Mathematical Model of Cold Cap?Preliminary One-Dimensional Model Development

The ultimate goal of batch-melting studies, laboratory-scale, large-scale, or mathematical modeling is to increase the rate of glass processing in an energy-efficient manner. Mathematical models are not merely an intermediate step between laboratory-scale and large-scale studies, but are also an important tool for assessing the responses of melters to vast combinations of process parameters. In the simplest melting situation considered in this study, a cold cap of uniform thickness rests on a pool of molten glass from which it receives a steady uniform heat flux. Thus, as the feed-to-glass conversion proceeds, the temperature, velocity, and extent of feed reactions are functions of the position along the vertical coordinate, and these functions do not vary with time. This model is used for the sensitivity analyses on the effects of key parameters on the cold-cap behavior

Retention of Halogens in Waste Glass

In spite of their potential roles as melting rate accelerators and foam breakers, halogens are generally viewed as troublesome components for glass processing. Of five halogens, F, Cl, Br, I, and At, all but At may occur in nuclear waste. A nuclear waste feed may contain up to 10 g of F, 4 g of Cl, and ≤100 mg of Br and I per kg of glass. The main concern is halogen volatility, producing hazardous fumes and particulates, and the radioactive iodine 129 isotope of 1.7x10^7-year half life. Because F and Cl are soluble in oxide glasses and tend to precipitate on cooling, they can be retained in the waste glass in the form of dissolved constituents or as dispersed crystalline inclusions. This report compiles known halogen-retention data in both high-level waste (HLW) and low-activity waste (LAW) glasses. Because of its radioactivity, the main focus is on I. Available data on F and Cl were compiled for comparison. Though Br is present in nuclear wastes, it is usually ignored; no data on Br retention were found

Modeling of Spinel Settling in Waste Glass Melter

Each 1% increase of waste loading (W), defined as the high-level waste (HLW) mass fraction in glass, can save the U.S. Department of Energy (DOE) over a half billion U.S. dollars for vitrification and disposal. For a majority of Hanford and Savannah River waste streams, W is limited by spinel precipitation and settling in waste glass melters. Therefore, a fundamental understanding of spinel behavior is crucial for economy and the low-risk operation of HLW vitrification. The goal of this research is to develop a basic understanding of the dynamics of spinel formation and motion in velocity, temperature, and redox fields that are characteristic for the glass-melting process. This goal is being achieved by directly studying spinel formation and settling in molten glass and by developing a mathematical tool for predicting the spinel behavior and accumulation rate in the melter. The main potential benefit of this study is achieving a lower waste-glass volume, which translates into a shorter cleanup time, a smaller processing facility, a smaller repository space, and, hence, a reduced investment of time and money to reach acceptable technical risks. Additional benefits include (1) more accurately assessing sensible limits for problem constituents (such as chromium) in the melter feed, (2) reducing the blending requirements, and (3) comparing cost and risk with other options (pretreatment, blending or diluting the waste) to determine the best path forward. The results of this study will allow alternate melter designs and operating conditions to be evaluated. The study will also address the option of removing the settled sludge from the melter

Glass Property Data and Models for Estimating High-Level Waste Glass Volume

This report describes recent efforts to develop glass property models that can be used to help estimate the volume of high-level waste (HLW) glass that will result from vitrification of Hanford tank waste. The compositions of acceptable and processable HLW glasses need to be optimized to minimize the waste-form volume and, hence, to save cost. A database of properties and associated compositions for simulated waste glasses was collected for developing property-composition models. This database, although not comprehensive, represents a large fraction of data on waste-glass compositions and properties that were available at the time of this report. Glass property-composition models were fit to subsets of the database for several key glass properties. These models apply to a significantly broader composition space than those previously publised. These models should be considered for interim use in calculating properties of Hanford waste glasses

Preliminary Investigation of Sulfur Loading in Hanford LAW Glass

A preliminary estimate was developed for loading limits for high-sulfur low-activity waste (LAW) feeds that will be vitrified into borosilicate glass at the Hanford Site in the waste-cleanup effort. Previous studies reported in the literature were consulted to provide a basis for the estimate. The examination of previous studies led to questions about sulfur loading in Hanford LAW glass, and scoping tests were performed to help answer these questions. These results of these tests indicated that a formulation approach developed by Vienna and colleagues shows promise for maximizing LAW loading in glass. However, there is a clear need for follow-on work. The potential for significantly lowering the amount of LAW glass produced at Hanford (after the initial phase of processing) because of higher sulfur tolerances may outweigh the cost and effort required to perform the necessary testing

Foaming of E-Glass II (Report for G Plus Project for PPG)

In a previous study, the effect of the furnace atmosphere on E glass foaming was investigated with the specific goal to understand the impact of increased water content on foaming in oxy-fired furnaces. The present study extended the previous study and focused on the effect of glass batch chemical composition on E-glass foaming. The present study also included reruns of foam tests performed in a previous study, which resulted in the same trend: the foaming extent increased nearly linearly with the heating rate and no foam was produced when CO2 + 55% H2O atmosphere was introduced at 300°C. It was shown that the lack of foaming in the test with CO2 + 55% H2O atmosphere introduced at 300°C was caused by a loss of sulfate at T <1250°C because of higher water content at the early stages of melting. The tests with new batches in the present study showed that replacing quicklime with limestone tend to decrease foaming, possibly caused by increased sulfate loss during early stages of melting in the batch with limestone. The batches where Na2SO4 was replaced with NaNO3, NaNO3 + CeO2, or CeO2, produced only very limited foaming regardless of the replacing components. As expected, the foaming extent increased as the sulfate content in the batch increased. The results of the present study suggest that foaming can be reduced by using limestone over quicklime and by decreasing the sulfate addition to a minimum required for refining

Kinetics of Cold-Cap Reactions for Vitrification of Nuclear Waste Glass Based on Simultaneous Differential Scanning Calorimetry - Thermogravimetry (DSC-TGA) and Evolved Gas Analysis (EGA)

For vitrifying nuclear waste glass, the feed, a mixture of waste with glass-forming and modifying additives, is charged onto the cold cap that covers 90?100% of the melt surface. The cold cap consists of a layer of reacting molten glass floating on the surface of the melt in an all-electric, continuous glass melter. As the feed moves through the cold cap, it undergoes chemical reactions and phase transitions through which it is converted to molten glass that moves from the cold cap into the melt pool. The process involves a series of reactions that generate multiple gases and subsequent mass loss and foaming significantly influence the mass and heat transfers. The rate of glass melting, which is greatly influenced by mass and heat transfers, affects the vitrification process and the efficiency of the immobilization of nuclear waste. We studied the cold-cap reactions of a representative waste glass feed using both the simultaneous differential scanning calorimetry-thermogravimetry (DSC-TGA) and the thermogravimetry coupled with gas chromatography-mass spectrometer (TGA-GC-MS) as complementary tools to perform evolved gas analysis (EGA). Analyses from DSC-TGA and EGA on the cold-cap reactions provide a key element for the development of an advanced cold-cap model. It also helps to formulate melter feeds for higher production rate

Database and Interim Glass Property Models for Hanford HLW Glasses

The purpose of this report is to provide a methodology for an increase in the efficiency and a decrease in the cost of vitrifying high-level waste (HLW) by optimizing HLW glass formulation. This methodology consists in collecting and generating a database of glass properties that determine HLW glass processability and acceptability and relating these properties to glass composition. The report explains how the property-composition models are developed, fitted to data, used for glass formulation optimization, and continuously updated in response to changes in HLW composition estimates and changes in glass processing technology. Further, the report reviews the glass property-composition literature data and presents their preliminary critical evaluation and screening. Finally the report provides interim property-composition models for melt viscosity, for liquidus temperature (with spinel and zircon primary crystalline phases), and for the product consistency test normalized releases of B, Na, and Li. Models were fitted to a subset of the screened database deemed most relevant for the current HLW composition region

Testing of Large-Scale ICV Glasses with Hanford LAW Simulant

Preliminary glass compositions for immobilizing Hanford low-activity waste (LAW) by the in-container vitrification (ICV) process were initially fabricated at crucible- and engineering-scale, including simulants and actual (radioactive) LAW. Glasses were characterized for vapor hydration test (VHT) and product consistency test (PCT) responses and crystallinity (both quenched and slow-cooled samples). Selected glasses were tested for toxicity characteristic leach procedure (TCLP) responses, viscosity, and electrical conductivity. This testing showed that glasses with LAW loading of 20 mass% can be made readily and meet all product constraints by a far margin. Glasses with over 22 mass% Na2O can be made to meet all other product quality and process constraints. Large-scale testing was performed at the AMEC, Geomelt Division facility in Richland. Three tests were conducted using simulated LAW with increasing loadings of 12, 17, and 20 mass% Na2O. Glass samples were taken from the test products in a manner to represent the full expected range of product performance. These samples were characterized for composition, density, crystalline and non-crystalline phase assemblage, and durability using the VHT, PCT, and TCLP tests. The results, presented in this report, show that the AMEC ICV product with meets all waste form requirements with a large margin. These results provide strong evidence that the Hanford LAW can be successfully vitrified by the ICV technology and can meet all the constraints related to product quality. The economic feasibility of the ICV technology can be further enhanced by subsequent optimization

Low Temperature Waste Immobilization Testing Vol. I

The Pacific Northwest National Laboratory (PNNL) is evaluating low-temperature technologies to immobilize mixed radioactive and hazardous waste. Three waste forms—alkali-aluminosilicate hydroceramic cement, “Ceramicrete” phosphate-bonded ceramic, and “DuraLith” alkali-aluminosilicate geopolymer—were selected through a competitive solicitation for fabrication and characterization of waste-form properties. The three contractors prepared their respective waste forms using simulants of a Hanford secondary waste and Idaho sodium bearing waste provided by PNNL and characterized their waste forms with respect to the Toxicity Characteristic Leaching Procedure (TCLP) and compressive strength. The contractors sent specimens to PNNL, and PNNL then conducted durability (American National Standards Institute/American Nuclear Society [ANSI/ANS] 16.1 Leachability Index [LI] and modified Product Consistency Test [PCT]) and compressive strength testing (both irradiated and as-received samples). This report presents the results of these characterization tests