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Published: 2010

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High level radioactive wastes are being vitrified at the Savannah River Site for long term disposal. Many of the wastes contain sulfate at concentrations that can be difficult to retain in borosilicate glass. This study involves efforts to optimize the composition of a glass frit for combination with the waste to improve sulfate retention while meeting other process and product performance constraints. The fabrication and characterization of several series of simulated waste glasses are described. The experiments are detailed chronologically, to provide insight into part of the engineering studies used in developing frit compositions for an operating high level waste vitrification facility. The results lead to the recommendation of a specific frit composition and a concentration limit for sulfate in the glass for the next batch of sludge to be processed at Savannah River.


Additive Testing for Improved Sulfur Retention

Additive Testing for Improved Sulfur Retention

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Published: 2011

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The Savannah River National Laboratory is collaborating with Alfred University to evaluate the potential for additives in borosilicate glass to improve sulfur retention. This preliminary report provides further background on the incorporation of sulfur in glass and outlines the experiments that are being performed by the collaborators. A simulated waste glass composition has been selected for the experimental studies. The first phase of experimental work will evaluate the impacts of BaO, PbO, and V2O5 at concentrations of 1.0, 2.0, and 5.0 wt % on sulfate retention in simulated high level waste borosilicate glass. The second phase of experimental work will evaluate the effects of time at the melt temperature on sulfur retention. The resulting samples will be characterized to determine the amount of sulfur remaining as well as to identify the formation of any crystalline phases. The results will be used to guide the future selection of frits and glass forming chemicals in vitrifying Department of Energy wastes containing high sulfur concentrations.


Immobilization of Simulated High-level Radioactive Waste in Borosilicate Glass

Immobilization of Simulated High-level Radioactive Waste in Borosilicate Glass

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Published: 1991

Total Pages: 14

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The Integrated DWPF Melter System (IDMS), operated by the Savannah River Laboratory, is a pilot scale facility used in support of the start-up and operation of the Department of Energy's Defense Waste Processing Facility. The IDMS has successfully demonstrated, on an engineering scale (one-fifth), that simulated high level radioactive waste (HLW) sludge can be chemically treated with formic acid to adjust both its chemical and physical properties, and then blended with simulated precipitate hydrolysis aqueous (PHA) product and borosilicate glass frit to produce a melter feed which can be processed into a durable glass product. The simulated sludge, PHA and frit were blended, based on a product composition program, to optimize the loading of the waste glass as well as to minimize those components which can cause melter processing and/or glass durability problems. During all the IDMS demonstrations completed thus far, the melter feed and the resulting glass that has been produced met all the required specifications, which is very encouraging to future DWPF operations. The IDMS operations also demonstrated that the volatile components of the melter feed (e.g., mercury, nitrogen and carbon, and, to a lesser extent, chlorine, fluorine and sulfur) did not adversely affect the melter performance or the glass product.


Chemical Analysis of Simulated High Level Waste Glasses to Support Sulfate Solubility Modeling

Chemical Analysis of Simulated High Level Waste Glasses to Support Sulfate Solubility Modeling

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Published: 2014

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The U.S. Department of Energy (DOE), Office of Environmental Management (EM) is sponsoring an international, collaborative project to develop a fundamental model for sulfate solubility in nuclear waste glass. The solubility of sulfate has a significant impact on the achievable waste loading for nuclear waste forms both within the DOE complex and to some extent at U.K. sites. The development of enhanced borosilicate glass compositions with improved sulfate solubility will allow for higher waste loadings and accelerated cleanup missions. Much of the previous work on improving sulfate retention in waste glasses has been done on an empirical basis, making it difficult to apply the findings to future waste compositions despite the large number of glass systems studied. A more fundamental, rather than empirical, model of sulfate solubility in glass, under development at Sheffield Hallam University (SHU), could provide a solution to the issues of sulfate solubility. The model uses the normalized cation field strength index as a function of glass composition to predict sulfate capacity, and has shown early success for some glass systems. The objective of the current scope is to mature the sulfate solubility model to the point where it can be used to guide glass composition development for DOE waste vitrification efforts, allowing for enhanced waste loadings and waste throughput. A series of targeted glass compositions was selected to resolve data gaps in the current model. SHU fabricated these glasses and sent samples to the Savannah River National Laboratory (SRNL) for chemical composition analysis. SHU will use the resulting data to enhance the sulfate solubility model and resolve any deficiencies. In this report, SRNL provides chemical analyses for simulated waste glasses fabricated SHU in support of sulfate solubility model development. A review of the measured compositions revealed that there are issues with the B2O3 and Fe2O3 concentrations missing their targeted values by a significant amount for several of the study glasses. SHU is reviewing the fabrication of these glasses and the chemicals used in batching them to identify the source of these issues. The measured sulfate concentrations were all below their targeted values. This is expected, as the targeted concentrations likely exceeded the solubility limit for sulfate in these glass compositions. Some volatilization of sulfate may also have occurred during fabrication of the glasses. Measurements of the other oxides in the study glasses were reasonably close to their targeted values.