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At least 649 records · Page 36

Harnessing the potential of oilcane waste mud for recovering biobased waxes

Abstract Oilcane is an engineered sugarcane with the ability to hyper‐accumulate vegetative lipids. It is processed to obtain juice and bagasse as a potential substrate for the production of biofuels and biochemicals. The juice comprises solid particles that are separated as waste mud before the fermentation of the juice. In this study, the oilcane waste mud (OWM) generated from 1000 liters of oilcane juice was quantified and evaluated as a potential resource for recovering biobased waxes. Hexane and ethyl acetate were evaluated as two different solvents for extracting waxes from OWM followed by its purification using acetone. The extracted biobased wax samples were characterized for their chemical and thermal profiles which were then compared with commercial natural waxes. Detailed mass balance shows that 53.6 ± 2.6 kg (dry basis) of solid OWM gets generated upon processing 1000 L (~1068 kg) of oilcane juice. Hexane and ethyl acetate led to a crude wax yield of 25.6 ± 0.2% and 16.6 ± 0.4% (wt/wt, dry basis) respectively from OWM at the end of 8 h. The relative purification of the wax samples was reported in the range of 58%–65% (wt/wt). The purified OWM wax has a melting point of 74.7°C. The waste mud was valorized as a source of biobased waxes with characteristic chemical and thermal profiles comparable to commercial natural waxes (carnauba and beeswax). Considering the decline in the supply of petroleum wax in the future coupled with the switch to “greener” alternative products by consumers, OWM could be a valuable source of natural wax in the industrial sector reducing the dependence on petroleum waxes. Eventually, recovering biobased wax as a co‐product from OWM would bring in an additional stream of revenue leading to the development of a zero‐waste biorefinery based on bioenergy crops.

09 BIOMASS FUELS↗

The DECOVALEX international collaboration on modeling of coupled subsurface processes and its contribution to confidence building in radioactive waste disposal

Abstract The long-lived radiotoxicity of the high-level radioactive waste generated by nuclear power plants requires safe isolation from the biosphere for many hundreds of thousands of years. An international consensus has emerged that such isolation can best be provided by disposal in mined geologic repositories, a strategy that today is pursued by most countries dealing with radioactive waste. However, the need to predict the performance of such repositories over very long time periods generates large uncertainties that have to be accounted for in safety assessments. The findings from such safety assessments need to be conveyed to all stakeholders in a clear way, such that public confidence in geologic disposal solutions can be achieved. It is suggested here that close international collaboration on the technical aspects of geologic waste disposal has helped, and will continue to help, building trust and increasing confidence. This paper discusses a particular international collaboration initiative referred to as DECOVALEX, which brings together multiple teams and disciplines to collectively tackle complex experimental and modeling challenges related to geologic disposal. By describing how DECOVALEX works and by providing joint research examples, a case is made that such international collaboration contributes to knowledge transfer and confidence building in radioactive waste disposal science.

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Evaluating the potential of plastic waste upcycling using thermochemical technologies: A case study in Spain

A plastic waste upcycling value chain model has been applied to assess the potential of processing packaging waste in Spain using thermo-chemical technologies to produce low-density polyethylene (LDPE) and polypropylene (PP), which are highly valuable materials. The model projects an annual profit of 120.6 M$\$$/yr, with a capital investment of 789.3 M$\$$, generating 3285 jobs and contributing 65.5 M$\$$/yr to Spain’s economy. The achieved circularity rate of the waste processing infrastructure exceeds 40 %, incorporating recycled HDPE and PET. Despite these advantages, regulatory gaps and market hesitancy toward recycled materials due to quality concerns hinder adoption. Additionally, economies of scale remain underutilized in Spain due to lower plastic waste collection levels compared to countries such as the United States. This network, while less profitable, is environmentally superior, yielding upcycled products with a Global Warming Potential 20–35 % lower than their virgin, fossil-fuel counterparts, confirming this as a viable and sustainable alternative.

Chemical upcycling↗

Glass waste form options for rare-earth fission products from electrochemical reprocessing

Herein, we describe a first-of-a-kind study where lead tellurite (Pb-Te-O), iron phosphate (Fe-P-O), and lanthanide aluminoborosilicate (LABS) waste forms are evaluated for treating and/or immobilizing waste streams containing high rare-earth (RE) content, e.g., RECl 3 , REOCl, and/or REO x . Results from this study show that NdOCl can be immobilized in 78TeO 2 -22PbO glass at up to 10 mass%. Higher loadings of up to 15 mass% were demonstrated, but with a small fraction of crystallization. Two Fe-P-O glasses produced from either RECl 3 (RE = Nd,Ce) or NdOCl revealed products with very similar properties, demonstrating that the phosphate process can be used to chlorinate a variety of RE-containing waste streams. Two LABS glasses produced from Nd 2 O 3 or NdOCl showed similar properties, but the LABS-NdOCl glass did have some residual Cl present. Characterization is provided for all waste forms including chemical analysis, X-ray diffraction, and bulk density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synergistic Effects of Inexpensive Mixed Metal Oxides for Catalytic Hydrothermal Liquefaction of Food Wastes

Industrial wastes and natural mixed oxide materials were evaluated as inexpensive heterogeneous catalysts for catalytic hydrothermal liquefaction (CHTL) of food wastes. Red mud and red clay achieved biocrude carbon yields of 47.0 and 39.5% with higher heating values (HHVs) of 40.2 and 37.7 MJ kg –1 , respectively, which were much greater than those without the catalyst (biocrude carbon yield of 19.7% and HHV of 36.1 MJ kg –1 ). Biocrude characterization revealed that similar families of molecules were formed in the presence and absence of catalysts, implying that the main role of the catalyst is to promote rates of thermal reactions, leading to biocrude production without opening new pathways. The crystalline structures of inexpensive mixed oxides were stable under hydrothermal conditions, with modest calcium leaching (7.5%) and trace leaching of other metals. Using red clay or red mud resulted in >40% recovery of the energy in food waste as biocrude, greater than that obtained under noncatalytic conditions (18%) or from any individual constituent oxide (19–27%). The improved CHTL performance of the mixed metal oxides compared with single-metal oxides was attributed to the synergistic effects of base and acid sites present on catalyst surfaces; mixed oxides presented balanced densities of acids and bases, whereas the constituent oxides were either primarily acidic or primarily basic. Lastly, the percent of energy recovered as biocrude oil was strongly correlated with the base-to-acid site density ratio, providing an important performance predictor for CHTL conversion of food waste to bioenergy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

National and regional waste stream in the United States: conformance and disparity

Accurate estimation of municipal solid waste (MSW) composition is critical for efficient waste management. In the United States, site-specific and material flow approaches determine the MSW composition at regional and national levels. The material flow-based national estimates are determined by the US EPA; the US EPA’s estimates are known to differ substantially from the aggregated tonnage of MSW managed by waste handling facilities in the United States. However, the material class-specific discrepancies of the US EPA’s material flow approach resulting in these differences are unknown. To find the basis of these discrepancies, we analyze the discarded MSW stream of 27 US states, which roughly accounts for 73 percent of the US population. Our analysis indicates that the material flow-based national estimates are accurate for the food, plastic, and glass material classes. In contrast, we find that the US EPA’s material flow-based predictions underestimate paper waste disposal by at least 15 million tons annually. These differences likely stem from incorrect assumptions of residence time. These results highlight the material class-specific strengths and drawbacks of the US EPA’s material flow-based MSW estimates.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Progress and Technology Assessment of Melt-Cast Ceramic Waste Forms

The Savannah River National Laboratory (SRNL) conducted research from FY2011 – FY2020 to develop ceramic waste forms to treat High-Level Waste (HLW) resulting from reprocessing of commercial Used Nuclear Fuel (UNF) as part of the Department of Energy (DOE) office of Nuclear Energy (NE) Fuel Cycle Technologies (FCT) research program. The objective of the research was to develop a reference ceramic waste form and process technology needed to immobilize the combined HLW raffinate stream, including undissolved solids and soluble technetium, and potentially the TRU waste stream resulting from reprocessing processes. This report compiles the relevant literature produced under, and pertinent to, the program objectives and provides a perspective on the technology development as well as prospects for future.

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Fluorine Limits and Impacts in High-Level Waste Glass Compositions

The impact of elevated fluorine (F) content on Hanford high-level waste (HLW) glasses has not previously been studied in detail. This effort represents the first systematic study to determine what F concentration limits should be used for the design of alkali-borosilicate-based Hanford Waste Treatment and Immobilization Plant (WTP) HLW glasses, and to document the technical basis for that limit. If alkali borosilicate glass made from Hanford HLW can accommodate a large amount of F, the large capital costs for complex sludge washing facilities may be avoided, as would much of the operational costs and negative schedule impacts associated with handling the large volumes of water required to dissolve these salts. In order to determine a limit for F in likely HLW glass compositions, an evaluation was conducted on glasses with F ≤ 0.90 mass% from previous nuclear waste glass studies. The collected dataset contains 239 glasses (232 HLW glasses and 7 LAW glasses) including 109 glasses with 0.9 ≤ F mass% ≤ 2.5, 116 with 2.5 < F mass% ≤ 8.0, and 14 with F mass% ≥ 8 (max. F mass% = 17.42). The collected composition and property data were analyzed to determine the basis for the F tolerance, i.e. the maximum F concentration that can be processed without potential issues. Fluorine volatility, product consistency test (PCT) response, liquidus temperature (T L ), glass melt viscosity, and crystallinity have been investigated. No limits for F concentration can be made based on F volatility, T L , or glass melt viscosity, because the data show that high F in glasses do not indicate, with high probability, being restricted by those property constrains. However, crystallinity and PCT response were used to estimate the F tolerance. The results show that glasses with high F (≥ 0.90 mass%) are more likely to form large fractions of F-containing crystal phases which may increase PCT responses, i.e. decrease the glass durability. Based on the results of crystallinity and PCT data, the F tolerance of 4.5 mass% is estimated. There is no evidence of other glass components, such as calcium oxides and alkali metal oxides have combined impacts with F on the glass properties. Overall, the available high-F glass data is limited, especially in the designed HLW glass composition regions. Future work on formulation and testing of HLW glasses with F ≥ 0.9 mass% will close the data gaps and expand operational flexibility with respect to the fluoride tolerances. Volatility of F from melters and corrosion of materials in contact with glass melts are important for processing of high-F wastes; yet no test data are currently available. It is recommended tests be conducted to address these two potential issues.

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Vapor-Liquid Partitioning of Methylmercury Compounds: Fundamental Data to Support the Savannah River Site Liquid Waste System: Henry's Law, Solubility and Vapor Pressure Determination for Representative Methylmercury Compounds

The Savannah River Site (SRS) Liquid Waste System (LWS) contains approximately 66 tons of mercury within the liquids, salts, and sludges that are currently being processed into final wasteforms for disposal. Mercury concentrations within the system exceed those typically experienced in environmental or industrial systems; thus, management of mercury compounds continues to be a priority for SRS. In the LWS, waste is vitrified into a borosilicate glass wasteform that contains most of the radioactivity, while the lower activity solutions are dispositioned in a low-level grout wasteform, or “saltstone”. The alkaline, high ionic strength caustic wastes are pumped, evaporated, and otherwise managed throughout the LWS and Defense Waste Processing Facility (DWPF) as they are stored and prepared for conversion to the final wasteforms. Because of the complexity of this system, a key component of effective mercury management in the LWS requires analysis of mercury in various physical phases. The high concentration of mercury within the SRS LWS has the potential to generate vapor-phase contamination. Elemental mercury (Hg 0 ), dimethylmercury ((CH 3 ) 2 Hg), and methylmercury (CH 3 Hg + ) are among species known or suspected to contribute to the flux of mercury from liquid to vapor phase (Iverfeldt and Lindquist, 1982). Chemical speciation affects not only mercury behavior in LWS operations but may also affect the performance of mercury treatment and removal technologies in the LWS.

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The Thermodynamics of Crystallization and Phase-Separation in Melt-Derived Nuclear Waste Forms

This project aimed to gain detailed and fundamental understanding of the stability of glass waste forms to be used for safe and reliable encapsulation of nuclear waste. The focus was to understand thermodynamic and structural properties involved in crystallization and phase separation in melt-derived waste form glasses and glass-ceramics by studying a baseline glass composition with varying additives. This was achieved by combining neutron total scattering, advanced calorimetric measurements, and extensive modeling study. This project harnessed diverse and complementary approaches and expertise from four collaborating interdisciplinary institutions (two universities, one national laboratory, and one UK university partner). Samples were prepared at the national laboratory and exchanged with the two university institutions. The thermodynamic data obtained by various advanced calorimetry techniques were linked to the underlying short-range structure of waste forms measured by state-of-the-art neutron total scattering experiments. An important element of this project was extensive modeling to interpret and fundamentally understand the experimental results.

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ALDWP NET- TA-55 Waste Management Item #53780 [Slides]

Waste is a Product. It must be manufactured in complete compliance with the customers’ (WIPP, various LLW sites) specification. Programmatic, facility, and maintenance personnel originate the waste. NPI-6 is the waste generator (key legal term). Our customers are the waste originators.

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Results for the October 2023 Semiannual Salt Waste Processing Facility Decontaminated Salt Solution Sample

In this Technical Report, the chemical and radionuclide contaminant results from the October 2023 Semiannual sample of the Salt Waste Processing Facility (SWPF) Decontaminated Salt Solution (DSS) salt solution are presented in tabulated form. The information from this characterization will be used by Savannah River Mission Completion (SRMC) for the transfer of aqueous waste from SWPF to the Saltstone Production Facility (SPF) where the waste will be treated and disposed in the Saltstone Disposal Facility. This Technical Report compares results, where applicable, to SPF Waste Acceptance Criteria (WAC) LIMITS and TARGETS that were established at the time the SWPF DSS sample was obtained. The October 2023 Semiannual sample of the SWPF DSS is a composite from the six months of SWPF processing during the Third Quarter Fiscal Year 2023 (3QFY2023) and the Fourth Quarter Fiscal Year 2023 (4QFY2023).

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Results for the April 2024 Semiannual Salt Waste Processing Facility Decontaminated Salt Solution Sample

In this Technical Report, the chemical and radionuclide contaminant results from the April 2024 Semiannual sample of the Salt Waste Processing Facility (SWPF) Decontaminated Salt Solution (DSS) salt solution are presented in tabulated form. The information from this characterization will be used by Savannah River Mission Completion (SRMC) for the transfer of aqueous waste from SWPF to the Saltstone Production Facility (SPF) where the waste will be treated and disposed in the Saltstone Disposal Facility. This Technical Report compares results, where applicable, to SPF Waste Acceptance Criteria (WAC) LIMITS and TARGETS that were established at the time the SWPF DSS sample was obtained.1 The April 2024 Semiannual sample of the SWPF DSS is a composite from the six months of SWPF processing during the First Quarter Fiscal Year 2024 (1QFY2024) and the Second Quarter Fiscal Year 2024 (2QFY2024). The following facts pertaining to the WAC are drawn from the analytical results provided in this report. WAC TARGETS and LIMITS were met for all analyzed chemical and radioactive contaminants for which the detection limits are below the WAC TARGETS and LIMITS. Nitrosamines were not detected in the SWPF DSS salt solution sample above the instrument detection limits of <1 mg/L. The minimum detection limit (<3.33E-01 pCi/mL) is reported for 94 Nb as determined from the minimum detectable activity associated with the radiochemical method used for this radionuclide. The reported detection limit is above the requested SRMC target minimum detection limit concentration. However, the minimum detection limit reported for the April 2024 semiannual SWPF DSS sample for 94 Nb is lower than the estimated detection limit of 4.38E-01 pCi/mL initially established by SRNL in 2009. Thus, per guidance from SRMC, 2 SRNL continues to achieve as low as practical detection limits for this radionuclide.

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Design and Materials of Reference Electrodes for Radioactive Waste Tank Service – A Literature Review

The Hanford site stores approximately 55 million gallons of radioactive and chemically hazardous wastes from the production of weapons materials. The wastes are stored in 177 underground, carbon steel storage tanks, 149 of these are single shell tanks (SSTs) and 28 of these are double shell tanks (DSTs). The DSTs provide critical retrieval and interim storage before the waste is vitrified in the Waste Treatment and Isolation Plant (WTP). The DSTs have been in service for 38 to 56 years and current plans indicate that WTP operations will be completed in 2075. Thus, the tanks will need to remain in service far beyond the initial 40-year life expectancy. For life extension of the tanks, effective corrosion control practices must remain in force. This effort includes direct measurements of the extent of corrosion (e.g., ultrasonic measurements and corrosion coupons) and electrochemical processes (e.g., linear polarization measurements).

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Corrosion Testing of Refractory in Contact with Molten Glasses Designed for Waste Vitrification - APPS1 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.

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Evaluation of Pozzolan-substituted Cast Stone for Pretreated Hanford Tank Waste

Portland cement. The future availability of quality Class F fly ash has come into question as coal-fired power plants are being converted to gas or taken offline. Consequently, alternative pozzolanic reagents are being evaluated for fly ash replacement in cementitious matrices for treating radioactive waste and debris. In 2023 and 2024, Savannah River National Laboratory (SRNL) was funded to evaluate natural pozzolans for the replacement of Class F fly in the Savannah River Site (SRS) Saltstone formulation. Based on the promising results and uncertain availability of Class F fly ash in the northwestern US, Hanford Tank Waste Operations & Closure, LLC (H2C) requested SRNL to evaluate the potential for substituting natural pozzolans in the Hanford West Area Pretreated Low Activity Tank Waste (PTW/LAW) Cast Stone formulation1 . Task 1 in this request was to determine the change in Cast Stone volume resulting from stabilization/solidification of 1 L of PTW/LAW tank waste. The densities of three (Hess Pumice, tephra pumice, and clinoptilolite zeolite) pozzolan-substituted Baseline Cast Stone mixes were determined, and volume changes relative to the fly ash-Baseline Mix with a water-to-dry mix = 0.40 were calculated.

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Results for the April 2025 Semiannual Salt Waste Processing Facility Decontaminated Salt Solution Sample

In this Technical Report, the chemical and radionuclide contaminant results from the April 2025 Semiannual sample of the Salt Waste Processing Facility (SWPF) Decontaminated Salt Solution (DSS) salt solution are presented in tabulated form. The information from this characterization will be used by Savannah River Mission Completion (SRMC) for the transfer of aqueous waste from SWPF to the Saltstone Production Facility (SPF) where the waste will be treated and disposed in the Saltstone Disposal Facility. This Technical Report compares results, where applicable, to SPF Waste Acceptance Criteria (WAC) LIMITS and TARGETS that were established at the time the SWPF DSS sample was obtained. The April 2025 Semiannual sample of the SWPF DSS is a composite from the six months of SWPF processing during the First Quarter Fiscal Year 2025 (1QFY2025) and the Second Quarter Fiscal Year 2025 (2QFY2025).

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Corrosion Testing of Refractory in Contact with Molten Glasses Designed for Waste Vitrification - HAL24 M1 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.

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