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At least 1,063 records · Page 59

Radionuclide Inventory Calculations for the Calcined Solid Storage Facility Performance Assessment - 19292

Originally named the Idaho Chemical Processing Plant when it was constructed in the early 1950's, the Idaho Nuclear Technology and Engineering Center reprocessed SNF to recover highly enriched uranium and other nuclear-related products for the U.S. DOE. Reprocessing SNF generated millions of gallons of aqueous radioactive waste. Calcination was a process developed at the INL Site to convert liquid waste into a solid, granular form from 1963 to 2000. The calcination process produced a safer product for storage while reducing the volume of stored liquid waste by an average factor of seven. Calcine is currently stored in the Calcined Solids Storage Facility (CSSF). The CSSFs are often called 'bin sets' because each CSSF (CSSFs 1 through 6) contains several stainless-steel storage bins housed in a concrete vault. The CSSF is an interim waste storage facility. In the future, calcine will be retrieved, treated (if necessary), and sent to an off-Site facility for storage or disposal. To close the CSSF, the bulk of the calcine will be removed and stored or disposed of elsewhere. The bins and vaults will then be placed in a configuration that is protective of human health and the environment. For purposes of the performance assessment, the depth of the residual calcine at closure was assumed to be 5-cm in each bin. The 5-cm of residual calcine in each bin is assumed to be mixed in grout during closure. The activities of the residual radionuclides are the inventory used for the dose assessment calculations for the CSSF performance assessment. The objective of this analysis was to calculate the radionuclide activity in the residual calcine remaining in the CSSF after closure. The purpose of this paper is to present the approach used to calculate the radionuclide inventory of the calcine currently stored in CSSF and the residual calcine in the CSSF after closure using data from the calcined waste Historical Processing Model (HPM). Limited sampling and analysis of the calcine in the CSSF bins was conducted in the past. Future similar calcine sampling and analysis efforts would be costly, generate additional mixed waste, and may not provide the desired detailed calcine composition data. However, during the later years of calcining, an alternative to calcine sampling and analysis was developed and the information was captured in the HPM. The HPM uses multiple sources to provide definitive calcine volume, mass, and composition, including: compositions and volumes of the liquid wastes that were calcined, ORIGEN2 - and ORIGEN-ARP-based radioactivity calculations, calciner and CSSF operating data, and process knowledge of INTEC fuel and waste-processing systems. HPM calcine composition was used to develop an inventory of radionuclides for use in the performance assessment evaluation for closure of CSSF. There are 43 bins that contain calcine, with six to twelve segments in each bin for a total of 337 bin segments for which the HPM calculates the average calcine composition. The HPM calculates the composition of each of the nearly 7,000 batches of material (startup bed, nonradioactive material, and radioactive waste) charged to the calciners. The calculations use the CSSF dimensions, including the CSSF number of bins, heights, outside diameters, annular air space diameter (if necessary), and volume of calcine currently in the bins. For each of the CSSFs, for a 5-cm residual, the percent of total calcine was calculated along with the residual activity for the radionuclides. Residual activity was estimated for 148 different radionuclides. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Conversion kinetics during melting of simulated nuclear waste glass feeds measured by dissolution of silica

In this work, we experimentally investigated the batch-to-glass conversion kinetics of two low-activity and two high-level nuclear waste melter feeds that represent widely different behavior during melting; tests comprised thermogravimetric analysis, the feed expansion test, evolved gas analysis, and x-ray diffraction. Our study indicates that the conversion processes, which include gas-evolving reactions, dissolution of crystalline phases, and primary foam expansion and collapse, are interconnected and influenced by the feed’s thermal history. The fraction of dissolved silica was adopted as a measure of the extent of conversion inside the cold cap—the floating layer of feed material on the top surface of the melt in an electric melter. The interface between the cold cap and the free-flowing melt below was associated with a constant fraction of dissolved silica. The estimated viscosity of glass-forming melt at this interface lies within a narrow range for the feeds studied.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Data for Tolerance of Engineered Rhodosporidium toruloides to Sorghum Hydrolysates During Batch and Fed-Batch Lipid Production

Oleaginous yeasts are a promising candidate for the sustainable conversion of lignocellulosic feedstocks into fuels and chemicals, but their growth on these substrates can be inhibited as a result of upstream pretreatment and enzymatic hydrolysis conditions. Previous studies indicate a high citrate buffer concentration during hydrolysis inhibits downstream cell growth and ethanol fermentation in Saccharomyces cerevisiae . In this study, an engineered Rhodosporidium toruloides strain with enhanced lipid accumulation was grown on sorghum hydrolysate with high and low citrate buffer concentrations. Both hydrolysis conditions resulted in similar sugar recovery rates and concentrations. No significant differences in cell growth, sugar utilization rates, or lipid production rates were observed between the two citrate buffer conditions during batch fermentation of R. toruloides . Under fed-batch growth on low-citrate hydrolysate a lipid titer of 16.7 g/L was obtained. Citrate buffer was not found to inhibit growth or lipid production in this engineered R. toruloides strain, nor did reducing the citrate buffer concentration negatively affect sugar yields in the hydrolysate. As this process is scaled-up, $131 per ton of hydrothermally pretreated biomass can be saved by use of the lower citrate buffer concentration during enzymatic hydrolysis.

Conversion↗

Organic Separation Test Results

Separable organics have been defined as “those organic compounds of very limited solubility in the bulk waste and that can form a separate liquid phase or layer” (Smalley and Nguyen 2013), and result from three main solvent extraction processes: U Plant Uranium Recovery Process, B Plant Waste Fractionation Process, and Plutonium Uranium Extraction (PUREX) Process. The primary organic solvents associated with tank solids are TBP, D2EHPA, and NPH. There is concern that, while this organic material is bound to the sludge particles as it is stored in the tanks, waste feed delivery activities, specifically transfer pump and mixer pump operations, could cause the organics to form a separated layer in the tank farms feed tank. Therefore, Washington River Protection Solutions (WRPS) is experimentally evaluating the potential of organic solvents separating from the tank solids (sludge) during waste feed delivery activities, specifically the waste mixing and transfer processes. Given the Hanford Tank Waste Treatment and Immobilization Plant (WTP) waste acceptance criteria per the Waste Feed Acceptance Criteria document (24590-WTP-RPT-MGT-11-014) that there is to be “no visible layer” of separable organics in the waste feed, this would result in the batch being unacceptable to transfer to WTP. This study is of particular importance to WRPS because of these WTP requirements.

complexants↗

Sample Results from Routine Salt Batch 7 Samples

Strip Effluent Hold Tank (SEHT) and Decontaminated Salt Solution Hold Tank (DSSHT) samples from several of the “microbatches” of Integrated Salt Disposition Project (ISDP) Salt Batch (“Macrobatch”) 7B have been analyzed for 238 Pu, 90 Sr, 137 Cs, Inductively Coupled Plasma Emission Spectroscopy (ICPES), and Ion Chromatography Anions (IC-A). The results from the current microbatch samples are similar to those from earlier samples from this and previous macrobatches. The Actinide Removal Process (ARP) and the Modular Caustic-Side Solvent Extraction Unit (MCU) continue to show more than adequate Pu and Sr removal, and there is a distinct positive trend in Cs removal, due to the use of the Next Generation Solvent (NGS). The Savannah River National Laboratory (SRNL) notes that historically, most measured Concentration Factor (CF) values during salt processing have been in the 12-14 range. However, recent processing gives CF values closer to 11. This observation does not indicate that the solvent performance is suffering, as the Decontamination Factor (DF) has still maintained consistently high values. Nevertheless, SRNL will continue to monitor for indications of process upsets. The bulk chemistry of the DSSHT and SEHT samples do not show any signs of unusual behavior.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Fiscal Year 2020 Filtration of Hanford Tank Waste 241-AP-105

Bench-scale filtration testing of 15 liters of 241-AP-105 supernatant was conducted using a Mott inline filter Model 6610 (media grade 5) backpulsed dead-end filter (BDEF) in the hot cells of the Radiochemical Processing Laboratory at Pacific Northwest National Laboratory. The as-received samples were diluted with raw water from the Hanford Site to assess the propensity for solids to form upon dilution and to assess the impact those solids have on filtration performance. The feed was split into two batches. The first batch was settled and decanted as planned in Tank Side Cesium Removal operations. The BDEF was used to filter this AP-105 feed at a targeted flux of 0.065 gpm/ft 2 and exhibited no measurable pressure increase during filtration. The second batch was fed to the BDEF with solids resuspended. This was also operated at the targeted flux of 0.065 gpm/ft 2 . In this case, the target pressure differential of 2 psid (resistance of 6.24 × 10 10 m -1 ) was reached in slightly more than 12 h. A backpulse restored the filter flux; however, the time to the next backpulse was slightly shorter. These tests indicate that after the addition of raw water, settle and decant effectively removed solids from the feed. It is not possible to assess the time required for these solids to settle based on the result from these tests. However, if sufficient time is allowed for the solids to settle, no measurable filter fouling was observed in current testing. In contrast, if insufficient time is allowed for solids to settle, filter fouling will occur relatively quickly and will likely require backpulses more frequently than every 12 hours (1.91 m 3 /m 2 volume filtered). Solids concentrated from backpulse solutions displayed large variability in composition with Al-silicates and mixed chromium-aluminum oxide phases. Amounts of Mg, Fe, and Ca were also found in the presence of Na and O. These solids could be grouped in three categories: (1) soluble Na-salts that formed large block-like particles but were made up of fibrous materials, (2) amorphous Al-phases, and (3) colloidal iron oxides with an average particle diameter of 4.2 µm.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

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↗

xSDK-batched Subcontract - Ginkgo Batched Iterative Solver Development (Final Report)

Iterative solvers are fundamentally different from direct solvers in terms of execution as they generally do not execute a pre-defined sequence of operations or steps, but adapt the number of iterations to the specific problem and the preset solution quality. Generally, the adaptation of the iteration count to the problem is realized by monitoring the solver convergence and stopping the iteration process once the monitored metric, e.g., the residual norm, hits a pre-defined threshold. When addressing a set of problems with different properties, it is necessary to monitor the threshold for each problem individually and break up the SIMD execution style to avoid excess iterations for “easier” problems. Ginkgo integrates a simple but customizable stopping criterion for the residual norm and generally uses a pre-defined (relative or absolute) residual norm as the stopping criterion. In order to avoid the overhead of launching a kernel at every iteration, the iteration convergence and iteration control is part of the solver kernel. Each thread maintains its own copy of the iteration count.

97 MATHEMATICS AND COMPUTING↗

Defense Waste Processing Facility (DWPF) Durability-Composition Models and the Applicability of the Associated Reduction of Constraints (ROC) Criteria for High TiO 2 Containing Glasses

Radioactive high-level waste (HLW) at the Savannah River Site (SRS) has successfully been vitrified into borosilicate glass in the DWPF since 1996. Vitrification requires stringent product/process (P/P) constraints since the glass cannot be reworked once it has been poured into ten foot tall by two foot diameter canisters. A unique “feed forward” statistical process control (SPC) was developed for this control rather than relying on statistical quality control (SQC). In SPC, the feed composition to the DWPF melter is controlled prior to vitrification. In SQC, the glass product would be sampled after it is vitrified. Individual glass property-composition models form the basis for the “feed forward” SPC. The models transform constraints on the melt and glass properties into constraints on the feed composition going to the melter in order to determine, at the 95% confidence level, that the feed will be processable and that the durability of the resulting waste form will be acceptable to a geologic repository. The DWPF SPC system is known as the Product Composition Control System (PCCS). One of the process models within PCCS is known as the Thermodynamic Hydration Energy Reaction MOdel (THERMO™). The DWPF will soon be receiving increased concentrations of TiO 2 -, Na 2 O-, and Cs 2 O-enriched wastes from the Salt Waste Processing Facility (SWPF). The SWPF has been built to pretreat the high-curie fraction of the salt waste to be removed from the HLW tanks in the F- and H-Area Tank Farms at the SRS. In order to validate the existing TiO 2 term in THERMO™ beyond 2.0 wt% in the DWPF, new durability data were developed over the target range of 2.00 to 6.00 wt% TiO 2 and evaluated against the 1995 durability model. The durability was measured by the 7-day Product Consistency Test. This study documents the adequacy of the existing THERMO™ terms. It is recommended that the modified THERMO™ durability models and the modified property acceptable region limits for the durability constraints be incorporated in the next revision of the technical bases for PCCS and then implemented into PCCS. It is also recommended that an reduction of constraints of 4 wt% Al 2 O 3 be implemented with no restrictions on the amount of alkali in the glass for TiO 2 values ≥2 wt%. The ultimate limit on the amount of TiO 2 that can be accommodated from SWPF will be determined by the three PCCS models, the waste composition of a given sludge batch, the waste loading of the sludge batch, and the frit used for vitrification.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Implementation of Ion Exchange Processes on Industrial Waste Streams for CO 2 Mineralization

Economic development and population growth will lead to an increase in global energy consumption. Large coal-fired power plants (>500 MW) account for almost half of the total CO 2 emissions from fossil fuel combustion, and nearly 26% of the global fossil fuel and industry CO 2 emissions. Long-term management of the more than 36 Gt of CO 2 that is emitted globally per year is urgently needed. CO 2 mineralization is an attractive method of sequestering CO 2 because it captures CO 2 as an insoluble carbonate mineral, mimicking the natural process of rock weathering. Here, we present a pathway for accelerated CO 2 mineralization enabled by divalent cations sourced from liquid streams. In this work, we investigate a mineralization route that converts flue gas CO 2 to precipitated calcium carbonate (PCC) using waste aqueous streams as the calcium source. The proposed mineralization route integrates CO 2 utilization and waste liquid management at coal power plants. Maintaining alkalinity during carbonation is the primary challenge in this process. Instead of relying on the consumption of costly and unsustainable sources of alkalinity (e.g., sodium hydroxide), we used regenerable solids to increase the pH of water by ion exchange. The increase in alkalinity creates a more thermodynamically favorable environment for calcite precipitation. The capacities for ion exchange of various commercially available zeolites and ion exchange resins in CO 2 -saturated water were studied through batch equilibrium and column ion-exchange experiments. During ion exchange, H + in the water exchanges with Na + , Ca 2+ or K + in the zeolite or resin. Batch equilibrium isotherms for H + –Na + exchange were collected by first adding varying amounts of the ion exchange solid (0 – 1.0 kg per kg of water) to CO 2 -saturated water (pCO 2 = 1 atm, pH 4) to determine the maximum H + –Na + exchange achievable. Ion-exchange column studies were performed to determine breakthrough capacity of the system. In both systems, an increase in pH coupled with an increase in Na concentration was observed, demonstrating the feasibility of forward ion exchange. Zeolitic materials increased the alkalinity of the solution from pH 4 to around 10, whereas ion exchange resins containing weakly acidic functional groups (e.g., carboxylic acid) exhibited higher affinity for H + , increasing pH to 11.3 and surpassing the pH shift induced by the zeolitic materials. The extent of calcite precipitation was evaluated by mixing the alkaline CO 3 2- -rich water obtained after passing through the ion-exchange column and a CaCl 2 solution. Calcite yields are as expected from chemical thermodynamics. Calcium carbonate yields found experimentally were about 26 and 8 mmol per kg water for the weakly acidic ion exchange resin and zeolitic materials, respectively. The results from these studies indicate that ion exchange processes can be used as an alternative to the addition of stoichiometric inorganic bases (e.g., sodium hydroxide) to induce alkalinity for the consequent precipitation of CaCO 3 . Instead, weakly acidic ion exchange resins commonly used for water hardness removal were alternatively used to induce pH swings in the aqueous solutions. The high calcium carbonate yields obtained for the materials examined demonstrate the potential application of this process. In addition, the successful operation of the calcium carbonate production process at standard temperature and pressure conditions support its potential for industrial implementation.

Simonetti, Dante↗

Biotransformation of furanic and phenolic compounds with hydrogen gas production in a microbial electrolysis cell

In this study, furanic and phenolic compounds are problematic byproducts resulting from the decomposition of lignocellulosic biomass during biofuel production. This study assessed the capacity of a microbial electrolysis cell (MEC) to produce hydrogen gas (H 2 ) using a mixture of two furanic (furfural, FF; 5-hydroxymethyl furfural, HMF) and three phenolic (syringic acid, SA; vanillic acid, VA; and 4-hydroxybenzoic acid, HBA) compounds as the sole carbon and energy source in the bioanode. The rate and extent of biotransformation of the five compounds, efficiency of H 2 production, as well as the anode microbial community structure were investigated. The five compounds were completely transformed within 7-day batch runs and their biotransformation rate increased with increasing initial concentration. At an initial concentration of 1,200 mg/L (8.7 mM) of the mixture of the five compounds, their biotransformation rate ranged from 0.85 to 2.34 mM/d. The anode coulombic efficiency was 44-69%, which is comparable to wastewater-fed MECs. The H 2 yield varied from 0.26 to 0.42 g H 2 -COD/g COD removed in the anode, and the bioanode volume-normalized H 2 production rate was 0.07-0.1 L/L-d. The major identified fermentation products that did not transform further were catechol and phenol. Acetate was the direct substrate for exoelectrogenesis. Current and H 2 production were inhibited at an initial substrate concentration of 1,200 mg/L, resulting in acetate accumulation at a much higher level than that measured in other batch runs conducted with a lower initial concentration of the five compounds. The anode microbial community consisted of exoelectrogens, putative degraders of the five compounds, and syntrophic partners of exoelectrogens. The H 2 production route demonstrated in this study has proven to be an alternative to the currently used process of reforming natural gas to supply H 2 needed to upgrade bio-oils to stable hydrocarbon fuels.

08 HYDROGEN↗

Round Robin Measurements of Molten Salt Properties for LiF-NaF-KF (FLiNaK) and NaCl-KCl Mixtures

The development, operation, and regulation of nuclear reactors that utilize molten salts as fuel or as heat transfer media require knowledge of the thermal properties of the salt systems and quantification of the corresponding uncertainties. Knowledge of molten salt properties is also necessary for applications in material synthesis, processing, separations, solar thermal power generation, and energy storage. A round robin was conducted with national laboratory and university participants from twenty-one laboratories in five countries to compare property measurements, to better understand uncertainties, and to identify possible best practices. Two salt mixtures, each from a common batch, were distributed to participants for evaluation: equimolar NaCl-KCl and 45.0LiF-13.7NaF-41.3KF mol % (FLiNaK). Measurements were performed to determine the major constituent composition, oxygen content, density, thermal expansivity, melting point, and thermal conductivity. Error analysis was performed on each measurement for uncertainty quantification for each type of property that was explored. Finally, the resulting discussion of the methodologies used in this work is meant to lay the groundwork for the development of standard methods and reference materials for future high-temperature property measurements on halide melts.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Tolerance of engineered Rhodosporidium toruloides to sorghum hydrolysates during batch and fed-batch lipid production

Abstract Background Oleaginous yeasts are a promising candidate for the sustainable conversion of lignocellulosic feedstocks into fuels and chemicals, but their growth on these substrates can be inhibited as a result of upstream pretreatment and enzymatic hydrolysis conditions. Previous studies indicate a high citrate buffer concentration during hydrolysis inhibits downstream cell growth and ethanol fermentation in Saccharomyces cerevisiae . In this study, an engineered Rhodosporidium toruloides strain with enhanced lipid accumulation was grown on sorghum hydrolysate with high and low citrate buffer concentrations. Results Both hydrolysis conditions resulted in similar sugar recovery rates and concentrations. No significant differences in cell growth, sugar utilization rates, or lipid production rates were observed between the two citrate buffer conditions during batch fermentation of R. toruloides . Under fed-batch growth on low-citrate hydrolysate a lipid titer of 16.7 g/L was obtained. Conclusions Citrate buffer was not found to inhibit growth or lipid production in this engineered R. toruloides strain, nor did reducing the citrate buffer concentration negatively affect sugar yields in the hydrolysate. As this process is scaled-up, $131 per ton of hydrothermally pretreated biomass can be saved by use of the lower citrate buffer concentration during enzymatic hydrolysis. Graphical Abstract

09 BIOMASS FUELS↗

Report on Assessment of Advanced Reactor Fuel Performance

Three activities have been performed in FY 2019 to support the Advanced Fuel Cycle Campaign, which include assessment of annular fuel performance in an ultra-high burnup sodium-cooled reactor (SFR), modeling of annular fuel behavior during a transient scenario, and feasibility of a sustainable closed fuel cycle utilizing melt-refining process. Annular fuel performance parameters, including temperature profile, swelling strain, and cumulative damage fraction (CDF), in a 3000 MWt Sustainable Sodium-cooled Fast Reactor (SSFR) were assessed using the BISON fuel performance code. The SSFR is once-through ultra-long-life core based on a 34-batch fuel management scheme with 1.5-year cycle length. The fuel residence time in the SSFR is 51 years and the average discharged burnup is about 30%. Annular fuel has potential to irradiate for ultra-high burnup without major fuel-cladding mechanical interaction. This feature is achieved by using a low smeared density (~55%). In the SSFR design, however, 75% smeared density and a thick fuel pin were preferred to maintain criticality for 51 years. Due to the high smeared density and thick fuel pin configuration, the annular fuel was predicted to suffer premature cladding failure before reaching the discharge burnup of the SSFR. The current fuel creep model predicts a prominent creep strain due to gravity over the half-century irradiation, which may significantly affect the evolution of CDF. Thus, in order to use the annular fuel in an ultra-high burnup core such as the SSFR, a low smeared density and thin annular fuel is strongly recommended.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Evaluation of Pu Solubility in Glass for Sludge Batch 11

Stainless-steel clad Pu from Japan’s Fast Critical Assembly (FCA) reactor is currently being dispositioned at the Savannah River Site. The electrolytic dissolver, operated by Savannah River Nuclear Solutions in H-Canyon, is being utilized to dissolve the material. The resulting solutions are transferred to the Concentration, Storage, and Transfer Facilities, operated by Savannah River Mission Completion (SRMC), for subsequent vitrification at the Defense Waste Processing Facility (DWPF). In support of the FCA mission startup, a preliminary evaluation was conducted by the Savannah River National Laboratory to assess the impact of the FCA discards on the liquid waste system.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Retention of Anionic Species on Granite: Influence of Granite Composition - 12129

Technetium (Tc-99, T{sub 1/2} = 2.1.10{sup 5} yrs) and selenium (Se-79, T{sub 1/2} = 6.5.10{sup 4} yrs) belong among fission products, being produced by fission of nuclear fuel. Both elements can significantly contribute to risk due to their complicated chemistry, long life times, high mobility and prevailing anionic character. Therefore, knowledge of migration behaviour under different conditions can significantly improve input into performance and safety assessment models. Granite is considered as a potential host rock for deep geological disposal of radioactive waste in many countries. Granitic rocks consist usually of quartz, feldspar, plagioclase (main components), mica, chlorite, kaolinite (minor components). The main feature of the rock is advection governed transport in fractures, complemented with diffusion process from fracture towards undisturbed rock matrix. The presented work is focused on interaction of anionic species (TcO{sub 4}{sup -}, SeO{sub 4}{sup 2-}, SeO{sub 3}{sup 2-}) with granitic rock. Furthermore, the importance of mineral composition on sorption of anionic species was also studied. The batch sorption experiments were conducted on the crushed granite from Bohemian Massive. Five fractions with defined grain size were used for static batch method. Mineral composition of each granitic fraction was evaluated using X-ray diffraction. The results showed differences in composition of granitic fractions, even though originating from one homogenized material. Sorption experiments showed influence of granite composition on adsorption of both TcO4{sup -} and SeO3{sup 2-} on granitic rock. Generally, Se(IV) showed higher retention than Tc(VII). Se(VI) was not almost sorbed at all. Fe containing minerals are pronounced as a selective Se and Tc sorbent, being reduced on their surface. As micas in granite are usually enriched in Fe, increased sorption of anionic species onto mica enriched fractions can be explained by this reason. On the other hand, fractions enriched in feldspar did not show increased sorption affinity to Tc and Se. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media(5-8) that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid, which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. Here, we find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolitesupported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. Finally, we anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful chemicals.

09 BIOMASS FUELS↗

Data-driven acoustic measurement of moisture content in flowing biomass

Measuring the moisture content in flowing biomass is critical to processes such as liquid biofuel conversion, such as biogasoline, biodiesel, bio jet kerosene, etc. However, biomass tends to flow in aggregates, which results in significant inhomogeneities in the amount of biomass flowing in front of a sensor at a given time, and there can be significant overlap in the material properties of dry vs wet biomass, leading to poor signal-to-noise ratio. We present a technique for identifying biomass moisture content using a series of acoustic pitch-catch measurements to quantify the sound speed and acoustic amplitude through the biomass, in conjunction with classical machine learning techniques, including Naive Bayes, Random Forest, and K-Nearest Neighbors classification. We amplify the differences between the acoustic measurements in different moisture levels by collecting a series of pulse-echo measurements, which we sort in order of ascending sound speed. We test the accuracy of the technique on experimentally-prepared batches of corn stover biomass with specified moisture levels and measure the average error in the estimated moisture level as a function of the number of pitch-catch measurements used. We observe average estimation errors as low as 6.7% by increasing the number of measurements and optimizing the hyperparameters. This work presents a novel method determining moisture content in flowing biomass with inhomogeneous flow. Additionally, this technique has application in optimizing biomass conversion processes, as well as other fields including, paper production, natural fiber processing, and mineral extraction.

09 BIOMASS FUELS↗