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At least 523 records · Page 29

Corrosion Testing of Refractory in Contact with Molten Glasses Designed for Waste Vitrification – VSL Touchpoint Matrix Glasses (Revision 1)

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).[1] 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.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Panel Session 24B: Records, Knowledge, and Memory for Radioactive Waste Repositories: Generational Equity Focus

This panel focused on the latest thoughts, ideas, and methodologies being explored throughout the world on how to communicate with future generations regarding nuclear waste disposal. Scientists determined many years ago that geological disposal in a repository was the preferred solution for nuclear waste disposal given the longevity concerns of the waste(s). Future generations must be informed through records, memory keeping and permanent markers to ensure they are aware of, and knowledgeable of, the dangers associated with nuclear waste isolated from the biosphere. Panelists with presentations: You Want to Drill Where? Human Intrusion Messaging Considerations (Thomas Peake, Jonathan Major); Ethical Reflections on the Basic Reasons for RK and M Measures (Carl-Reinhold Brakenhielm); NEA Activities on Information, Data and Knowledge Management (Rebecca Tadesse); Records, Knowledge and Memory (RK and M) Across Generations: Recent Activities and Progress in Sweden (Claudio Pescatore)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Multivariate Linear Models for In Situ Monitoring of Low-Activity Nuclear Waste Using Infrared and Raman Spectroscopy - 20218

This paper presents the use of in situ monitoring tools for molecular analysis of non-radioactive species found in the supernatant liquid and dissolvable salt cake of nuclear waste at Hanford. We have selected two in situ spectroscopic techniques that do not require any sample preparation or consumables: infrared (in the form of attenuated total reflectance Fourier transform infrared or ATR-FTIR) and Raman spectroscopy. This work aims to evaluate their performance for liquid waste simulants representative of the Hanford DFLAW (Direct Feed Low-Activity Waste) feed. In addition, we have evaluated the performance of four multivariate linear models that extract concentrations from spectral measurements for a data set that was designed to include key molecular species found in liquid low-activity waste. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Irradiation Assessment of a Lightweight Industrial Robot - Towards Faster, Safer and Sooner Waste Decommissioning - 20317

Robotic systems have been successfully applied in the nuclear industry for several decades as a safe approach to minimize the exposure dose of human operators. As nuclear waste management and decommissioning gathers pace, there is an emerging interest integrating modern off-the-shelf industrial robots in nuclear robotic systems which make use of complex electronics and software to improve functionality over traditional machines. The use of the industrial robots will significantly increase the pace of development of automated waste management systems at a reduced cost, and although these off-the-shelf robots are proven robust in typical industrial environments, performance in radioactive environments is less clear. This paper investigates the performance degradation of a lightweight industrial robot (KUKA iiwa 7 LBR 800) in a controlled radiation field, aiming to simulate conditions in highly radioactive nuclear waste handling facilities. The degradation of the industrial robot's performance is identified while measuring the air kerma dose-tolerance of sensitive components, via a systematic experimental methodology. The experience from this experiment has demonstrated the significant capabilities of industrial robots, which tolerated a large gamma dose of 164 Gy before a system failure. Future tests are planned, aiming to enable faster, safer and sooner waste management and decommissioning using complex robotic systems. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Closed‐Loop Recyclable Vitrimer Plastics from PET Waste: A Design for Circularity

Plastics are essential to modern society, but their low recycling rates and inefficient end-of-life management pose a significant environmental challenge. Herein, the efficient strategy for upcycling postconsumer poly(ethylene terephthalate) (PET) waste into robust, closed-loop recyclable vitrimer plastics and composites is presented to address this issue. The catalyst-free aminolysis utilizes readily available amines to deconstruct diverse PET wastes into macromonomers, which are upcycled into vitrimers, exhibiting superior mechanical properties and exceeding the ultimate tensile stress and Young's Modulus of virgin PET by 80% and 150% respectively. These vitrimers exhibit excellent healability, shape memory, thermal reprocessability, and closed-loop chemical recyclability, enabling quantitative macromonomer recovery even from mixed plastic waste streams and glass/carbon fiber reinforced vitrimer (G/CFRV) composites. Furthermore, the vitrimer resin yields robust GFRV and CFRV composites with tensile strengths exceeding those of traditional epoxy composites by 100% and 80%, respectively, while maintaining complete chemical recyclability of both constituent materials. A preliminary technoeconomic analysis confirms the costeffectiveness and competitiveness of the facile PET deconstruction approach, which is potentially adaptable to other condensation polymers. Further, this study presents a facile approach to upcycling plastic waste into circular plastics and composites, offering a sustainable solution to global plastic waste management and fostering a circular economy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A novel defoamer for processing nuclear waste: Testing and performance

Abstract Legacy radioactive waste from nuclear weapons material processing is the biggest environmental challenge in the state of South Carolina, and one of the biggest in the United States. Although substantial progress has been made in processing and vitrifying high‐level radioactive waste at the Savannah River site, approximately 35 million gallons remains to be treated and dispositioned. In this article, we show the development of a new defoamer for use in the processing of high‐level radioactive waste. The application of the new defoamer is not only more effective at controlling foam but will shorten the batch processing time leading to safer and more efficient processing. This has the potential to help shorten the overall site mission lifetime, saving the federal government hundreds of millions of dollars. The novel aspect of the new defoamer is its effectiveness and stability in the harsh conditions needed for processing high‐level radioactive waste: high temperatures, pH 4–13, strong oxidizing and reducing agents, and numerous metal catalysts. The defoamer will replace an existing antifoam agent that decomposes to form multiple flammable gases. Because the existing antifoam agent decomposes quickly, processing changes increased processing time. Statement of novelty We demonstrate that a new defoamer has been developed for use in processing high‐level radioactive waste. This novel defoamer is effective and stable in the harsh processing conditions with no detectable flammable by‐products. Because the existing antifoam agent decomposes quickly, processing changes, including lowering acid addition rates and evaporation rates, increased processing time. The new defoamer is not only more effective at controlling foam but will shorten the batch processing time and lead to safer and more efficient processing by eliminating the production of flammable gases. Statement of industrial relevance Foaming is of great concern in many industrial processes involving three‐phase gas/liquid/fine‐solids systems, like in water evaporation, mineral floatation, air sparging in situ remediation techniques, and in those found in the paper industry.

Lambert, Dan P.↗

Scaled melter testing of alternative reductants for Low-Activity Waste vitrification: Melter feed properties and processing behavior

This study examines the use of boron nitride (BN) and coke dust as alternative reductants for low-activity waste vitrification in scaled melter systems, intended to enhance operational flexibility at the Hanford Waste Treatment and Immobilization Plant. The baseline reductant, sucrose, while widely considered advantageous for glass production rates, produces challenging off gas emissions during processing. Early crucible-scale testing indicated that BN and coke effectively control foaming and glass redox, while significantly reducing acetonitrile emissions. Both real tank waste and simulant waste melter feeds were tested with BN and coke in this study. Rheological properties for melter feeds with both reductants were within operational limits, although the particle size of coke should be controlled and sufficient agitation is necessary to ensure smooth operations. While promising for handling and reduction of emissions, both simulant melter feeds demonstrated lower average glass production rates in the simulant melter system compared with sucrose. In the radioactive system, the rates were more comparable to previously measured low activity waste feeds on the order of 1285 kg m 2 day −1 for BN and 1671 kg m −2 day −1 for coke. Further scale-up testing is required to interpret the processing rates in the context of the full scale melter systems and evaluate the cost-benefit impact of these reductants on efficiency and sustainability.

Rigby, Jessica C. [Pacific Northwest National Labo↗

Thermal Oxo-degradation and Catalytic Upgrading of Plastic Waste to Light Olefins for a Circular Economy

The commercialization of conventional pyrolysis of plastic in an inert atmosphere has been hindered by large thermal requirements stemming from long reaction rates. The rate of thermal depolymerization of waste plastics can be accelerated by the addition of oxygen in a process known as thermal oxo-degradation (TOD). This study offers the prospect of TOD to upcycle postconsumer waste rapidly and efficiently. Using moderate temperatures and small amounts of air in a fluidized bed reactor, we demonstrated that waste high-density polyethylene and polypropylene are rapidly deconstructed to condensable products. These condensable products were catalytically upgraded in a micropyrolysis reactor using commercially available zeolite (HZSM-5) to monomeric olefins. The olefin yields proved to be greater than those achieved through the catalytic upgrading of condensable products from (nonoxidative) the pyrolysis of the same plastic wastes. The coupling of TOD with catalytic upgrading proves to be an energy-efficient pathway in a plastics circular economy for the production of light olefins from wastes.

Enthalpy↗

Quantification of Raman-Interfering Polyoxoanions for Process Analysis: Comparison of Different Chemometric Models and a Demonstration on Real Hanford Waste

The Hanford site represents a complicated environmental remediation challenge, remaining from the production of nuclear weapons. Over 100 million gallons of liquid radioactive waste of unknown composition will be chemically processed and vitrified, but the varying chemical composition and highly radioactive nature of the waste preclude the implementation of more developed, offline technologies to determine the composition. The only practical approach to waste treatment will require the significant utilization of real-time, chemometric modeling approaches. Although chemometric approaches have been applied to the analysis of Hanford waste, the models developed were highly tank-specialized, and limited discussion was provided on how models fared with interfering signals. As the tank waste is largely composed of oxoanions, which tend to have interfering Raman spectra, the general question was posed as to what chemometric approach is best suited to accurately quantify analytes in the presence of interfering signals. This was carried out by examining the ability of classical least square (CLS), principal component regression (PCR), partial least square (PLS), and locally weighted regression (LWR) to quantify NO 3 – and CO 3 2– using their bands around 1050 cm –1 . Finally, for all samples, the PLS-based model was found to be the most efficient approach from a model building and application perspective.

54 ENVIRONMENTAL SCIENCES↗

Analysis of Tar and Oil Derived from Pyrolysis and Copyrolysis of Waste Plastics and Biomass

Pyrolysis has been proposed as a potential technology for managing the growing volume of plastic waste generated worldwide. Co-pyrolysis of plastic waste with biomass is a promising technology for generating fuel and chemical products. However, this process generates tar as a waste product. The chemical properties of this tar have yet to be thoroughly analyzed. Further, this study presents the results of gas chromatography–mass spectrometry (GC–MS), Fourier-transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA) of oil and tar obtained from the pyrolysis of pure plastics including high-density polyethylene (HDPE), low-density polyethylene (LDPE), polyethylene (PE), polystyrene (PS), and plastic-biomass mixtures. GC–MS analysis revealed the presence of C 7 –C 37 carbon-containing hydrocarbons, which include alkanes and alkenes as the dominant products. FTIR data revealed the presence of various functional groups, including alcohols, aldehydes, ketones, and carboxylic acids, indicating the complexity of the pyrolysis and copyrolysis oil obtained from waste plastics and biomass. TGA data show that tar from all four plastics has a higher decomposition rate, suggesting the presence of heavier hydrocarbons compared with their corresponding oils. This research will be of interest to researchers looking to advance the study of plastic and biomass waste management.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Waste PET Chemical Processing to Terephthalic Amides and Their Effect on Asphalt Performance

The large amount of waste generated from polyethylene terephthalate (PET) packaging materials that have reached the end of life is creating a waste management issue that cannot be handled by mechanical recycling alone. Thus, it is imperative that alternate routes to recover and reuse these materials be pursued. A chemical recycling approach of mixed PET was demonstrated here that provides a mechanism by which PET waste can be efficiently recovered and repurposed to value-added products. The approach utilizes aminolysis of PET with a variety of amine nucleophiles, generating a small library of phthalimides with unique structures. In order to probe the high value of these products, the phthalimides were added to road-grade asphalt binder at 5 wt% and the resulting composite was evaluated. Specifically, rutting and fatigue characteristics as well as thermomechanical and creep performance were characterized and found to be improved by the inclusion of these additives by as much as 18%. In this work, additives made from deconstructed PET wastes were shown to improve the performance properties of asphalt at a variety of environmental conditions. These improvements would reduce the cost of road maintenance and provide a high-value market for waste PET. It is important to note that the asphalt binder utilized in this work was a commercial product already optimized for road conditions, not the raw bitumen; perhaps higher performance metrics could be obtained with virgin bitumen.

Recycling, Asphalt↗

Synthesizing Highly Crystalline Graphite Powder from Bulk Polyethylene Waste for Lithium-Ion Battery Anodes

Upcycling plastic waste into graphite can potentially be used, in conjunction with other methods, to manage existing waste materials and diversify graphite supply chains. However, synthesizing large quantities of crystalline graphite powder from plastic waste, particularly polyethylene (PE), remains a challenge because PE decomposes into light gases during thermal processing and simple methods do not exist at any appreciable size scale to address this challenge. In this work, a method is developed for air processing bulk forms of PE waste to create stable carbon char that does not readily decompose during high-temperature processing. This method employs solid additives in the form of salts, which are combined with the PE melt during air processing to increase the effective surface area of the melt and improve the oxygen-driven chemistry that stabilizes PE for high-temperature processing. After removal of the solid salt additives from the PE-derived char, it is converted into a highly crystalline bulk graphite powder using an Fe-based catalytic process. The PE-derived graphite anode in a lithium-ion coin cell showed a specific capacity of 345 mAh/g at 0.05C with an initial Coulombic efficiency of 87% and reversible capacity retention of ~100% at different current rates. It also showed a specific capacity of up to 313 mAh/g at 0.5 discharge/charge cycles per hour (0.5C) and Coulombic efficiency of 99.9% after 250 cycles, indicating excellent electrochemical performance as an anode material for lithium-ion batteries. This method illustrates that there are opportunities for upcycling large quantities of PE waste to produce graphite powders suitable for use in LIBs.

25 ENERGY STORAGE↗

Regional economic potential for recycling consumer waste electronics in the United States

Waste electronics are a growing environmental concern but also contain materials of great economic value. If properly recycled, waste electronics could enhance the sustainability of vital metal supply chains by offsetting the increasing demand for virgin mining. However, rapid changes in the size and composition of electronics complicate their end-of-life management. Here we couple material flow and geospatial analyses on over 90 critical consumer electronic products and find that over 1 billion devices, representing up to 1.5 million tonnes of mass, could be discarded annually in the United States by 2033. Emerging electronics such as connected home, health and augmented/virtual reality devices have become the fastest-growing types in the waste stream. Here we highlight policy opportunities to develop various sustainable circularity strategies around metal supply chains by showing the potential to integrate waste electronics and virgin mining pathways in western US regions, while new infrastructure designed specifically for waste electronics treatment is favourable in the central and eastern United States. Furthermore, we show the importance of building national-level refining and tear-down databases to improve electronics end-of-life management in the next decade.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Techno-economic and life cycle analysis of bio-hydrogen production using bio-based waste streams through the integration of dark fermentation and microbial electrolysis

Hydrogen derived from bio-based sources, or biohydrogen (bioH 2 ), has the potential to reduce GHG emissions from industrial and transportation sectors, owing to the low carbon footprint and myriad applications like refinery operation, ammonia production, steel production, fuel cell, etc. To evaluate the commercialization potential of bioH 2 production, we modeled bioH 2 production and conducted techno-economic analysis (TEA) and life cycle analysis (LCA) of two facilities producing 50 metric tonnes of bioH 2 per day from cheese whey (CW) and solid food waste (SFW) through the integration of dark fermentation (DF) and microbial electrolysis cell (MEC) technologies. LCA results showed that CW and SFW can produce carbon-negative bioH 2 , with emissions of −8.6 and −8.0 kg GHG kg −1 bioH 2 with carbon sequestration and renewable electricity resources, respectively, making bioH 2 potentially eligible for a tax credit of $\$3$ kg −1 H 2 based on provision 45 V of the U.S. Inflation Reduction Act (IRA). In this study, bioH 2 production treats waste streams to generate fresh water, thus, potentially can receive waste water treatment fee that varies with regions. The MEC capital cost dominates the bioH 2 cost, which is mainly determined by current density. With a current density of 20 A m −2 , the production cost for CW input varied between $\$17$ and $\$24$ kg −1 bioH 2 , while that for SFW input ranged from $\$29$ to $\$30$ kg −1 bioH 2 under different operating conditions, considering the 45 V tax credit, waste water treatment fee and production revenue. If the current density increases to 100 A m −2 , the bioH 2 cost decreases to a range of $\$4.0$–$\$6.9$ for CW and $\$5$–$\$6$ for SFW scenarios. This study also shows that low-cost bioH 2 can be produced using CW waste stream as feedstock.

Ganguly, Arna [Argonne National Laboratory (ANL), ↗

Recovery of terephthalic acid from solar PV backsheets using waste solvent from distilled spirits production

Current research on solar photovoltaic (PV) recycling mainly focuses on recovering valuable metals and glass, often neglecting the polymeric components, particularly the backsheets, which are typically landfilled or thermally decomposed. This study explores an innovative approach to upcycle PV backsheets into value-added products, specifically terephthalic acid (TPA), using waste ethanol solvent from the distilled spirits industry. Experimental results show that increasing both exposure time and ethanol concentration significantly enhances backsheet delamination efficiency. Using waste ethanol, a maximum delamination efficiency of 80% was achieved at room temperature after 24 hours. In decomposition trials, both sodium hydroxide (NaOH) and potassium hydroxide (KOH) demonstrated comparable efficiencies (96.6–97.5%) over 8 and 24 hour reactions. With virgin ethanol, NaOH yielded 94–97.5% TPA recovery. Notably, using waste ethanol achieved a TPA recovery efficiency of 96.8%, underscoring the process's economic viability and sustainability. Analytical characterization of TPA recovered after 8 hours showed consistent spectral patterns across both alkalis and solvents, indicating a similar chemical environment and functional groups. The recovered TPA can be repolymerized into high-purity PET, suitable for manufacturing new PV backsheets. This work advances polymer-recycling by demonstrating that an industrial waste solvent (distilled-spirits ‘heads’) can replace virgin ethanol without loss in delamination performance or TPA yield. While PV backsheet PET is a modest share of global PET, using waste ethanol to upcycle this currently under-recycled stream demonstrates a transferable solvent-reuse pathway that can extend to higher-volume PET sources.

Nain, Preeti [Michigan State Univ., East Lansing, ↗

An Application of Molecular Recognition for the Efficient Removal of Cesium from Hanford Nuclear Waste by Modular Solvent Extraction

In this work, experimental results leading to flowsheet design are presented showing how a calixarene-crown ether based solvent-extraction process can meet the challenge of cesium removal from nuclear tank wastes stored at the US Department of Energy Hanford site. Cleanup of legacy Cold War nuclear waste stored in underground tanks represents one of the greatest environmental challenges facing the US Department of Energy in terms of risk, cost, and effectiveness of applicable science and technology. Planning for the cleanup at the Hanford Site calls for the removal of the radioactive fission product 137Cs from its alkaline salt waste, including the use of modular processes that can be deployed near the tank farms. To meet the resulting need for extremely high selectivity, the Next-Generation Caustic-Side Solvent Extraction (NG-CSSX) process employing a calix[4]arene-crown ether in modified kerosene has been adapted to remove sub-millimolar cesium in competition with molar sodium and potassium in a high-nitrate alkaline matrix. Potassium loading in the solvent was determined in extraction, scrubbing, and stripping, leading to an empirical model closely approximating cesium distribution ratios for a variety of Hanford waste types. Process chemistry has been developed based on this molecular-recognition approach, focusing on the competitive effect of potassium loading and the mitigating process modifications needed, including extending the scrub section. The result is a modular flowsheet design that can achieve cesium decontamination factors well in excess of 15,000 even for the worst-case Hanford waste.

Williams, Neil [ORNL] (ORCID:000000023159226X)↗

Hanford Tank Waste Matrix Impact on Ion Exchange Performance Using Crystalline Silicotitanate

The removal of radiocesium from Hanford tank waste supernate is a critical step in preparing feed for low-activity waste immobilization. This study evaluated cesium ion exchange performance using crystalline silicotitanate (CST) media in a series of tests designed to evaluate the influence of waste matrix variability on capacity and kinetics. Tank waste supernate subsampled from five Hanford double-shell tanks encompassed a range of sodium, hydroxide, nitrate, and nitrite concentrations in order to assess the impact of feed variability on the performance of the ion exchange system. Both equilibrium and dynamic ion exchange tests were conducted to quantify cesium distribution coefficients and breakthrough behavior under prototypic operating conditions. Results indicated that effective cesium capacity varied by up to a factor of five across the matrices tested, with higher sodium concentrations significantly reducing uptake. Kinetic behavior was similarly matrix-dependent, with solution viscosity contributing to a twofold variation in mass-transfer rates. These results demonstrate the strong dependence of CST ion exchange performance on waste composition and must be incorporated into predictive models for future treatment system design and optimization.

Westesen, Amy M.↗

Technology Assessment on Low-Temperature Waste Heat Recovery in Industry

The purpose of this report is to discuss the magnitude of low-temperature waste heat available in the US manufacturing sector and to identify current and emerging low-temperature heat recovery technologies and equipment. The primary focus of the study is on the industries that produce the lowest-temperature waste heat: the chemical, primary metal, petroleum, nonmetallic mineral, fabricated metal, food, paper, and wood industries. In addition to identifying the waste streams, their characteristics, and currently available heat recovery technologies, the study also explored future research opportunities and economic barriers for recovery technology implementation. Special attention was given to applicable heat to power conversion technologies such as the organic Rankine cycle, thermoelectric conversion, and the supercritical CO 2 cycle. The study included investigations in research and new developments, including turbine and heat exchanger cost for waste heat to power systems, size, efficiency, and intermittency of waste heat streams.

30 DIRECT ENERGY CONVERSION↗