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At least 19 records

Heat transfer enhancement due to cold cap motion from bubbling in a waste glass melter

In this study, a computational fluid dynamics (CFD) model was developed to model the motion of a solid cold cap in a waste glass melter. Forced convection bubblers at the base of the melter release air into the molten glass, which forms large bubbles that travel upwards to the cold cap and augment heat transfer from the glass to the cold cap. The CFD model employs the Navier- Stokes equations to solve for the fluctuating flowfield using a rigid body motion dynamic fluid body interaction module. This allows for movement of the floating body in response to the bubbling forces calculated at each time step. Further, the heat flux delivered to the cold cap by the convective bubbling is studied as a function of the bubbling rate. Results for the moving cold cap are compared with the computed heat flux trends for a stationary cold cap. The heat flux delivered to the cold cap from the glass is 25% higher for the case with the moving cold cap. The heat flux was found to be proportional to v0.6 as opposed to v0.9 (where v is the normalized bubbling rate) for the stationary cold cap.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Compositional Variation Tests on DuraMelter 100 with LAW Sub-Envelope A1 Feed (LAWA44 Glass) in Support of the LAW Pilot Melter, VSL-02R62N0-4, Rev. 0 (Nov 2002)

The two tests described in this report utilized blended feed (glass formers plus waste simulant) prepared by Optima Chemicals according to VSL specifications generating about 1. 7 metric tons of glass. Sugar was added (at VSL) to the nominal feed at a "sugar ratio" of 0.5 for each of the two variation tests1; however, since the sugar addition is assumed to be "blind" to the variations, the actual sugar ratios were 0.57 and 0.44. The DMl00-WV melter was used in order to provide a direct comparison with the LAW tests previously conducted on the same melter. Two 100-hour melter tests were conducted: one with a 15% deficiency in simulant and one with 15% excess in simulant. Key operating parameters including cold cap coverage, feed rate, and glass pool temperature were held constant to investigate the effects of the glass compositional changes on processing characteristics (including salt formation) and the product glass. The bubbling rate was adjusted to provide the desired glass production rate with a near complete cold cap (90-100% of melt surface covered with feed). Quantitative measurements of glass production rates, melter operating conditions (temperatures, pressures, power, flows, etc.), and off-gas characteristics (NOx, SO 2, CO, particulate load and composition, and acid gases) were made for each test.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effect of cold-cap-bottom shear stress on primary foam stability

Here, we analyze the heat transfer between the melt pool and the layer of reacting materials called cold cap, which is the determining factor for the glass production rate in Joule-heated air-bubbled nuclear waste glass melters. We consider the effects of bubbling rate, melt viscosity, melt thermal conductivity, conversion kinetics, and shear rate at the cold-cap bottom, and develop simple relationships for the cold-cap bottom temperature and glass production rate. We show that the melt convection enhances the heat transfer to the cold cap by suppressing the thermal boundary layer and primary foam, while the conversion kinetics opposes these effects. Additionally, we mention how dissolving silica particles affects the primary foam stability and discuss the limitations of the presented approach for vigorously foaming feeds.

36 MATERIALS SCIENCE↗

Implementation of a High-Fidelity Interface Resolving Method in Nek5000

The development and utilization of computational fluid dynamics (CFD) models for large, high-temperature electric melters in the Waste Treatment and Immobilization Plant (WTP) in eastern Washington State have proven to be valuable for various purposes. These models allow for a better understanding of the physio-chemical processes occurring within the melter vessels and can contribute to improving operational efficiency, throughput, and addressing operational issues related to vitrification. The CFD models employed for these melter vessels incorporate multiphase fluid flow and heat transfer simulations in different regions, including the plenum, cold cap, and molten glass regions. As the tank waste and glass formers are introduced into the melter, a reacting batch layer known as the cold cap forms on top of the molten glass. To enhance the melt rate, forced convection bubblers located at the bottom of the melters generate convection currents that help homogenize the molten glass and provide heat to the cold cap. As the bubbles rise through the highly viscous glass, they adopt a spherical-cap shape [1]. Meanwhile, the conversion of the batch to glass generates significant amounts of gases (such as water vapor, carbon dioxide, sulfur dioxide, and NOx) due to thermal decomposition [2]. These gases become trapped between the cold cap and molten glass, forming a foam layer [3]. For modeling multiphase flow in CFD and heat transfer simulations of waste glass melters at different scales, efforts are underway to augment the capabilities of the Nek5000 [4] and NekRS [5] open-source codes [6]. Nek5000/NekRS is a scalable and efficient spectral element code that has been successfully applied to a wide range of fluid dynamics problems. By leveraging the Nek5000/NekRS software, it becomes possible to model the melter systems more affordably and with lower computational requirements compared to currently utilized commercial CFD software. The specific objectives of this ongoing effort include: 1. Implementation of a level set method in Nek5000/NekRS: The level set method is a numerical technique commonly employed in CFD simulations to track and represent the interface between different phases or materials accurately. By incorporating this method into Nek5000/NekRS, the ability to simulate multiphase flows in waste glass melters at a high level of fidelity can be achieved. 2. Demonstration of capability for air bubbling through molten glass: As part of the development process, a specific case of air bubbling through molten glass will be simulated using the augmented Nek5000/NekRS code. This demonstration aims to showcase the ability of the software to accurately capture and analyze the complex phenomena involved in the multiphase flow within waste glass melters. By achieving these objectives, the improved Nek5000/NekRS code will offer a powerful computational tool for simulating and analyzing waste glass melter systems, enabling better understanding, optimization, and troubleshooting of these vitrification processes. The ability to accurately model and simulate multiphase flows has broad relevance across many industries and scientific domains, and the improved functionality can contribute to advancements in various fields beyond waste glass melter simulations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Phase distribution in Fischer-Tropsch mimicked slurry bubble column via computed tomography

This study aims to investigate the phases distribution and hydrodynamics in an air-Therminol LT-glass beads slurry bubble column reactor in bubbly and churn-turbulent flow regimes by implementing a gamma-ray computed tomography. It is found that gas holdup increases with increasing superficial gas velocity and operating pressure while increasing solids loading has an opposite effect on gas holdup measurements. It is noticed that the pressure effect is more significant at high solids loading and the solids loading is relatively more substantial at lower pressure. Solids loading has the most significant a stronger effect on the solids holdup profile than on the gas holdup profile. Current results were compared with the Sedimentation-Dispersion Model (SDM) predictions. Overall, the findings of this study advance the knowledge of the true behavior of phases distribution in FT mimicked slurry bubble columns which are pertinent in designing such reactors.

42 ENGINEERING↗

Reduced-Order CFD Modeling to Support Waste Loading Optimization in Hanford WTP Vitrification

The U.S. DOE Hanford Site stores over 56 million gallons of radioactive liquid tank waste that must be treated and immobilized for long-term disposal The Waste Treatment and Immobilization Plant (WTP) will vitrify this waste by feeding it into Joule-heated melters, where it is incorporated into a stable borosilicate glass Computational fluid dynamics (CFD) simulations of glass melters can provide insight into the maximum achievable waste loading under varying melter operating conditions Fully resolved VOF multiphase simulations were used as the reference model to capture bubble-driven convection in the melter, including bubble formation, rise behavior, and induced glass melt circulation Effective bubble column diameter and rise velocity were extracted from the resolved simulations, compared with empirical correlations, and refit across relevant viscosity and gas flow rate conditions Explicit gas–liquid interface tracking was replaced with a single-phase momentum source term model, enabling faster steady-state CFD simulations while preserving the dominant hydrodynamic effects of bubbling New empirical correlations were developed for effective bubble column diameter and bubble rise velocity by fitting resolved simulation data across expected melter viscosity and gas flow rate ranges, providing improved inputs for the momentum source term model compared with existing literature correlations The momentum source term model reduced fluid-domain mesh size by 89% and achieved an 8.4× computational speedup relative to resolved bubbling simulations The validated momentum source term approach enables prediction of process-relevant heat transfer behavior in the integrated melter model, including heat transfer from the molten glass to the cold cap, plenum, refractory walls, and surrounding structural regions under varying melter operating conditions

12 - MGMT OF RADIOACTIVE AND NON-RADIOACTIVE WASTE↗

Sensitivity Effects of Hollow Glass Micro-Balloon Doping on RDX-Based Explosives

Sensitivity to initiation is an important characteristic of high explosives. Many chemical and physical properties are fine-tuned to deliver an energetic material that behaves according to the user’s specifications exactly. In some cases, it is advantageous to study the effects that non energetic additives have on the performance of an explosive material. Following on the promising results obtained in other experiments, a study is conducted on the effects of hollow glass micro-balloons (bubbles, spheres), or HGMB, on a material’s sensitivity. Threshold test data is compared between several formulations of explosives. The control formulation is an RDX-based explosive with a non-energetic binder, and the test formulations are identical in composition, but with the addition of HGMB, up to 6% by volume. Safety testing of the new HGMB-doped explosive formulations is conducted to ensure they can be produced and handled safely prior to intentional detonation. This experiment utilizes an attenuation card of varying thicknesses between the initiator and the test article to attenuate the shock imparted, and a witness plate is analyzed for each test article to determine a GO or NO GO result. The data collected and the conclusions of this study affect how additives like HGMB are utilized in future explosive sensitivity threshold experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advanced Computational Modeling of High-Level Waste Vitrification at the Hanford Site

The U.S. Department of Energy (DOE) has selected vitrification for stabilizing legacy tank waste at the Hanford site, where radioactive waste from plutonium production was historically stored in underground tanks. This waste will be separated into low-activity waste (LAW) and high-level waste (HLW) fractions and processed at the Waste Treatment and Immobilization Plant (WTP). At WTP, glass melters are used for the vitrification of radioactive tank waste, transforming it into a stable borosilicate glass form for safe long-term storage. The melter vessel is constructed from highly durable and heat-resistant materials, where the vitrification process occurs. The main regions that are modeled are the melt pool, plenum, cold cap, riser/discharge chamber, and surrounding structure with insulation layers. Forced convection induced by air bubblers at the base of the melter ensure uniform temperature distribution and provide heat to the cold cap layer. The cold cap is a region of reacting batch feed that floats on top of the molten glass and is where the batch-to-glass reactions occur. Joule heating provided by electrodes mounted along the vertical walls of the melter and immersed directly in the glass, generates the necessary heat for the net endothermic conversion processes that occur in the cold cap. The high temperatures, radioactivity, and opaque nature of the glass prevent direct observation inside the melters. Therefore, computational models are essential for providing insight into factors that affect melter throughput. Thermocouples in the plenum provide operators with plenum temperature measurements. Operational adjustments include bubbling rate, voltage supplied to the electrodes, feed adjustments, and glass removal rate. Different computational fluid dynamics (CFD) models have been developed, each serving a specific purpose. There are CFD models of different scale melters, as well as models that capture the two-phase flow interfaces of rising bubbles in the molten glass or models with a simplified molten glass region so that the surrounding structure and plenum can be feasibly incorporated. Pilot-scale melter models have been developed to serve as validation of the methods employed in the simulation of the full-scale WTP melters. Models incorporating resolved bubbling are used to develop momentum source terms to implement into a single phase, multi-region, steady-state flow model that is being validated by measured process parameters such as glass production rate, voltage, input power, plenum temperatures, etc. The resolved bubbling model uses the multiphase volume of fluid approach to model the system with a high-resolution interface capturing scheme to maintain sharp interfaces between the molten glass and the air phase. The suite of CFD models is continually being improved to incorporate more realistic physics and achieve faster turnaround time. For example, an incremental controller is implemented to automatically adjust electrode voltage within the simulation to a molten glass set point temperature of 1150°C. Newer models feature improved meshes to ensure conformal meshes between regions and eliminate unnecessary mesh refinement in areas that are not of interest (such as boundary layers in offgas ports). Instead of explicitly modeling the structural, refractory, and insulation layers of the melter, a thermal resistance approach is used with published correlations used for boundary conditions. The development of robust and efficient CFD models will be instrumental in enabling the WTP to successfully fulfill its mission of safely stabilizing legacy nuclear waste.

12 - MGMT OF RADIOACTIVE AND NON-RADIOACTIVE WASTE↗

Temperature Controlled Glass Additive Manufacturing

Glass additive manufacturing (AM) is an emerging technology with a wide range of applications in chemistry, biology, optical science, and engineering. A custom laser-based glass 3D printer was developed by a group of engineers at Los Alamos National Laboratory (LANL) and is being optimized to produce hardware for chemical processing equipment, microfluidic systems, as well as optical elements. AM glass using a filament deposition modeling (FDM) approach allows for generation of parts with high optical quality. The quality of the glass can be affected by the generation of defects such as bubbles and vaporization which affect the optical quality of the glass. The defects can also affect the mechanical performance of the glass and lead to sample cracking.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Corrosion Testing of Refractory inContact with Molten Glasses Designed for Waste Vitrification - VSL Touchpoint Matrix Glasses

It is known that the predictive life of the refractory ceramic liner of nuclear waste glass melters is conservative, as demonstrated by performance of these materials such as in the Defense Waste Processing Facility (DWPF). The motivation for this task is to maximize the useful life of the melters that will be operated at the Waste Treatment and Immobilization Plant (WTP), which will in turn minimize procurement and disposal costs and melter outage times, as well as to identify maximum loadings in the waste glass of those species that corrode melter components. This task was initiated jointly with Pacific Northwest National Laboratory (PNNL) with the objective to develop a methodology and model to enable more accurate prediction of refractory service life under prototypic conditions from laboratory-scale material corrosion tests. Refractory corrosion is generally reported as physical material loss, measured in units of distance (e.g., inch) or as physical material loss rate, measured in units of distance per time (e.g., inch/day). In post-operational melters, the refractory corrosion is measured directly, sometimes reported as corrosion depth. Crucible tests are used in the laboratory to accelerate the refractory corrosion to facilitate a meaningful measurement in a commensurate amount of time. Crucible tests are particularly useful in understanding refractory corrosion across a large glass composition space, where operational testing would be prohibitive. Some of the critical parameters that are known to influence refractory corrosion by molten glass in a crucible test are temperature, system redox, molten salt phases, glass chemistry, and test duration. The majority of data collected for Monofrax® K-3 (hereafter referred to as K-3) corrosion is from crucible tests, but a small amount comes directly from scaled and production melters. Crucible test data has been collected under varying conditions, whereas data collected from operational melters is relatively fewer and represents conditions specific to the melter campaign. The result is that the published data can be grouped and analyzed in multiple ways, not all of which are readily comparable. The Standard Test Method for Isothermal Corrosion Resistance of Refractories to Molten Glass (ASTM C621) outlines the general guidelines used across industry. That method describes a sealed, static test in which the surface area of the refractory coupon and the volume of glass are fixed. A significant portion of the crucible data pertaining to nuclear waste glasses has been collected in a modified configuration; the most notable differences being the surface area of the refractory coupon to volume of the glass and use of a method for bubbling the melt. To our knowledge, the influence of those parameters on the refractory corrosion has not been quantified. In this work, it was determined that static tests and bubbled tests would be performed. Savannah River National Laboratory (SRNL) was tasked with setting up and performing static testing while PNNL was tasked with setting up and performing bubbled testing. Initial activities were performed to establish laboratory methods that reproduce data comparable to existing data sets of K-3 refractory corrosion by low activity waste (LAW) and high-level waste (HLW) glass compositions. Later activities were focused on refining the test parameters to establish a standard test practice to be used between Laboratories and collecting additional data to be used in the enhanced waste glass model development. This document serves primarily to convey the refractory loss measurement results from corrosion testing of K-3 refractory with waste glass compositions developed for use in the WTP melters. The data will be used in the enhanced property/composition models being developed for waste glass vitrification and melter operations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Measuring the density, viscosity, and surface tension of molten titanates using electrostatic levitation in microgravity

Rare earth and barium titanates are useful as ferroelectric, dielectric, and optical materials. Measurements of their thermophysical properties in the liquid state can help guide melt processing technologies for their manufacture and advance understanding of fragile liquids' behavior and glass formation. Here, we report the density, thermal expansion, viscosity, and surface tension of molten BaTi 2 O 5 , BaTi 4 O 9 , and 83TiO 2 -17RE 2 O 3 (RE = La or Nd). Measurements were made using electrostatic levitation and droplet oscillation techniques in microgravity, which provide access to quiescent liquid droplets and deep supercooling of 510–815 K below the equilibrium melting points. Densities were measured over 900–2400 K. Viscosities were similar for all four compositions, increasing from ~10 mPa s near 2100 K to ~30 mPa s near 1750 K. Surface tensions were 450–490 dyn cm -1 for the rare earth titanates and 383–395 dyn cm -1 for the barium titanates; surface tensions of all compositions had small or negligible temperature dependence over 1700–2200 K. In conclusion, for solids recovered after melt quenching, x-ray microtomography revealed the fracture mechanics in crystalline products and minimal internal porosity in glass products, likely arising from entrapped gas bubbles. Internal microstructures were generally similar for products processed either in microgravity or in a terrestrial aerodynamic levitator.

42 ENGINEERING↗

Small Scale Melter Testing of HLW Algorithm Glasses: Matrix 1 Tests

The principal objectives of the DM100 tests were to determine the effects of glass property extremes (glass viscosity, electrical conductivity, and T1%), minimum and maximum concentrations of several major and minor glass components, +/-15% batching errors in the addition of Glass Forming Chemicals (GFCs) to the feed, and variation in the sources of boron and sodium used in the GFCs on processing rates and melter conditions (off-gas characteristics, glass processing, foaming, cold cap, etc.) at constant bubbling rate.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Viscosity of glass-forming melt at the bottom of high-level waste melter feed cold caps: Effects of temperature and incorporation of solid components

At the final stages of conversion of melter feed (glass batch) to molten glass, the transient glass-forming melt becomes a continuous liquid phase encapsulating dissolving solid particles and gas bubbles that produce primary foam at the bottom of the cold cap (the reacting melter feed in an electric glass melting furnace). The glass-forming melt viscosity plays a dominant role in primary foam formation, stability, and eventual collapse, thus affecting the rate of melting (the glass production rate per cold cap area). For several melter feeds designed for nuclear waste vitrification, we have traced the glass-forming melt viscosity during the final stages of feed-to-glass conversion as it changes in response to changing temperature and composition (resulting from dissolving solid particles). Starting with a relatively low values at the moment when the melt connects, melt viscosity reaches maximum within the primary foam layer and then decreases to its final melter-operating temperature value. We paid a particular attention to the cold-cap bottom—the boundary between the primary foam layer and the thermal boundary layer—where the melt viscosity affects the rate of melting predominantly through its effect on the temperature at which primary foam is collapsing.

Lee, Seung Min↗

Integrated DM1200 Melter Testing of HLW AZ-102 Composition Using Bubblers (Final Report)

This report documents melter and off-gas performance results obtained on the DM1200 HLW Pilot Melter during processing of simulated HLW AZ-102 feed. The principal objectives of the DM1200 melter testing were to determine the achievable glass production rates for simulated HLW AZ-102 feed; determine the effect of bubbling rate on production rate; characterize melter off-gas emissions; characterize the performance of the prototypical off-gas system components as well as their integrated performance; characterize the feed, glass product, and off-gas effluents; and to perform pre- and post test inspections of system components.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Synergistic foam stabilization and transport improvement in simulated fractures with polyelectrolyte complex nanoparticles: Microscale observation using laser etched glass micromodels

Inaccessibility to direct pore scale observation in hydrocarbon recovery of tight shale formations poses a great challenge to water-energy nexus initiatives and necessitates the use of high throughput technologies to emulate environmentally friendly processes. Herein, we employ a precise glass micromodel fabrication and visualization method to isolate the supercritical CO 2 bubbles surrounded by CO 2 -water lamella prepared in saline produced water stabilized with molecular complexation of zwitterionic surfactants (ZS) and polyelectrolyte complex nanoparticles (PECNP). The Selective Laser Enhanced Etching (SLE) technique was selected for micromodel simulation of high-pressure flow. Two representative designs, (1) fracture/micro-crack network 28 and (2) fracture/matrix were etched on fused silica glass with a laser printing machine and scCO 2 foam was injected to study the foamability, propagation, stability, and fluid loss properties. The highly monodispersed and uniformly distributed array of scCO 2 bubbles were detected in flow of scCO 2 foam in highly saline brine containing ionic complexes of positively charged PECNPs and ZS, whereas foam flow with the lamella containing ZS in fractures offered a noticeably large and polydisperse array of scCO 2 bubbles. scCO 2 bubble motion and deformation were traced, and local description of foam flow was visually examined. The confined array of scCO 2 bubbles stabilized by ZS in microcracks was affected by bubble growth and coalescence, whereas the super-populated array of monodispersed scC O2 bubbles with lamella containing complexes of PECNP and ZS were able to fill the channels with stable configurations within the timeframe of comparative stability measurements. The ability of complex fluid to prevent the formation damage was evaluated through fluid loss visualization in micromodels. Probing scCO 2 foam transport in homogenous porous media revealed smaller volume leak-off for scCO 2 foam containing PECNP-ZS ionic complexes.

04 OIL SHALES AND TAR SANDS↗

DM1200 Tests with C-104/AY-101 HLW Simulants (Final Report)

This report documents melter and off-gas performance results obtained on the DM1200 HLW Pilot Melter during processing of simulated HLW C-104/AY-101 feed. The principal objectives of the DM1200 melter testing were to determine the achievable glass production rates for simulated HLW C-104/AY-101 feed; determine the effect of bubbling rate on production rate; characterize melter off-gas emissions; characterize the performance of the prototypical off-gas system components as well as their integrated performance; characterize the feed, glass product, and off-gas effluents; and to perform pre- and post test inspections of system components.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Vitrification of High-Cr Glass in Research-Scale Melter

This test report describes the experimental results from a small-scale test using the research-scale melter (RSM) at Pacific Northwest National Laboratory to demonstrate processing of a high-Cr simulated feed stream, designated HLW-HCr-16. The RSM is a small, joule-heated melter capable of processing melter feed continuously. The melter is equipped with Inconel ® 693 electrodes, Monofrax ® K-3 refractory, and an Inconel 690 pour spout. An electric kiln surrounds the melter body and minimizes heat loss from the melter body during operation. The RSM is equipped with an offgas treatment system that employs quenching, wet scrubbing, and high-efficiency mist elimination. The glass-discharge section is heated to facilitate pouring of the glass. The melter is fitted with a melt cavity that is ~25 cm (10 in.) in diameter with a nominal glass depth of 8.9 cm (3.5 in.). The melter was operated with a target glass temperature of 1150°C and target plenum temperature between 550°C and 700°C for this test. The air bubbling rate was 4.2 L/min. Overall, during the continuous operation of the melter for ~ 103 hours, ~ 141 kg of glass was produced. At the conclusion of the test, the melter and exhaust lines were visually inspected for particulate deposition and corrosion. Entrained material had adhered to the underside of the melter lid and to the exhaust piping. Enrichments in elements such as Cl, F, B, K, Li, P, Na, and S were measured in these deposits through inductively coupled plasma–optical emission spectroscopy and X-ray fluorescence analysis. When the melter electrodes and air bubbler tube were removed from the glass in the RSM, the electrodes appeared discolored, but no significant loss of metal was observed. The processing of a high-Cr simulant, HLW-HCr-16, in the RSM produced glass at an average rate of 1.36 kg/h, equaling a melter-surface-area normalized glass generation rate of 654 kg/day/m 2 . The resulting glass met the toxicity characteristic leaching procedure requirement. Test results of crystallinity, electrical conductivity, and viscosity showed good processing properties of this high-Cr high-level waste glass. RSM offgas was also sampled and analyzed at periodic intervals during steady-state operating conditions. The total decontamination factor averaged by four sampling periods was 134. The concentrations of CO and NO x in emissions were 237 to 422 and 69 to 94 parts per million by volume, respectively.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effect of feed composition on the production of off-gases during vitrification of simulated low-activity nuclear waste

During the vitrification of nuclear waste, hazardous and radioactive emissions are generated from the feed-to-glass conversion reactions, in addition to discharges from forced air bubbling and air inleakage. Although the major gaseous emissions are water vapor, nitrogen, and carbon dioxide, various monitored environmental pollutants are also released, such as nitrogen oxides or sulfur dioxide. In addition, reactions between organics and nitrates in the feed may also form products of incomplete combustion such as carbon monoxide and acetonitrile. Although off-gas emissions are commonly measured during both laboratory- and pilot-scale melter testing, no predictive tool is currently available to a priori estimate the composition of gaseous emissions during nuclear waste vitrification. This work forms a basis for the development of such predictive tool by measuring gas evolution from a broad range of simulated low-activity waste melter feeds using evolved gas analysis data and developing correlations between the feed and off-gas compositions. Using reaction stoichiometry and regression analysis, we demonstrate that next to the content of nitrogen and organic carbon in the feed, the gaseous emissions are affected by the feed reduction-oxidation conditions – the more the feed is reduced, the less nitrogen monoxide, and more carbon monoxide and acetonitrile evolves. In conclusion, the results presented in this work provide a first step towards reducing the amount of expensive physical melter testing and the regression analysis provides a simple tool for rapid optimization of feed composition with respect to off-gas composition.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗