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At least 847 records · Page 47

Implementation of the Glycolate Destruction Process with Sodium Permanganate in the Defense Waste Processing Facility (DWPF) - 20141

The Savannah River Site (SRS) seeks to replace formic acid with glycolic acid as a chemical reductant in the Defense Waste Processing Facility (DWPF), where borosilicate glass is mixed with high-level radioactive waste, melted at high temperatures, then poured into stainless steel canisters for safe storage. Prior research and development have demonstrated the feasibility and advantages of the new nitric-glycolic acid flowsheet over the current nitric-formic acid flowsheet to chemically adjust the radioactive sludge slurry waste in the Sludge Receipt and Adjustment Tank (SRAT) prior to vitrification. Use of glycolic acid reduces hydrogen and ammonia generation during the reduction process, thus reducing flammability hazards and purge requirements in the DWPF processing vessels. In addition, glycolic acid will support the new Salt Waste Processing Facility (SWPF) by allowing for receipt of higher volumes of waste due to reduction of flammable gases, increased boil-up rates in the vessels, and easing the processing of future sludge batches containing high levels of mercury. However, during DWPF operations, trace amounts of glycolate are anticipated to be entrained in the recycle stream and sent to the Concentration, Storage, and Transfer Facilities (CSTF) via the Recycle Collection Tank (RCT). The RCT receives condensate from the Slurry Mix Evaporator Condensate Tank (SMECT) and Off-gas Condensate Tank (OGCT) that may contain unreacted glycolate. A literature review found the potential for hydrogen generation due to thermolysis of glycolate in caustic CSTF conditions. Savannah River National Laboratory (SRNL) conducted several tests on simulant and radioactive waste from various tanks at SRS and confirmed that glycolate added to waste at concentrations of approximately 1000 mg/L and higher generates hydrogen through thermolysis. There are potential operating scenarios in the future where glycolate concentration could exceed 1000 mg/L in the 2H Evaporator Drop Tank, the highest accumulation point for DWPF organics received via recycle. These findings presented a need to develop another process to mitigate the impact of glycolic acid to the CSTF. Several DWPF compatible options were evaluated for their ability to destroy glycolate in the DWPF recycle stream under various processing conditions, thereby mitigating its introduction to the CSTF. Downselection testing identified sodium permanganate as the most promising and simplest option to oxidize glycolate. It has been demonstrated to be effective in various RCT simulant compositions, operating temperatures, oxidant addition rates, solution pH, and initial glycolate concentrations. A feasibility study identified existing tanks within the facility that could be used for receiving and storing the commercially available sodium permanganate, as well as feeding it to the RCT for processing. The use of existing equipment as well as the ability to purchase the pre-mixed chemical reduces implementation and operational complexity. The downstream impacts of the sodium permanganate reaction were also evaluated and demonstrated to have minimal impact on other chemical species present in the RCT and CSTF, as well as on the materials of construction of the RCT and CSTF vessels and associated piping and instrumentation. Future work is in progress to validate the glycolate destruction process with testing in actual radioactive RCT waste before implementation in DWPF. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Mercury Reduction and Removal from High Level Waste at the Defense Waste Processing Facility - 12511

The Defense Waste Processing Facility processes legacy nuclear waste generated at the Savannah River Site during production of enriched uranium and plutonium required by the Cold War. The nuclear waste is first treated via a complex sequence of controlled chemical reactions and then vitrified into a borosilicate glass form and poured into stainless steel canisters. Converting the nuclear waste into borosilicate glass is a safe, effective way to reduce the volume of the waste and stabilize the radionuclides. One of the constituents in the nuclear waste is mercury, which is present because it served as a catalyst in the dissolution of uranium-aluminum alloy fuel rods. At high temperatures mercury is corrosive to off-gas equipment, this poses a major challenge to the overall vitrification process in separating mercury from the waste stream prior to feeding the high temperature melter. Mercury is currently removed during the chemical process via formic acid reduction followed by steam stripping, which allows elemental mercury to be evaporated with the water vapor generated during boiling. The vapors are then condensed and sent to a hold tank where mercury coalesces and is recovered in the tank's sump via gravity settling. Next, mercury is transferred from the tank sump to a purification cell where it is washed with water and nitric acid and removed from the facility. Throughout the chemical processing cell, compounds of mercury exist in the sludge, condensate, and off-gas; all of which present unique challenges. Mercury removal from sludge waste being fed to the DWPF melter is required to avoid exhausting it to the environment or any negative impacts to the Melter Off-Gas system. The mercury concentration must be reduced to a level of 0.8 wt% or less before being introduced to the melter. Even though this is being successfully accomplished, the material balances accounting for incoming and collected mercury are not equal. In addition, mercury has not been effectively purified and collected in the Mercury Purification Cell (MPC) since 2008. A significant cleaning campaign aims to bring the MPC back up to facility housekeeping standards. Two significant investigations are being undertaken to restore mercury collection. The SMECT mercury pump has been removed from the tank and will be functionally tested. Also, research is being conducted by the Savannah River National Laboratory to determine the effects of antifoam addition on the behavior of mercury. These path forward items will help us better understand what is occurring in the mercury collection system and ultimately lead to an improved DWPF production rate and mercury recovery rate. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Oxidation of Glycolate in the Defense Waste Processing Facility (DWPF) Recycle Collection Tank - 20305

The Savannah River Site's Defense Waste Processing Facility (DWPF) operations are being upgraded with the introduction of the Nitric-Glycolic Flowsheet. Glycolic acid has been shown superior to formic acid as the reducing acid used during chemical processing. The new flowsheet improves or maintains necessary parameters such as 1) reduction of mercury, 2) adjustment of feed rheology and 3) adjustment of melter oxidation/reduction potential. Further, the potential for catalytic hydrogen generation in DWPF processing is virtually eliminated. DWPF process condensates are collected and returned to the SRS Concentration, Storage and Transfer Facilities (CSTF). The Recycle Collection Tank (RCT) collects off-gas condensate during chemical processing, vitrification, and other unit operations performed in DWPF and is the singular return vessel delivering recycle effluent back to CSTF. Each batch of recycle may contain a small amount of glycolate from chemical processing and melter off-gas condensates. To avoid potential flammability issues due to thermolysis of glycolate in the CSTF, chemical oxidation within the RCT has been investigated as an option for mitigating the transfer of glycolate. Sodium permanganate has been down-selected as the best option for oxidation of glycolate. Testing was performed using both 2-L and 22-L reactors (16,800:1 and 1,530:1 scale by volume) with non-radioactive waste simulants to approximate the expected RCT compositions. RCT simulants were evaluated at various process pH and temperature conditions. Also, RCT operations, namely the sequence of addition of corrosion inhibitors (NaOH and NaNO{sub 2}) versus a permanganate strike, were evaluated. Glycolate was introduced via a sludge simulant to mimic both expected entrainment and abnormal process foam-over conditions - the range being between 68 and 5100 mg/kg glycolate. Glycolate destruction was monitored by ion chromatography (IC). The corresponding manganese behavior was monitored in real-time using in situ ultraviolet-visible (UV-Vis) spectroscopy. RCT glycolate content can be reduced to below the IC detection limit within 90 minutes for all concentrations investigated. Ion Chromatography analysis revealed that under alkaline conditions, glycolate is primarily oxidized to oxalate with no significant formation of CO{sub 2} or carbonate, and nitrite is not oxidized to nitrate. Initially, complete oxidation of organics species and nitrite was assumed. Determination of the mechanistic chemical reaction has allowed the required amount of permanganate to be more accurately predicted and the total addition to be significantly reduced. UV-Vis measurements reveal that permanganate (Mn{sup 7+}) is reduced to manganate (Mn{sup 6+}) in the RCT. The oxidant stoichiometry is defined by using the initial permanganate to glycolate (P/G) molar ratio. At low initial glycolate concentration (68 and 140 mg/kg), the minimum required initial permanganate to glycolate (P/G) molar ratio was found to be 5-6. With high initial glycolate concentrations (5100 mg/kg) a lower (P/G) molar ratio of ∼2.5 was needed. The final portion of this effort supporting the nitric/glycolic flowsheet will be to test actual (fully radioactive) RCT samples as per the above simulant tests. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Measurement Acceptance Region (MAR) Assessment Results Based On Sludge Batch 10 Projections from December 2021, February 2022 and August 2022

The Defense Waste Processing Facility (DWPF) is currently preparing to initiate processing of Sludge Batch 10 (SB10), which is comprised of material from Tanks 11H, 13H, 15H, and 26F, Alternate Feed Stock-2 and Sodium Reactor Experiment material from H-Canyon. Frit 473 (8B 2 O 3 -8Li 2 O-5Na 2 O-79SiO 2 , in weight percent) was recommended for sludge-only (SO) and coupled processing with the Salt Waste Processing Facility (SWPF) based on previous assessments of SB10 projections with the DWPF Product Composition Control System (PCCS) glass property models and their associated Measurement Acceptance Region (MAR) constraints. Due to the lower processing rate of Sludge Batch 9 (SB9), the heel in Tank 40 is anticipated to be greater than 40 inches at the projected start of SB10 processing to meet the upcoming Accelerated Basin Deinventory addition dates in Tank 51 for Sludge Batch 11. In December 2021 and February 2022, Savannah River Remediation System Planning provided updated SB10 Tank 40 blend projections based on heels of 74 inches, 84 inches, 94 inches and 103.4 inches. Savannah River Mission Completion (SRMC) subsequently pursued Wash Cycle Y to further reduce the total sulfur in the sludge batch and increase processing flexibility at DWPF. In August 2022, SRMC System Planning provided an updated SB10 Tank 40 blend projection with a 76 inch-heel representing Decant Y2 and 60 kilogallons of bearing water inleakage that is anticipated during the Tank 51 to Tank 40 transfer. The objectives of this task were to: • Determine the impact on the operating windows for SO and coupled processing • Determine whether any composition gaps exist between the already completed SB10 variability study and the reprojected SB10 glass composition region • Compare the SB10 reprojected glass composition region to the DWPF PCCS model development and validation ranges to ensure that compositional gaps do not exist between the data sets. This report documents the results of these evaluations. Calculation-based frit assessments were performed using the DWPF PCCS glass property models and their associated MAR constraints. Evaluated parameters for coupled processing included the following transfer volumes per Sludge Receipt and Adjustment Tank batch: 5700 gallons of Tank 40 sludge, 2400-4500 gallons of the SWPF monosodium titanate (MST) and sludge solids stream, and 15,000 gallons of strip effluent. Based on these MAR assessment results, Frit 473 remains viable for SB10 processing. A target waste loading (WL) of 36% is possible for SO operation and single strike (0.4 g/L MST) coupled processing up to 600 mg/L of SB9 insoluble sludge solids at a nominal transfer volume of ~2800 gallons. Increasing the single strike transfer volume to 4500 gallons may reduce the maximum WL below 40%. Operating windows are 12 percentage points for SO processing and 14-16 percentage points for coupled processing. Frit 625 allows for a target WL of 36% and is acceptable for use during the SB9 to SB10 transition to deplete remaining inventory as needed. Operating windows are 8 percentage points for SO processing and 12-14 percentage points for coupled processing. Predictive PCCS evaluations performed at DWPF will provide insight into batch-specific acceptability at desired WLs for compositions having expected oxide ratios during processing versus the extreme vertices (corner points) evaluated in this study. The reprojected SB10 glass composition region generally overlaps the previously evaluated SB10 variability study composition region. Thus, the minor composition shift of these updated SB10 projections indicates that no additional glasses are necessary to demonstrate acceptability relative to the chemical durability of the Environmental Assessment benchmark glass and predictability using the current PCCS models for durability. Based on a comparison of the PCCS model development and validation data to the reprojected SB10 glass composition region, the viscosity and liquidus temperature models will reliably predict SB10 compositions. No additional glasses are necessary to demonstrate predictability of these models.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Amphiphilic Block Copolymers for Flocculation and Hydrophobization of Legacy Waste Suspensions in Flotation Driven Dewatering Operations - 20162

Flotation has been effectively demonstrated as a low footprint, high efficiency separation process when utilising simple anionic surface modifying agents such as sodium dodecyl sulphate (SDS). These agents increase hydrophobicity to remove suspended cationic surface charged particulates such as Mg(OH){sub 2} from waste suspensions similar to those at British nuclear fuel management sites- where corrosion processes have degraded fuel cladding. The technology is advantageous as it could effectively be retrofitted into existing waste management facilities at nuclear waste management sites such Sellafield and Hanford as the simplicity (no moving parts) and size of this technology coupled with low cost of construction could be rapidly deployed to aid in risk and hazard reduction decommissioning operations with minimum impact to secondary waste generation. Previously, sodium dodecyl sulphate has been deployed as a collector agent to increase the hydrophobicity of Mg(OH){sub 2} suspended particles, achieving a maximum particulate extraction percentage of 93%. To achieve further particulate extraction, flotation performance has been determined to be a function of the hydrodynamic limitations extracting fine material (>20 μm). Fine particulates have been shown in the minerals industry to have an inability to overcome slipstreams created from rising bubbles in flotation cells, likely due to the low mass and thus momentum of the colloidal material, preventing interaction between the hydrophobized particles and air-water interfaces (bubbles). To combat this mass transfer resistance poly(acrylic acid)-block-poly(n-butyl acrylate) amphiphilic diblock copolymers were synthesised via reversible addition-fragmentation chain-transfer (RAFT) polymerisation. The anticipated mode of action of these polymers involves the hydrophilic poly(acrylic acid) block polymer acting as a flocculation agent to increase the mass of the aggregates, and the hydrophobic poly(n-butyl acrylate) modifies the hydrophobicity of the resulting flocs. The concentration of this polymer (termed a macro-collector) was varied and the change in particle size distribution of the particulate suspension was analysed using static light scattering. The flotation performance was then characterised by several methods including percentage particulate recovery, volume reduction factor and residual bulk particulate concentration. This was then benchmarked against the traditional surfactant collector agent SDS. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Utilizing Commercial Submersible Mixer Pumps for Sludge Removal in Savannah River Site's Tank 26 - 20289

The Savannah River Site (SRS) Liquid Waste System (LWS) safely manages, stores, treats, and dispositions liquid radioactive waste. The LWS consists of 51 underground waste storage tanks (eight of which are operationally closed and filled with grout), waste evaporators, treatment facilities, and solidification facilities, known as the Defense Waste Processing Facility (DWPF) and Saltstone Production Facility (SPF). One of the waste storage tanks, Tank 26, was placed into service in 1980 as an F Tank Farm (FTF) Evaporator Feed Tank. From 1980 to 2013, Tank 26 received F Canyon receipts and dilute supernate that was then transferred to the 242-16F FTF Evaporator for volume reduction. In 2013, the steam tube bundle failed in the FTF Evaporator, and the decision was made not to repair/resume evaporator operation. During operation of Tank 26, solids built up to a level of 2.03 m in the tank with a volume of 1062.9 kL. Due to the evaporator failure and subsequent shutdown, the solids in Tank 26 were selected to feed Sludge Batch 10, which is collected and prepped prior to being sent to DWPF for final disposition. To accomplish solids removal, Commercial Submersible Mixer Pumps (CSMPs) were selected to slurry the solids in preparation to be sent to Tank 51. Four CSMPs were installed in Tank 26 with each one installed in a separate quadrant of Tank 26. This work would mark the first deployment of CSMPs in an SRS waste tank. The CSMPs were developed in response to operational issues from previous mixing pumps and budgetary constraints. The CSMPs use the concept of modifying commercially available equipment for nuclear waste applications. The CSMPs consist of a 230-horsepower submersible mixing pump (manufactured by GPM, Inc.) joined to a mast fabricated at SRS. For this application, Savannah River Remediation (SRR) design services was challenged to provide a mast design that required no steel superstructure support system on top of Tank 26. Also, SRR design services provided a simplified Tank 26 riser interface that did not require extensive machine parts to adjust height of the suction screen of the CSMP within the tank. Other design improvements include no requirements for tank top radiation monitors and no requirements for flushing of the CSMPs during startup/shutdown operations. The CSMPs were operated at an initial height of 2.29 m above the Tank 26 bottom for 10 days. After sludge sounding, the CSMPs were lowered to a height of 1.52 m with no issues due to proper work planning and the simplified riser interface. With the CSMPs lowered to a level of 1.52 meters above the tank bottom, the CSMPs were operated for 12 days and another sounding was performed. The sounding level came back matching the disturbance depth results of the first pump run. Chemistry samples were analyzed while the tank was left to settle. The analysis revealed enough weight percent solids to provide good feed to Sludge Batch 10. Also, the results revealed the supernate within the mixture would provide good salt solution feed to Salt Waste Processing Facility (SWPF) Salt Batch 3. So, the plan was modified to let the disturbed solids settle and decant the salt solution for addition to SWPF Salt Batch 3. Then water will be added back to Tank 26, and the CSMPs run in order to wash the solids to decrease settling time prior to being sent to Tank 51 for Sludge Batch 10. Utilizing CSMPs for waste removal in an SRS Tank has provided a cost-effective means for further waste removal efforts. In addition, the CSMPs are easier to operate by utilizing a robust and simplified design. The CSMPs performed quite well with no process shutdown or delays during operation. As a result, CSMPs are integral to the future of removing radioactive waste from storage tanks at SRS. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Localizing Low-Grade Heat Using Hybrid Photonic-Phononic Materials

Creating next-generation devices capable of transducing waste heat into useful work will require building blocks designed to direct low-grade thermal energy at length scales well below the diffraction limit. Characterizing thermally induced energy transfer at the nanoscale, however, is a formidable task due to the simultaneous demand of high spatial and spectral resolution at infrared energies. Leveraging recent advancements in electron energy loss (EEL) and gain (EEG) spectroscopy, we reveal that individual nanostructures can concentrate energy by the resonant thermal excitation of their photonic Fabry–Pérot modes. Specifically, we show that the spatially localized gain signal increases upon in situ heating. Finally, theoretical modeling elucidates the mechanism for these observations by showing that a Purcell enhancement in the local photonic density of states drives the increased rate of infrared energy transfer from the ambient environment to each nanostructure.

36 MATERIALS SCIENCE↗

IMPACTS Results Summary for CY 2010

Working in partnership with industry, the U.S. Department of Energy’s (DOE’s) Advanced Manufacturing Office (AMO) is helping reduce industrial energy use, carbon emissions, and waste while boosting productivity and economic competitiveness. Operating within the Office of Energy Efficiency and Renewable Energy (EERE), ITP conducts research, development, and demonstration (RD&D) projects and technology transfer activities that are producing substantial benefits to industry and helping the nation to address some of its biggest challenges in the areas of energy security and environmental performance. This document summarizes some of the impacts of ITP’s programs through 2010. The selection of 2010 as the timeframe for this report recognizes the fact that it takes at least two years to gain a full perspective on program performance and to assess the results of commercialization efforts for the technologies and practices at issue.

Energy Conservation↗

Development of Corrosion- and Erosion-Resistant Coatings for Advanced Ultra-Supercritical Materials

This final report summarized the research efforts and major findings of the Phase I Project “Development of Corrosion- and Erosion-Resistant Coatings for Advanced Ultra-Supercritical Materials”, for the period of October 1, 2019 – Sept. 30, 2021. This project is a collaborative endeavor between Tennessee Tech University, Purdue University, Oak Ridge National Laboratory, Siemens Corporation, and Eastern Plating, LLC, aiming at improving the durability and lifetime of high-pressure (HP) steam turbine blades in advanced ultra-supercritical (A-USC) coal-fired power plants through the development of corrosion/erosion-resistant coatings manufactured via a low-cost electrolytic codeposition process. While Tribaloy alloy T-400C was identified by the U.S. A-USC Materials Consortium as a promising coating composition, further composition optimization is needed to enhance its corrosion and erosion resistance for protecting the A-USC Ni-base turbine components. An integrated computational and experimental approach was employed to optimize coating composition/microstructure and processing parameters. In order to identify candidate coating compositions that could offer balanced properties, thermodynamic calculations were performed to explore the γ+Laves composition space in the Co-Ni-Cr-Mo-Si system with different alloying additions at 600-800 °C. Guided by the calculation results, experimental assessment of selected alloys led to the development of a new generation of Tribaloy compositions with the optimal levels of Cr, Mo and Si, reactive element (e.g., 0.4-0.6 wt.% Y) and other alloying additions. The low-cost and non-line-of-sight electro-codeposition process was employed to deposit a Ni(Co)-CrMoSiY composite coating on commercial Haynes 282 (H282) Ni-base alloy. A diffusion treatment was subsequently applied to convert the composite to the Tribaloy-type coating. Both the codeposition parameters and heat treatment conditions were varied to achieve the desired coating composition, microstructure and phase constituents. In addition, since additive manufacturing (AM) may be an alternative cost-saving option for potential A-USC turbine repair, laser direct deposition was explored to fabricate the H282 alloy with minimal defects. The electro-codeposited Tribaloy coating was also applied to the AM H282 substrate to demonstrate the viability of the coating process in improving the surface finish of AM alloys. Both high-temperature oxidation performance and solid particle erosion (SPE) resistance of model alloys and electro-codeposited coatings were evaluated. About 25 model alloys with various Cr/Mo ratios and reactive element levels, as well as partial substitution of Mo with Nb were evaluated with regard to their oxidation resistance in both air and pure steam at 760-800°C. Compositions based on Ni(Co)-20Cr-18Mo-2.6Si-0.6Y (wt.%) showed significantly improved oxidation resistance over the baseline T400-C. Based on the alloy development results, three generations of new Tribaloy coatings (Gen-1, Gen-2, and Gen-3) with various Mo/Cr contents and Y levels were prepared via electro-codeposition and their microstructure/performance were evaluated. Outstanding air and steam oxidation resistance was achieved for the Gen-2 and Gen-3 coatings. Furthermore, while the SPE resistance of the coatings depended on many factors such as temperature, environment, erodent, velocity and impact angle, the coated samples exhibited similar or better SPE resistance compared to the H282 substrate when magnetite was used as erodent (which is a realistic erodent in A-USC steam turbines). The new Tribaloy coatings also had good long-term compatibility with the H282 alloy substrate. The two large-sized rotating barrels were designed, constructed, and employed to coat dummy HP blades. Uniform coating thickness and microstructure were achieved at various blade locations. Also, a preliminary techno-economic analysis of the proposed coating process was conducted to quantify the cost-effectiveness and to assess the commercial viability of the corrosion- and erosion-resistant coatings. It is estimated that a cost reduction of ~30% could be achieved with the electro-codeposition coating process over the state-of-the-art high velocity oxygen fuel (HVOF) thermal spray. Compared to the leading Tribaloy coating technologies such as HVOF and plasma transfer alloying, electro-codeposition based process has advantages such as low-cost process equipment, uniform deposition even for complex shapes, low levels of contaminants/porosities, reduction of powder waste, and potentially better surface finish and longer turbine service life. The Phase 1 study has demonstrated that it is feasible to develop an electro-codeposited Tribaloy coating with balanced corrosion and erosion properties, even though additional research efforts such as further coating process scale-up and longer-term performance evaluation under realistic A-USC conditions are clearly needed.

20 FOSSIL-FUELED POWER PLANTS↗

Waste heat recovery lube oil management

A waste heat recovery system comprising a thermal circuit. The thermal circuit includes a boiler and an expander fluidly coupled to the boiler. The thermal circuit further includes a power transfer system integrated to the expander. The power transfer system is configured to receive mechanical energy from the expander. The thermal circuit further includes an ejector fluidly coupled to the boiler and to the power transfer system. The ejector is configured to receive a motive flow of working fluid from the boiler. The ejector is further configured to receive a suction flow of working fluid from the power transfer system. The ejector is further configured to combine the motive flow of working fluid and the suction flow of working fluid.

Ernst, Timothy C.↗

Regulatory Control of Sealed Sources in Germany including Regulations Regarding Spent and Disused Sources - 13176

Effective regulatory control is essential to ensure the safe and secure use of radioactive material and the appropriate management of radioactive waste. To ensure a sustainable control of high radioactive sources, the European Commission published the Council Directive 2003/122/EURATOM on the control of high-activity sealed radioactive sources and orphan sources, which had to be transferred into national legislation by all member states of the European Union. Major requirement of the Directive is a system to ensure traceability of high-activity sealed sources from 'cradle to grave' as well as the provision to take back disused sources by the supplier or manufacturer. With the Act on high-activity sealed radioactive sources Germany implemented the requirements of the Directive 2003/122/EURATOM and established a national registry of high-activity sealed sources in 2006. Currently, about 27.000 high-activity sealed sources are recorded in this national registry. (authors)

07 ISOTOPE AND RADIATION SOURCES↗

Field Validation of Thermoelectric Generation System at Holcim Cement Plant in Alpena, Michigan

Executive Summary Project Background The Industrial Technology Validation (ITV) program aims to identify and demonstrate the performance of new, emerging, and underutilized energy-saving technologies in the industrial sector to help inform decisions to help accelerate their commercialization and deployment, as well as to help make industries more competitive. This ITV demonstration evaluated a thermoelectric generation (TEG) technology at a cement plant, aiming to reduce energy demand in the cement industry. A median cement plant consumes 5.73 million British thermal units per ton of clinker production (resulting in 0.838 metric tons of carbon dioxide [CO₂] emissions per ton of clinker) (Boyd and Zhang 2011, EPA 2021), equivalent to approximately 6.9 trillion British thermal units (TBtu) per year in energy consumption at a cement plant producing 3,300 tons of clinker per day.¹ Collaborating with Holcim, Advanced Thermovoltaic Systems (ATS) developed and deployed a pilot-scale thermoelectric power system to efficiently capture and convert waste heat to electricity. The system leverages the Seebeck effect to convert temperature differences on two sides of semiconductor cartridges into electrical power (ScienceDirect, n.d.). This generation is realized with minimal moving parts compared to existing waste-heat-to-generation solutions and allows capture from heat sources with temperatures as low as 150°C. This project aimed to validate a scalable solution applicable for capturing medium-temperature waste heat, including ambient losses from other high-temperature processes, and high-temperature sources less suitable for other waste-heat-to-power solutions. By recovering this otherwise wasted heat, this project intends to validate improvements to overall process efficiency through reduction in purchased electricity, thereby reducing operational costs while enhancing resiliency and competitiveness. Description and Scope This study evaluated the performance of a TEG system from ATS as a solution to convert waste heat into useful power at a Holcim cement plant in Alpena, Michigan. This plant is a fully integrated cement plant that has been operating since 1907. The facility operates continuously (24/7/365) with approximately 250 employees and five long dry kilns, yielding a total production capacity of 7,852 tons of cement per day (EPA 2023). Currently, the Alpena plant uses waste heat boilers to convert waste heat from the exhaust of each kiln into steam, which drives steam turbine generators. The ATS TEG is being evaluated for its potential to supplement the steam turbines by capturing the remaining lower grade heat. This technology is also being considered for other Holcim plants where steam turbines are not a viable option. ATS installed a pilot-scale TEG unit with an array of 582 individual thermoelectric semiconductor cartridges, of which 573 were operational. The cartridges are sandwiched between 48 hot plates and 49 cold plates. Each cartridge is designed to generate 20 watts (W) of gross power at a hot-side temperature of 240°C and cold-side temperature of 20°C. As such, the total gross generation capacity of the installed system is 11.5 kilowatts (kW) at design conditions. The system configuration for the evaluation was designed to prioritize convenience of installation and minimize disruption to production at the site, while ensuring that the heat required can be obtained for evaluating the TEG system at various operational conditions. To accomplish this, a portion of the steam supplied to Alpena’s steam turbine generation system was diverted to be used as the heat source for the TEG system, while water was supplied to the cold side of the system from nearby Lake Huron. This configuration was designed for the evaluation of the pilot-scale system to assess the performance at different conditions. A commercial-scale system will likely vary from the pilot system depending on typical configurations, including both scale and application. Future commercial applications of the ATS system would involve integrating the system into the exhaust from kiln preheaters, clinker coolers, or radiant heat capture from kiln shells for the heat source. For the cold source, a range of cooling solutions can be considered, including a mechanical cooling system, depending on the location and the application. To increase the generation capacity for commercial applications, the technology provider is working toward developing a commercial-scale TEG system, which would combine multiple TEG units (each similar in design to the pilot system) together. The scope of this evaluation includes the pilot-scale TEG system and all impacted equipment including pumps, controllers, and power handling equipment. Study Objectives The evaluation's goal was to assess the potential of the ATS TEG system to generate useful electrical power by capturing waste heat from cement production kilns. The objectives of this study are to evaluate and verify the following claims made by ATS regarding the pilot-scale system installed at the Holcim Alpena plant. The following design parameters and claims are also outlined in Table ES- 1 and Table ES- 2: • Gross Power: The thermoelectric system converts heat into power to create gross power, the total measured power generated by the system. The 573 active cartridge pilot-scale system is expected to generate 11.5 kW of gross power at the designed hot-side temperature of 240°C and cold-side temperature of 20°C. Power production is dependent on the temperature difference between the heat source (ultimately from the waste heat) and cold temperature supply source. • Net Power: The net power is the total usable power provided to the site by the TEG system after deducting parasitic power loads from the gross generated power. Supplementary equipment is required to operate the TEG system including pumps, controllers, and, in certain anticipated applications, mechanical cooling, which introduce parasitic loads to system operation. After deducting the parasitic loads from the gross power generation, ATS anticipates achieving a net power generation of 7.5 kW from the pilot-scale system. • Thermal Efficiency: The thermal efficiency is the percent of the total heat transferred to the TEG system that is converted to gross power. Historically, TEGs have a thermal efficiency of 2%–5% (DOE 2008). Prior industrial-scale TEG systems, such as the E1 TEG offered by Alphabet Energy, operated at an efficiency of 2.5% (Lamonica, 2014). ATS anticipates achieving an average efficiency of 4.8% or higher in converting heat energy to usable electricity. • Cartridge Performance: The TEG system comprises 573 active individual semiconductor cartridges, each of which generates a portion of the total power. Cartridge optimization and selection is an important design consideration for potential future TEG system design performance. Therefore, understanding the distribution of gross power and efficiency within the pilot system is vital to understanding what is achievable. At a design hot-side temperature of 240°C and cold-side temperature of 20°C, ATS anticipates a cartridge performance of 20 W of gross power per cartridge at an efficiency of 4.8% per cartridge. In addition to evaluating the claimed performance of the TEG pilot-scale unit, the study estimated the potential annual impacts of a scaled-up commercial system used to capture kiln waste heat over annual operations. The evaluation estimated the gross and net annual electric generation achievable by capturing heat from the two proposed tap-in points: the kiln exhaust and the clinker cooler exhaust; see Section 2.1 for details. Two use cases were examined: • Holcim Alpena: The Holcim Alpena site consists of long dry kilns with superheater boilers, which differs from the rest of Holcim’s cement plant portfolio and results in lower waste heat temperatures. The study estimates gross and net annual generation using the superheater boiler exhaust and clinker cooler exhaust, based on 2023 operational data. • Typical Installation: Common cement plants have preheater kilns with higher exhaust temperatures than Holcim Alpena across a range of production rates. The study estimates gross and net annual generation using the preheater exhaust and clinker cooler exhaust, with a sensitivity analysis to account for the typical range of preheater exhaust temperatures, clinker cooler exhaust temperatures, and clinker production rates. Methodology The evaluation methodology followed a measurement and verification (M&V) strategy based on the International Performance Measurement and Verification Protocol Option B through comprehensive measurements and analyses of the affected systems. Evaluation data was collected from March 9 to March 11, 2024, the test period of the pilot TEG system. During the test period, in coordination with the ITV team, the ATS team adjusted system operations to capture the range of variability expected for each of the variables pertinent to performance of the system. The methodology consisted of two parts: evaluating the performance of the pilot unit's TEG system and estimating the annual TEG impact in terms of gross and net power based on a given waste heat profile. First, the evaluation of the thermoelectric generation performance of the pilot unit relative to the claims was performed by analyzing the collected test data. Gross power of the pilot TEG system was directly measured. Net power was determined by deducting the measured parasitic power from the gross power. The gross power generation was compared to heat transferred to the system by the working fluid (which was heated by steam generated from the kiln waste heat) to calculate the thermal efficiency achieved by the system. Performance of individual semiconductor cartridges within the pilot array was also assessed in terms of measured gross cartridge power and calculated cartridge thermal efficiency. The second part of the evaluation estimated the annual TEG impacts in terms of gross power and net power (calculated from the difference between gross power and parasitic power). This analysis comprised development of mathematical regression models for gross power and parasitic power, with assessment of each model’s goodness-of-fit characteristics to ensure satisfaction of statistical requirements. The models predicted the gross power generation, the parasitic load based on the temperature difference between the hot working fluid and the cold-side fluid (cold water from Lake Huron) entering the system, the volumetric flow rate of the cold-side fluid at the inlet, and the volumetric flow rate of the hot working fluid at the inlet. The annual impact analysis considered a theoretical commercial-scale system sized to capture the available waste heat at a cement plant, consisting of linked pilot-scale units that receive heat from a theoretical gas-to-working-fluid heat exchanger. To estimate annual impacts at the Alpena plant, the gross power and parasitic power regression models were applied to the arrays in the theoretical commercial-scale system. The heat supplied to the unit was calculated based on the kiln run time, annual production, kiln exhaust waste heat, and clinker cooler waste heat derived from 2023 Holcim Alpena kiln operational data. Net power impacts were calculated by deducting the resulting parasitic power from the estimated gross power. Inputs for the model were generated from a combination of hourly data, assumed design considerations for TEG system scale-up from the pilot-scale unit, and assumptions regarding TEG system operations. This analysis was then used as the basis for estimating annual impacts of typical TEG installation at cement plants, by applying sensitivity analyses to key kiln operational characteristics including kiln preheater exhaust temperatures, cooler clinker exhaust temperatures, and plant daily production rates across a range of expected values. Project Results/Findings Table ES- 2 and Table ES- 2 provide a summary of the operating conditions and evaluation results compared to the stated claims from the technology provider. Key takeaways include: • Gross Power: The peak gross power achieved during the testing period was 10.0 kW, compared to the 11.5 kW expected for 573 active cartridges. The claimed gross power was associated with a target hot side of 240°C; however, the system only received a maximum hot-side mean plate temperature of 212°C during the testing period. • Net Power: The pilot-scale unit exceeded the claims for net power, achieving a peak of 7.7 kW net compared to a claim of 7.5 kW. One factor contributing to the higher achieved net power is the relatively high water pressure available through Lake Huron. The pilot TEG system did not require cold-side pumps during the test, whereas most installations would. This reduced the parasitic loads on the system, ultimately contributing to higher net power relative to the gross power. • Thermal Efficiency: The pilot-scale unit outperformed the claimed efficiency, achieving a peak system efficiency of 5.0% thermal efficiency compared to the stated 4.8%. • Cartridge Performance: To compare cartridge performance against claims, the study focused on the third day of testing, which aimed for conditions closest to the design specifications, with a hot side of 240°C and cold-side exit temperature of 6.4°–30°C. On this day, the mean gross power observed in the cartridges within the TEG array was 18.1 W/cartridge, and the peak performance was 34.7 W/cartridge. The estimated mean cartridge efficiency was 5.2%, and the estimated efficiency at peak gross cartridge power was 10%. The regression models developed for gross power generation and parasitic loads were used to estimate the generation impact for given heat input to the TEG from the working fluid (captured from the waste heat) and from the cold loop (Lake Huron) on an hourly basis for a year of operation. Based on this analysis, installation of a commercial-scale TEG system at the Holcim cement plant in Alpena, Michigan, with a waste heat exchanger of 0.85 effectiveness, would generate up to 391 kW of net power, translating to between 920,000 and 1,800,000 kilowatt-hours (kWh) in net electricity per year. Based on typical grid emissions for Alpena, this would avoid estimated net emissions by 752 metric tons of CO₂ annually.² The sensitivity analysis estimated that typical TEG system installations at cement plants could generate an average of 56–1,040 kW of net power, or between 488,000 and 9,110,000 kWh of net energy. This generation potential is most significantly affected by plant production rates and also influenced by preheater and clinker cooler exhaust temperatures. Applying the national average emission rate, typical commercial-scale installations at Holcim plants are projected to avoid between 182 and 3,401 metric tons of CO₂ annually per site. Table ES- 3 shows a summary of the estimated annual impacts.³ While parasitic loads are significant and vary by application, this analysis assumed the use of heating loop pumps and access to Lake Huron as a cold sink. This setup assumed no need for cooling loop pumps due to the available water pressure at the test site. Applications that require cooling towers or additional equipment are likely to experience higher parasitic loads. Therefore, the study’s estimates are most applicable to scenarios with similar parasitic load configurations—namely, access to a high-pressure cold sink. Applicability to other locations may be limited, as differing conditions could necessitate additional pumps and cooling systems, potentially impacting performance significantly.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Upcycling of polyethylene to gasoline through a self-supplied hydrogen strategy in a layered self-pillared zeolite

Conversion of plastic wastes to valuable carbon resources without using noble metal catalysts or external hydrogen remains a challenging task. Here we report a layered self-pillared zeolite that enables the conversion of polyethylene to gasoline with a remarkable selectivity of 99% and yields of >80% in 4 h at 240 °C. The liquid product is primarily composed of branched alkanes (selectivity of 72%), affording a high research octane number of 88.0 that is comparable to commercial gasoline (86.6). In situ inelastic neutron scattering, small-angle neutron scattering, solid-state nuclear magnetic resonance, X-ray absorption spectroscopy and isotope-labelling experiments reveal that the activation of polyethylene is promoted by the open framework tri-coordinated Al sites of the zeolite, followed by β-scission and isomerization on Brönsted acids sites, accompanied by hydride transfer over open framework tri-coordinated Al sites through a self-supplied hydrogen pathway to yield selectivity to branched alkanes. This study shows the potential of layered zeolite materials in enabling the upcycling of plastic wastes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Alternative reductants for foam control during vitrification of high-iron High Level Waste (HLW) feeds

Foaming during vitrification of radioactive waste in Joule-Heated Ceramic Melters (JHCM) is exacerbated by trapping of evolving gases, such as CO 2 , NO x and O 2 , beneath a viscous reaction layer. Foaming restricts heat transfer during melting. Sucrose is employed as the baseline additive at the Hanford site in Washington State, USA to reduce foaming. Alternative carbon-based reductant additives were explored in simulated, inactive Hanford high-iron HLW-NG-Fe2 feeds, for both their effect on foaming and to give insight to the behaviour of multivalent species in glass melts under different redox conditions. Graphite, coke (93% C), formic acid and HEDTA additives were compared with sucrose, and a feed with no additive. Graphite and coke additions proved most effective in reducing the maximum foam volume by 51 ± 3% and 54 ± 2%, respectively, compared with 24 ± 5% for sucrose. Lower foaming could result in more efficient vitrification in JHCMs. Reductants also affected redox ratios in the multivalent species present in the feed. The order of reduction, Mn 3+ /Mn 2+ > Cr 6+ /Cr 3+ > Ce 3+ /Ce 4+ > Fe 3+ /Fe 2+ was as predicted on the basis of their redox potentials. There is less reduction overall, particularly in the Fe 3+ → Fe 2+ , than predicted by the calculations, attributed to the oxygenated atmosphere of the experiments.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Adaptive Evolution of Sphingobium hydrophobicum C1 T in Electronic Waste Contaminated River Sediment

Electronic waste (e-waste) has caused a severe worldwide pollution problem. Despite increasing isolation of degradative microorganisms from e-waste contaminated environments, the mechanisms underlying their adaptive evolution in such habitats remain unclear. Sphingomonads generally have xenobiotic-degrading ability and may play important roles in bioremediation. Sphingobium hydrophobicum C1 T , characterized with superior cell surface hydrophobicity, was recently isolated from e-waste contaminated river sediment. To dissect the mechanisms driving its adaptive evolution, we evaluated its stress resistance, sequenced its genome and performed comparative genomic analysis with 19 other Sphingobium strains. Strain C1 T can feed on several kinds of e-waste-derived xenobiotics, exhibits a great resistance to heavy metals and possesses a high colonization ability. It harbors abundant genes involved in environmental adaptation, some of which are intrinsic prior to experiencing e-waste contamination. The extensive genomic variations between strain C1 T and other Sphingobium strains, numerous C1 T -unique genes, massive mobile elements and frequent genome rearrangements reflect a high genome plasticity. Positive selection, gene duplication, and especially horizontal gene transfer drive the adaptive evolution of strain C1 T . Moreover, presence of type IV secretion systems may allow strain C1 T to be a source of beneficial genes for surrounding microorganisms. This study provides new insights into the adaptive evolution of sphingomonads, and potentially guides bioremediation strategies.

comparative genomics↗

On the influence of the power plant operational history on the inventory and the uncertainties of radionuclides relevant for the final disposal of PWR spent fuel - 15149

A mandatory requisite for official granting safe final disposal approval of SNF is the comprehensive specification and declaration of the nuclear inventory in SNF by the NPP-operators. The whole radiochemical characterization of each spent fuel assembly hides many difficulties such as very high radiation burden, destruction method, the inhomogeneous burn-up of fuel assembly, very high cost. Thus, non-destructive characterization is usually applied on industrial scale. In this case only several nuclides can be measured, and the rest is calculated using simulations and typical irradiation history. Like any other German rad-waste acceptance requirements all these declarations will have to be checked and verified by an independent inspector. In this verification process not only values of radionuclide (RN) activities are important, but also their uncertainties. The simple simulation using burn-up calculations based on typical and generic reactor operational parameters do not answer the question about possible uncertainties observed in real reactor operations. At the same time, the details of irradiation history are often unknown, which complicates the assessment of declared RN inventories. Therefore, the development of dedicated generic proof tools, which can be applied to different types of waste, often of unknown origin and history is worth a serious consideration. Here, we have compiled a set of burn-up calculations considering the operational history of 339 published or anonymized real PWR fuel assemblies. This gives us the possibility to calculate the realistic variation or spectrum of RN inventories. These histories were used as a basis for 'SRP analysis', to provide information about the range of the values of the associated secondary reactor parameters (SRP's), i.e. initial enrichment (IE), specific power (SP), irradiation time (IT), downtime (DT), boric acid concentration (BA), moderator and fuel density (MD and FD) and temperatures (MT and MT) used as input parameters for the simulation models. Then, burn-up calculation codes provide the anticipated results for the entire nuclear inventory such as characteristic activity values and the corresponding minimum and maximum limits as a function of the fuel burn-up. These results are being validated with the experimental data from various publications and the online database - SFCOMPO and subsequently transferred and summarized into our own database. Ultimately, this database will provide the basis of proof tools for the operator independent verification of the declared nuclear inventories for the quality and safety assessment of a radioactive waste compound and bounding values for certain RN as a function of burn-up. The RN inventory can hence be verified without taking credit of the whole of the operational history of the SNF. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Characterizing a High-Level Waste Cold Cap via Elemental and Structural Configuration

The process of converting high-level waste feed to an immobilized glass form takes place within a cold cap which covers a high-temperature (1150°C) glass melt in a Joule or induction heated melter. Liquid slurry feed is continuously charged through the top of a melter. Within the cold cap, many glass forming reactions occur and the glass-forming melt becomes connected. Gases trapped in the glass-forming melt arrange into bubbles which create a layer of foam below the reacting feed that collapses into cavities. This foam layer thermally insulates the reacting feed limiting heat transfer from the molten glass below, thus affecting the rate of glass formation. Information about the glass formation is desired for incorporation in a mathematical model designed to simulate the melting in a cold cap. To explore this, a set of high-level waste feed simulant samples were heat-treated at 5 K min-1 to temperatures ranging from 400°C to 1200°C for comparison with cold cap sections generated in a laboratory-scale melter. To estimate the temperature distribution in laboratory-produced cold caps, structural (bubble size and shape) and optical (color) properties of heat-treated samples and cold-cap sections were compared along with elemental maps, the shapes and sizes of the silica particles, and the connectivity of the glass matrix. These results will be used to verify the recently developed mathematical model of the cold-cap.

Cold Cap↗

DOE-EM/HBCU Projects for Environmental Management Research and Workshop Development at SCSU [Conference Papers/Proceedings]. Final Report

The Department of Energy’s Office of Environmental Management (DOE-EM) established a Memorandum of Understanding (MOU) with nine HBCUs in South Carolina and Northeast Georgia. The nine HBCUs (Allen University, Benedict College, Claflin University, Clinton Junior College, Demark Technical College, Morris College, South Carolina State University, Voorhees College and Paine College of Northeast Georgia) have formulated a consortium to address the technical and workforce development needs of the DOE’s Office of Environmental Management. These institutions have the qualifications and expertise to provide the technical cooperation and operations support in the areas of environmental remediation, nuclear regulatory and transportation safety, modeling, technology transfer and workforce development. Several of the HBCUs have received awards from the DOE to address issues related to ground water, surface water, plant communities, the development of an interdisciplinary waste management institute, and the establishment of an environmental science field station. Also, the acquisition of these grant awards have afforded the participating institutions with the ability to instruct students by providing them with the appropriate skill sets to address the future employment needs of DOE to include: Hands-on field experiences; Classroom demonstrations; and, Research and education experiences. South Carolina State University will build upon its existing relationships with DOE-EM by creating a "pipeline" for minorities in Mathematics, Science & Technology, Engineering, Research, and other related fields. Students will be specifically trained and mentored to enter the DOE workforce in these technical areas of need. The integration of technology in research and education is essential for meeting the demanding need to develop a workable mechanism to optimize the effectiveness of research and education in this nation. This is extremely critical in this age of unprecedented technological advances when information delivery, training, and continuous research to improve performance and skill enhancement hold the key to competition. This development relies on a program of applied science to identify and help implement the technologies, as well as programs that energize and mentor the next generation of scientists and engineers. To foster these goals, SCSU proposes research and educational projects that will support the integration of technology in research and education.

54 ENVIRONMENTAL SCIENCES↗