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At least 433 records · Page 24

Effects of Sulfate on Rhenium Incorporation into Low-Activity Waste Glass

Technetium-99 (99Tc) is a major radionuclide of concern in the Hanford low-activity waste (LAW), which will be vitrified into borosilicate glass at the Waste Treatment and Immobilization Plant (WTP). Sulfate content in LAW has been known to be a critical factor affecting the volatile loss of 99Tc during melting of the LAW glass feed (a mix of liquid LAW and mineral/chemical additives). We investigated rhenium (a nonradioactive surrogate for 99Tc) incorporation into glass by performing crucible melting tests of two representative simulated LAW glass feeds, each prepared with varied sulfur levels. The sulfate content varied from the original content to half of the original (½S) and to zero (0S), in the range of 0 to 0.8 mass % SO3 in glass if 100% retained. The slurry feeds were dried at 105°C and heated to 400–1100°C. Deionized water leach at room temperature and at 80°C was conducted on the dried feed and heat-treated samples to analyze the chemical compositions of soluble and insoluble phases separately and to profile the partitioning of various components into different phases during the melting process. Different partitioning behavior of rhenium, sulfate, and chlorine is discussed in connection with major feed-to-glass conversion reactions. The mechanism on how sulfate affects rhenium incorporation during feed-to-glass conversion reactions, and so final retention of rhenium in glass, is proposed based on the two hypotheses that segregated sulfate-rich phase forms during feed conversion reactions and Re preferentially partitions to this sulfate-rich phase.

Jin, Tongan↗

Redox-Dependent Solubility of Technetium in Low Activity Waste Glass

The solubility of technetium was measured in a Hanford low activity waste glass simulant. The simulant glass was melted, quenched and pulverized to make a stock of powdered glass. A series of glass samples were prepared using the powdered glass and varying amounts of solid potassium pertechnetate. Samples were melted at 1000°C in sealed fused quartz ampoules. After cooling, the bulk glass and the salt phase above the glass (when present) were sampled for physical and chemical characterization. Technetium was found in the bulk glass up to 2000 ppm (using the glass as prepared) and 3000 ppm (using slightly reducing conditions). The chemical form of technetium obtained by x-ray absorption near edge spectroscopy can be mainly assigned to isolated Tc(IV), with a minority of Tc(VII) in some glasses and TcO 2 in two glasses. The concentration and speciation of technetium depends on glass redox and amount of technetium added. Solid crystals of pertechnetate salts were found in the salt cake layer that formed at the top of some glasses during the melt.

LAW glass↗

Fluoropolymer Composites from Partially Perfluoroalkylated Waste Polyethylene

Chemically modified plastics have emerged as practical solutions to plastic waste increases. Here, the inherent novelty of decorating polymer chains with chemical functionality results in distinct properties that expand the available application space. Nevertheless, developing designer materials for specific applications beyond compatibilization or mild property enhancement is difficult due to the synergistic effects of both the polar functionality imparted and the parent materials' intrinsic properties. By incorporating perfluoro-alkyl side-chains onto the backbone of dehydrogenated waste HDPE, unique surface properties intermediate between polytetrafluoroethylene (PTFE, the model fluoropolymer) and HDPE become apparent, while the overall material mechanical and thermal properties result in more LLDPE-like materials. This is demonstrated through moderate decreases in the surface free energy of the perfluoroalkylated polyolefin surface (increase in H 2 O contact angle of ~ 6°) and increased ordering under shear when blended with PTFE nanoparticles where the crossover point occurred at higher strains. Critically, perfluoroalkylated HDPE possesses improved rheological modification properties at elevated temperatures with PTFE nanoparticles, resulting in more thermally robust and stable composite materials.

fluoropolymer↗

Role of Bifunctional Ru/Acid Catalysts in the Selective Hydrocracking of Polyethylene and Polypropylene Waste to Liquid Hydrocarbons

Hydrogenolysis of C–C bonds over Ru-based catalysts has emerged as a deconstruction strategy to convert single-use polyolefin waste to liquid alkanes at relatively mild conditions, but this approach exhibits limitations, including methane formation resulting from terminal C–C bond scission. In this study, a variety of catalysts were investigated for the reductive deconstruction of polyethylene (PE) and polypropylene (PP) to identify supports that promote nonterminal C–C bond scission. We found that Ru nanoparticles supported on Brønsted-acidic zeolites with the faujasite (FAU) and Beta (BEA) topologies were highly active for the cleavage of C–C bonds in PE and PP, exhibiting improved liquid yields and suppressed methane formation. For the deconstruction of PE, supporting ruthenium nanoparticles (5 wt %) on FAU increased the yields of liquid alkanes to 67% compared to 33% over an inert silica support (5 wt % Ru/SiO 2 ) at 200 °C, 16 h, under 30 bar of H2. A dramatic selectivity enhancement toward liquid hydrocarbons was also observed for PP over Ru/FAU and Ru/BEA compared to Ru/SiO 2 . To understand the origin of this selectivity improvement, a combination of ex situ and operando characterization techniques were used to reveal that both catalyst structure and acidity play key roles in PE and PP conversion. Operando X-ray absorption spectroscopy studies with model polyolefins over Ru-supported catalysts with varying acidity levels revealed that the local chemical environment of Ru [0] during the reaction is consistent across multiple acidic supports, although the onset of reduction during synthesis of the nanoparticles varies across different supports. These results, combined with reactivity data, demonstrate the importance of the acid-noble metal cooperativity in promoting selective C–C bond scission toward liquid alkanes that shifts the mechanism from hydrogenolysis to ideal hydrocracking.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High Chrome Refractory Characterization: Part II . Accumulation of Spinel Corrosion Deposits in Radioactive Waste Glass Melters

High Cr 2 O 3 containing Monofrax ™ K‐3 is a robust refractory that is used in radioactive waste glass melters worldwide. Monofrax ™ K‐3 contains highly reduced phases. Conversely, many of the radioactive feeds being processed are highly oxidizing. The K‐3 refractory corrosion rates in oxidizing (high nitrate) feeds were ~1.8–2.8 times higher than the rates determined using reducing feeds. The corrosion product formed is a mixture of spinel and glass (slag) that can accumulate on the melter floor. A methodology to calculate the depth of slag deposits from refractory corrosion is presented and verified with slag measurements from the Defense Waste Processing Facility ( DWPF ) melter after it had processed oxidized feeds for 1.75 years. The calculations show that had the facility continued to process oxidized feeds the melter lifetime (based on when the deposits could have reached and blocked the pour spout riser) would have been ~4.5 years. The DWPF changed to a reducing flow sheet after ~3 years of operation. The lifetimes of Melter #1 and Melter #2, assuming a failure due to pour spout blockage, are calculated as 7.7–12 years based on corrosion rates measured with reducing feeds. Lifetimes of 9 and >11 years have actually been achieved.

Jantzen, Carol M.↗

Foaming during Nuclear Waste Melter Feeds Conversion to Glass: Application of Evolved Gas Analysis

During the final stages of batch-to-glass conversion in a waste-glass melter, gases evolving in the cold cap produce primary foam, the formation and collapse of which control the glass production rate via its effect on heat transfer to the reacting batch. We performed quantitative evolved gas analysis (EGA) for several HLW melter feeds with temperatures ranging from 100 °C to 1150 °C, the whole temperature span in a cold cap. EGA results were supplemented with visual observation of batch-to-glass transition using the feed expansion tests. Upon heating, most of the gases—mainly H2O, CO2, NO, NO2, N2 and O2—evolve at temperatures below 700 °C and escape directly to the atmosphere through open porosity. However, as open porosity closes when enough glass-forming melt appears at 720 °C, the residual gas evolution leads to the formation of primary foam. We found that primary foaming is mostly caused by the decomposition of residual carbonates, though oxygen evolution from iron-redox reaction can also play a role. We also show that the gas evolution shifts to a higher temperature when the heating rate increases. The implications for the mathematical modeling of foam layer in the cold cap are presented.

Hujova, Miroslava↗

Compositional control of radionuclide retention in hollandite-based ceramic waste forms for Cs-immobilization

Hollandite materials, as a class of crystalline nuclear waste forms, are promising candidates for the immobilization of radioactive elements, such as Cs, Ba, as well as a variety of lanthanide and transition-metal fission products. In this study, three Ga-doped titanate hollandite-type phases, Ba 1.33 Ga 2.67 Ti 5.33 O 16 , Ba 0.667 Cs 0.667 Ga 2 Ti 6 O 16 , and Cs 1.33 Ga 1.33 Ti 6.67 O 16 , were synthesized using a solid-state reaction route. All synthesized phases adopted a single phase tetragonal structure, as determined by powder X-ray diffraction (XRD), and elemental analysis confirmed the measured stoichiometries were close to targeted compositions. Extended X-ray absorption fine structure spectroscopy (EXAFS) was used to determine the local structural features for the framework of octahedrally coordinated cations. EXAFS data indicated that Cs 1.33 Ga 1.33 Ti 6.67 O 16 possessed the most disordered local structure centered around the Ga dopant. The enthalpies of formation of all three hollandite phases measured using high-temperature oxide melt solution calorimetry were found to be negative, indicating enthalpies of formation of these hollandites from oxides are thermodynamically stable with respect to their constituent oxides. Furthermore, the formation enthalpies were more negative and hence more favorable with increased Cs content. Finally, aqueous leaching tests revealed that high Cs content hollandite phases exhibited greater Cs retention as compared to low Cs content hollandite. While preliminary in nature, this work draws attention to the links between the capacity for radionuclide retention, atomistic level structural features and bulk thermodynamic properties of materials.

nuclear (including radiation effects), materials a↗

Effect of sucrose on foaming and melting behavior of a low-activity waste melter feed

Reductants, such as sucrose, are added to nuclear waste melter feeds containing high fractions of nitrates and nitrites to reduce excessive foaming during feed-to-glass conversion and to decrease sulfate segregation and increase technetium retention. The sucrose effect on foaming and melting reactions during the conversion was examined using the feed volume expansion, thermogravimetric analysis, evolved gas analysis, X-ray diffraction, and scanning electron microscopy with energy dispersive X-ray spectrometry. Different sucrose additions were used to vary the carbon to nitrogen (C/N) ratio in the melter feed. As C/N ratio increased, the extent of foaming decreased and N2/NO ratio increased in the gas phase evolved. Significant foam suppression, rapid gas release at approximately 250°C, and reduction of transition metal oxides were observed at C/N > 1.1.

Appel, Connor J.↗

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↗

Recycled water reuse permit renewal application for the materials and fuels complex industrial waste ditch and industrial waste pond

This renewal application for the Industrial Wastewater Reuse Permit (IWRP) WRU-I-0160-01 at Idaho National Laboratory (INL), Materials and Fuels Complex (MFC) Industrial Waste Ditch (IWD) and Industrial Waste Pond (IWP) is being submitted to the State of Idaho, Department of Environmental Quality (DEQ). This application has been prepared in compliance with the requirements in IDAPA 58.01.17, Recycled Water Rules . Information in this application is consistent with the IDAPA 58.01.17 rules, pre-application meeting, and the Guidance for Reclamation and Reuse of Municipal and Industrial Wastewater (September 2007). This application is being submitted using much of the same information contained in the initial permit application, submitted in 2007, and modification, in 2012. There have been no significant changes to the information and operations covered in the existing IWRP. Summary of the monitoring results and operation activity that has occurred since the issuance of the WRP has been included. MFC has operated the IWP and IWD as regulated wastewater land treatment facilities in compliance with the IDAPA 58.01.17 regulations and the IWRP. Industrial wastewater, consisting primarily of continuous discharges of nonhazardous, nonradioactive, routinely discharged noncontact cooling water and steam condensate, periodic discharges of industrial wastewater from the MFC facility process holdup tanks, and precipitation runoff, are discharged to the IWP and IWD system from various MFC facilities. Wastewater goes to the IWP and IWD with a permitted annual flow of up to 17 million gallons/year. All requirements of the IWRP are being met. The Operations and Maintenance Manual for the Industrial Wastewater System will be updated to include any new requirements.

99 GENERAL AND MISCELLANEOUS↗

Spent Nuclear Fuel and Reprocessing Waste Inventory: Spent Fuel and Waste Disposition

This report provides information on the inventory of spent nuclear fuel (SNF) in the United States located at Nuclear Power Reactor (NPR) and Independent Spent Fuel Storage Installation (ISFSI) sites, as well as SNF and reprocessing waste located at U.S. Department of Energy (DOE) sites and other research and development (R&D) centers as of the end of calendar year 2021. Actual or estimated quantitative values for current inventories are provided along with inventory forecasts derived from examining different future nuclear power generation scenarios, based on information available and assumptions made at the time the scenarios were developed in the spring of 2022. The report also includes select information on the characteristics associated with the wastes examined (e.g., type, packaging, heat generation rate, decay curves).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Study of extraterrestrial disposal of radioactive wastes. Part 2: Preliminary feasibility screening study of extraterrestrial disposal of radioactive wastes in concentrations, matrix materials, and containers designed for storage on earth

The results are reported of a preliminary feasibility screening study for providing long-term solutions to the problems of handling and managing radioactive wastes by extraterrestrial transportation of the wastes. Matrix materials and containers are discussed along with payloads, costs, and destinations for candidate space vehicles. The conclusions reached are: (1) Matrix material such as spray melt can be used without exceeding temperature limits of the matrix. (2) The cost in mills per kw hr electric, of space disposal of fission products is 4, 5, and 28 mills per kw hr for earth escape, solar orbit, and solar escape, respectively. (3) A major factor effecting cost is the earth storage time. Based on a normal operating condition design for solar escape, a storage time of more than sixty years is required to make the space disposal charge less than 10% of the bus-bar electric cost. (4) Based on a 10 year earth storage without further processing, the number of shuttle launches required would exceed one per day.

Hyland, R. E.↗

Study of extraterrestrial disposal of radioactive wastes. Part 1: Space transportation and destination considerations for extraterrestrial disposal of radioactive wastes

A feasibility study of extraterrestrial disposal of radioactive waste is reported. This report covers the initial work done on only one part of the NASA study, that evaluates and compares possible space destinations and space transportation systems. The currently planned space shuttle was found to be more cost effective than current expendable launch vehicles by about a factor of 2. The space shuttle requires a third stage to perform the waste disposal missions. Depending on the particular mission, this third stage could be either a reusable space tug or an expendable stage such as a Centaur.

Thompson, R. L.↗

Direct oxidation of strong waste waters, simulating combined wastes in extended-mission space cabins

The applications of modern technology to the resolution of the problem of solid wastes in space cabin environments was studied with emphasis on the exploration of operating conditions that would permit lowering of process temperatures in wet oxidation of combined human wastes. It was found that the ultimate degree of degradation is not enhanced by use of a catalyst. However, the rate of oxidation is increased, and the temperature of oxidation is reduced to 400 F.

Ross, L. W.↗

Supercritical waste oxidation of aqueous wastes

For aqueous wastes containing 1 to 20 wt% organics, supercritical water oxidation is less costly than controlled incineration or activated carbon treatment and far more efficient than wet oxidation. Above the critical temperature (374 C) and pressure (218 atm) of water, organic materials and gases are completely miscible with water. In supercritical water oxidation, organics, air and water are brought together in a mixture at 250 atm and temperatures above 400 C. Organic oxidation is initiated spontaneously at these conditions. The heat of combustion is released within the fluid and results in a rise in temperature 600 to 650 C. Under these conditions, organics are destroyed rapidly with efficiencies in excess of 99.999%. Heteroatoms are oxidized to acids, which can be precipitated out as salts by adding a base to the feed. Examples are given for process configurations to treat aqueous wastes with 10 and 2 wt% organics.

Modell, M.↗