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At least 523 records · Page 29

Energy Analysis of Combi Heat Pump System Configurations for Space Conditioning and Domestic Hot Water Heating in Residential Buildings

Combi heat pump systems, also referred to multifunctional variable refrigerant flow heat recovery (MF-VRFHR) systems, are specifically designed for residential applications to manage both space conditioning and domestic hot water (DHW). They have attracted attention due to their potential for energy conservation through heat recovery. The incorporation of a hot water tank introduces various system configurations, each characterized by distinct pros and cons related to energy efficiency, system stability, and maintenance. Despite this, a critical gap exists as the specific energy performance remains unquantified under diverse operational modes (e.g., heating mode and heat recovery mode). This paper aims to bridge this gap by conducting a comprehensive comparative analysis of two prevalent system configurations while considering feasible proposed control logics. Configuration 1 integrates a separate hot water tank and a refrigerant-to-water heat exchanger (HEX), also known as a Hydro Kit while Configuration 2 incorporates a refrigerant-wrapped hot water tank. To facilitate this analysis, we developed high-fidelity system models for both configurations in Modelica, capturing system dynamics and detailed control sequences effectively. These system models were built upon the TIL library for HVAC equipment components and the Buildings library for residential building thermal load calculations. The validation of the simulation testbed utilized data from experiments conducted in the PNNL lab home for Configuration 1. To establish the simulation testbed for Configuration 2, we extended the modeling setup derived from Configuration 1. This extension specifically involved substituting the separate hot water tank and Hydro Kit with a refrigerant-wrapped hot water tank of similar sizing sourced from an actual product. The simulation analysis of heating-only and heat recovery modes reveals that Configuration 2 not only saves energy and maintains warmer tank temperatures but also demonstrates faster water heating capabilities. This is attributed to decreased energy loss and improved heat transfer. The study encompasses a wide range of scenarios, considering diverse thermal loads and water usage patterns across heating and heat recovery modes. Overall, the comprehensive results indicate that Configuration 2 achieves energy savings ranging from 3.5% to 12.2% compared to Configuration 1, depending on factors such as water usage patterns, thermal loads, and operational modes.

Configuration, Comparison, Multi-functional, Resid↗

Advanced metal hydride heat transfer system utilizing an electrochemical hydrogen compressor

An electrochemical heat transfer device for a hot water tank utilizes an electrochemical hydrogen compressor to pump hydrogen into and out of a tank having a metal hydride forming alloy therein. The absorption of hydrogen by the metal hydride forming alloy is exothermic, produces heat, and the desorption of the hydrogen from the metal hydride forming alloy is endothermic and draws heat in. An electrochemical hydrogen compressor may be configured between to tanks and pump hydrogen back and forth to form a heat transfer device, such as a hot water heater. A heat transfer device may be coupled with the tank or may comprise the outer surface of the tank to transfer heat to an object or to the surroundings. A closed loop may be configured having two tanks and one or two electrochemical hydrogen compressors to pump the hydrogen in a loop around the system.

Bahar, Bamdad↗

System for roll-to-roll electrocoating of battery electrode coatings onto a foil substrate

The present invention is directed toward a coating system for electrodepositing a battery electrode coating onto a foil substrate, the system comprising a tank structured and arranged to hold an electrodepositable coating composition; a feed roller positioned outside of the tank structured and arranged to feed the foil into the tank; at least one counter electrode positioned inside the tank, the counter electrode in electrical communication with the foil during operation of the system to thereby deposit the battery electrode coating onto the foil; and an in-line foil drier positioned outside the tank structured and arranged to receive the coated foil from the tank. Also disclosed are methods for electrocoating battery electrode coatings onto conductive foil substrates, coated foil substrates, and electrical storage devices comprising the coated foil substrates.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Development of Methane Emissions Model to Assess Fuel Recovery Potential at Gas Well Sites Using On Site Compression

The U.S. natural gas production and consumption has increased 85.5% since 2005 primarily due to the unconventional production methods of horizontal drilling and hydraulic fracturing. Natural gas used as a fuel has a lower greenhouse gas (GHG) footprint than coal and petroleum due to lower Carbon Dioxide (CO2) emissions when combusted. However, the “greener” benefit to natural gas may be negated by leaks in production and transmission systems. Methane (CH4), the primary hydrocarbon in natural gas, has an estimated Global Warming Potential (GWP) of 28-36 over 100 years, meaning it can absorb 28-36 more energy than CO2 which has a GWP of 1.0. Natural gas well sites are prone to methane emissions, or leaks and irregular gas releases, vented to atmosphere throughout production and transmission. The U.S. Department of Energy (DOE) and the National Energy Technology Laboratory (NETL) has recently granted West Virginia University (WVU) funding under agreement DE-FOA-0002005, to “Advance technologies to mitigate methane emissions and increase the efficiency of the natural gas transportation infrastructure”. As part of this funding WVU was tasked with identifying and quantifying sources of methane emissions at unconventional well sites, processing this data, and developing a system to recapture these emissions. A 0-D Simulink model was developed, utilizing standardized methodologies, data from previously conducted studies, as well as collected data from well sites in the Marcellus shale play region. The model was developed to predict emission rates from various components at natural gas well sites as well as the potential to utilize these emissions as fuel for the natural gas powered compressor engines on-site. This model was utilized to run high, medium, and low cases for four identified emission sources, engine size, pneumatic controller count, liquid level production which dictates tank emissions, and compressor packing vent emissions. Due to discrepancies in transient tank emission data, a high and low emission factor for tanks was used, resulting in two sets of 81 executed cases, and 162 unique cases of total site emissions and potential for fuel consumption. Each of the cases were run over 86,400 seconds at a 1 Hz, representative of a full 24 hour day of operation. The fuel consumption offset an average of 557% of fuel consumption on an energy density basis across all 81 cases with the high tank emission factor with a maximum offset of 2334%. The fuel consumption offset was an average of 82.9% for all 81 cases with the low tank emission factor with a maximum offset of 337%. This study highlights flaws in the use of publicly available methane number calculations to determine natural gas’s suitability as an engine fuel as well as the lack of public data for transient liquid storage tank emissions.

03 NATURAL GAS↗

Project Development of an Electrochemical Denitration and Caustic Generation System for HLW Pretreatment at Hanford - 26350

An engineering-scale electrochemical processing skid is proposed to perform the denitration of Hanford tank waste, which would help to mitigate a key process concern with the direct feed processing of the Hanford Tank Waste Treatment and Immobilization Plant (WTP). The reduction of nitrates and organic compounds in the waste feed will directly reduce hazardous NOx and ammonia gases generated during the vitrification process, which in turn will aid in addressing potential regulatory and safety challenges associated with processing large volumes of tank waste. This paper highlights the past legacy work, project layout, accomplishments from Phase 1 and research and development envisioned for Phase 2. An innovative electrochemical denitration and caustic generation (EDCGe) process was demonstrated for the pretreatment of tank waste at the Savannah River Site (SRS) in the early 2000s. The denitration electrolyzer, off-gas abatement system, and caustic generator electrolyzer are being developed with the intent that the denitration electrolyzer will convert nitrate and nitrite anions to nitrogen gas while also yielding other gaseous byproducts, which may include N2O, NH3, VOCs, and H2. The gaseous byproducts will be managed via a tandem off-gas catalyst-bed treatment system. The caustic generation electrolyzer will recycle NaOH from the feed to produce a clean caustic stream for use within the batching tanks at Hanford, aiding in the preparation of waste for WTP. The reduction in hazardous emissions and improved waste treatment processes provides a robust solution for nuclear waste management, contributing to environmental safety and regulatory compliance. The EDCGe technology is being adapted, modified, and updated for the preparation of the Direct Feed-High Level Waste (DF-HLW) flowsheet at Hanford. Phase 1 demonstrated a bench-scale proof-of-concept for reactions involving the denitration electrolyzer and gas phase abatement of ammonia. The electrochemical technology is drawing on the scientific outcomes that were reported in the legacy work. The results from Phase 1 demonstrated the viability of the EDCGe system in reducing the nitrogen species of simple non-radioactive waste simulants. Commercially available alloys used as electrode materials and membranes are being studied for the denitration and caustic generation electrolyzers. The continuation of this project holds promise for broader applications, such as energy-efficient ammonia production, and contributes significant advancements in nuclear waste management. Additional material discovery has been investigated into ceramic Na super ion conductive (NaSICON) materials and off-gas abatement catalyst discovery. NaSICON is of interest for selective transport of Na within the electrolyzers to make a clean caustic stream. Future integration and optimization efforts, informed by Phase 1 results and ongoing research, will continue to drive advancements in nuclear waste management technology. The technology developed for the EDCGe treatment of tank waste will also have broader potential to inform other fields, such as energy-efficient ammonia production, as well as ammonia abatement catalysis through the lessons learned in electrochemical nitrate reduction. The applications and benefits of this research extend beyond Hanford and the Savannah River Site, supported by a collaborative team of scientists and engineers from national labs, academia, and industry, ensuring a comprehensive approach to solving complex waste treatment challenges. The team is leveraging advanced electrochemical technologies, machine learning, novel catalysts tailored for gaseous nitrogen species, and cutting-edge reactor systems to enhance the process efficiency and effectiveness of the denitration process.

Rodene, Dylan [Savannah River National Laboratory ↗

Parametric Studies of Heat Pump Water Heater Using Low GWP Refrigerants

A storage heat pump water heater (HPWH) comprises a vapor compression system and a hot water tank. It can lead to more than 70% energy saving, compared with electric resistance heating. HPWH usually uses a wrapped-tank coil as the water heater. The wrapped coil has a strong interaction with the water tank and impose a new challenge for the engineering design and simulation study. Based on the US DOE/ORNL Heat Pump Design Model (HPDM), i.e., a public-domain, component-based thermal system modelling platform, a segment-to-segment wrapped-tank coil model coupled with a one-dimensional stratified water tank model were developed, which facilitates modeling and design HPWHs having various configurations and components. Additionally, the hardware-based design model was used to evaluate refrigerants having lower global warming potentials to replace R-134a, including R-1234yf, R-1234ze, R-290, R-513A and R-450A, when effects of compressor size, refrigerant charge on 24-hour uniform energy factor (UEF) and first-hour rating (FHR) were investigated.In the drop-in replacements, R-1234ze achieved the best UEF, and R-290 resulted in the lowest UEF. When downsizing the compressor to maximize the UEFs, the UEFs of R-134a, R-290, R1234yf, R-450A and R-513A ascended to the range of 4.4 to 4.53, with R-513A having the highest UEF. The R-1234ze ended up having the lowest UEF of 4.27. Refrigerants having larger volumetric vaporization heat led to higher FHRs if using the fixed-size compressor, that R-290 resulted in the highest FHR.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Technical and economic feasibility of molten chloride salt thermal energy storage systems

A techno-economic study is performed to assess the feasibility of molten chloride salt thermal energy storage (TES) systems for next generation concentrating solar power. Refractory liners internally insulate tanks to allow tank shells to be constructed from carbon steel. The liner must not be wetted by salt to maintain predictable thermal properties and manageable heat loss out of the tank. The commercial scale tank liner is an anchored brick and mortar design with expansion joints to accommodate thermal expansion. Furthermore, finite element analysis is performed to optimize the thermal and mechanical profile of the tank. Equalizing the shell temperature between the water-cooled foundation and the shell wall is necessary to minimize differential thermomechanical stress and lower overall stress values below industrial allowable limits. The cost of the TES system is estimated to be $60/kWhth, which is four times greater than Department of Energy targets. Solutions to reduce system cost and overall risk are proposed.

14 SOLAR ENERGY↗

Technical Gaps in Hanford High-Level Waste Solids Settling Behavior and Settling Time Evaluation for Direct Feed High-Level Waste (DFHLW) Operations

Settling of high-level waste (HLW) solids in process vessels is a key conceptual process step in providing HLW feed directly to the Hanford Waste Treatment and Immobilization Plant (WTP) HLW Vitrification Facility. Direct Feed High-Level Waste (DFHLW) is a potential approach to initiating HLW vitrification prior to completing of the WTP Pretreatment Facility. Settling would be used with subsequent supernatant decant to concentrate HLW feed. To support planning for DFHLW, Washington River Protection Solutions (WRPS) requested support from the Pacific Northwest National Laboratory to evaluate the current data set available to predict the time needed for HLW solids to settle, to identify gaps in the understanding and predictive capability of HLW solids waste settling times, and to provide scoping estimates of the potential settling time. Eight technical gaps were identified for predicting settling times and characteristics of the formed sediment layers including: Gap 1: In-Tank Settling Rates Faster than Settling of Laboratory Samples, Gap 2: Effect of Sludge Leaching/Washing on Predicted Settling Times, Gap 3: Predicting Waste Settling from Waste Chemistry (Waste Type), Gap 4: Predicting Waste Settling from Particle Size and Density Distributions (PSDDs), Gap 5: Insufficient Laboratory and In-Tank Settling Data to Represent Hanford Waste, Gap 6: Methods for Real-Time, In-Tank Tracking of Settling, Gap 7: Prediction of Sediment Erosion Resistance as a Function of Settling Time, and Gap 8: Prediction of Sediment Solids Content as a Function of Settling Time. In addition to the data gaps, an overarching observation of the settling rate and settled layer data is the significant variation in behavior. At similar solids concentrations, settling rates can vary by as much as 3 orders of magnitude depending on the source waste tank, and significantly different settling rates are noted between laboratory and in situ tests for the same waste tank. The range of average solids concentration in existing HLW sediment, which may have been quiescent for decades, can vary from less than 7 wt% to greater than 74 wt% solids. The shear strengths (or yield stresses) measured on laboratory samples range from less than 27 Pa to greater than 6400 Pa. These variations can challenge process planning for the application of a settle/decant process for DFHLW. This report describes the significance of the gaps to the settle/decant process and presents uncertainties by way of examples. Potential technical approaches for resolving these gaps are described and the estimated difficulty in resolving these gaps is evaluated. Based on the significance of the gap and the difficulty of resolution, recommendations are made to address specific gaps. Scoping estimates of the potential settling times for DFHLW solids have been made based on the existing data set with its associated gaps. Depending on the process vessel depth and final sediment concentration, substantial fractions of the scoping estimate results for settling times for characterized HLW exceed the 2-week period that has been previously assumed for process planning. There is also significant disparity, potentially greater than a factor of 5000 difference, in the estimated settling times depending on process vessel depth and final sediment solid concentration. This variation in results underscores the significance of the identified gaps and uncertainties with respect to process planning for utilizing settle/decant operations for DFHLW.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

WRPS Hanford Update [Slides]

The purpose of this report is to coordinate with the staff from WRPS, the current contract holder for operations at the Hanford site to better inform design decisions for the Autonomous systems for Hanford waste tank handling project. The project goals are to support risk reduction associated with monitoring, inspection and mapping of Hanford tank underground pits and includes: 1. A pit mock-up demonstration of Idaho National Laboratory’s (INL) Autonomous Pit Exploration System (APES) technology, which has two configurations: A. The Autonomous Robotic Arm, which is a proposed collaboration with Florida International University (FIU) and has capabilities to visually inspect, monitor, map and conduct simple tool manipulation tasks in the tank pits, and B. The robotic crawler configuration, which has capabilities to deploy to the bottom of the pits and conduct closer and bottom-up visual inspections. 2. An Implementation Plan that identifies Hanford site-wide application of the INL remote robotics technologies to enhance the performance of the tank farm systems and the characterization of the waste they contain to mitigate risk and optimize the overall waste mission. 3. A first-of-a-kind environmental digital twin will be produced. Digital twins to date require permanently installed sensors in order to produce asset specific predictions. This project will use the intermittent signals during inspections from deployed sensors on robotic systems to produce the data sets used by AI/ML to enable predictions of issues on tanks.

42 - ENGINEERING↗

Computationally-Aided Design of a Small-Scale Radioactive Waste Glass Melter

To provide mission support to the Hanford Waste Immobilization and Treatment Plant for the vitrification of legacy nuclear tank waste, a reduced-scale vitrification pilot system is being designed to process simulated and actual radioactive tank wastes. The tank waste will be separated into high-level waste (HLW) and low-activity waste (LAW) fractions, where the majority by mass (~90%) is LAW and by activity (>95%) is HLW. The first tank waste to be processed at the WTP will be LAW. Since Hanford tank waste and the resultant melter feed compositions are known to vary widely, pilot-scale operations are essential to identify potential problems, provide needed data, confirm assumptions, and determine impacts to full-scale melters and off-gas systems from these different feeds. In addition, the reduced-scale melter system must be capable of quickly providing results to operations without the typically high costs of radioactive operations and provide an engineering platform in close proximity to local operations staff. The objective is to produce similar process conditions to those encountered in the full-scale LAW melters and minimize the volume of radioactive waste necessary for the evaluations. To this end, melter design features are being explored to increase production without significantly increasing surface area, melter glass volumes or compromising data quality. In support of these objectives, a set of computational fluid dynamic models have been developed to provide insight into the flow patterns within these small melters and evaluate design features to increase production without significantly increasing glass inventory. Computed velocities were evaluated at the interface between the cold cap and the molten glass pool and within the bulk glass pool. A method was developed to correlate results to an estimated melt rate and down-select design features that produce the highest gains.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Computationally Aided Design of a Small-Scale Waste-Glass Melter - 20452

To provide mission support to the WTP for the vitrification of legacy nuclear tank waste at the Hanford site, a reduced-scale vitrification pilot system is being designed to process simulated and actual radioactive tank wastes. The waste stored in underground tanks will be separated into HLW and LAW fractions, where the majority is LAW by mass (approximately 90%) and HLW by activity (greater than 95%). The first tank waste to be processed at the WTP will be LAW. Because Hanford tank waste and the resultant melter feed compositions are known to vary widely, pilot-scale operations are essential to identify potential problems, provide needed data, confirm assumptions, and determine impacts to full-scale melters and off-gas systems from these different feeds. In addition, the reduced-scale melter system must be capable of quickly providing results to operations without the typically high cost of full-scale radioactive operations and to provide an engineering platform in close proximity to local operations staff. The objectives of this computational modeling effort are to produce process conditions like those encountered in the WTP LAW melters and to minimize the volume of radioactive waste necessary for the evaluations. To this end, melter design features are being explored to increase production without significantly increasing surface area or melter-glass volumes or compromising data quality. In support of these objectives, a set of computational fluid dynamic models was developed to provide insight into the flow patterns within these small melters and evaluate design features to increase production without significantly increasing glass inventory. Computed velocities were evaluated at the interface between the cold cap and the molten-glass pool and within the bulk-glass pool. Since melt rate correlates with the velocity underneath the cold cap, this information can be used to select design features that produce the highest gains. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Decade of Innovative Approaches to Treating and Dispositioning Radioactive Waste at the Savannah River Site - 20620

This year marks the 70. anniversary of the U.S. Department of Energy's (DOE) Savannah River Site (SRS), located near Aiken, South Carolina. SRS is a key industrial complex responsible for environmental stewardship, environmental cleanup, waste management, and disposition of nuclear materials. SRS also continues to have a role in critical defense-related activities and the reprocessing of used reactor fuel. The SRS encompasses 803 square kilometers (310 square miles) in parts of Aiken, Barnwell, and Allendale counties. The Liquid Waste Mission starts with the safe receipt and storage of radioactive liquid waste in the waste tanks, which principally includes Cold War legacy waste, but also waste from support of National Aeronautics Space Administration missions, medical isotope production, and research activities. This 133,000 cubic meters (m{sup 3}) (35 million gallons [Mgal]) of high-level radioactive waste (HLW) is currently held in 43 large underground waste tanks. The capacity of each of these tanks range from 2,800 m{sup 3} to 5,000 m{sup 3} (0.75 to 1.33 Mgal) and were placed in operation between 1954 and 1986. In July 2009, the DOE awarded a stand-alone contract to execute the Liquid Waste Mission at SRS. The Liquid Waste Contractor selected was Savannah River Remediation LLC1 (SRR), which is responsible for receipt, storage, retrieval and treatment of all HLW, disposal of the decontaminated low-activity waste fraction, as well as operationally closing cleaned HLW tanks. Since July 2009, SRR has successfully grouted and operationally closed six large underground tanks, poured 1,476 canisters of vitrified HLW (a stable glass waste form), treated approximately 34,200 m{sup 3} (9.0 Mgal) of HLW, and dispositioned over 41,200 m{sup 3} (10.9 Mgal) of decontaminated salt solution as low-level waste (LLW) into the Saltstone Disposal Units (SDUs) being constructed by SRR on site. The innovative work performed by SRR in the LLW portion of its mission has earned it the Richard S. Hodes Award. The work conducted by SRR is the same work championed by the late Richard S. Hodes, a respected physician, statesmen, and Chairman of the Southeast Compact Commission for Low-Level Radioactive Waste Management. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Determining Drying Conditions to Mitigate Hanford Transfer Line Corrosion

Hanford Site Background • Hanford site located in Washington State and established in 1943: 1460 km2 • Since 1988 the site has been engaged in a comprehensive environmental clean-up effort. Waste Tanks • 177 underground tanks with 56 million gallons of high-level radioactive waste and chemical waste in 150 Single Shell Tanks (SSTs) and 27 Double Shell Tanks (DSTs)

Shukla, Pavan K. [Savannah River National Laborato↗

Thermodynamic parametric analysis of refueling heavy-duty hydrogen fuel-cell electric vehicles

Reliable design and safe operation of heavy-duty hydrogen refueling stations are essential for the successful deployment of heavy-duty fuel cell electric vehicles (FCEVs). Fueling heavy-duty FCEVs is different from light-duty vehicles in terms of the dispensed hydrogen quantities and fueling rates, requiring tailored fueling station design for each vehicle class. In particular, the selection and design of the onboard hydrogen storage tank system and the fueling performance requirements influence the safe design of hydrogen fueling stations. A thermodynamic modeling and analysis are performed to evaluate the impact of various fueling parameters and boundary conditions on the fueling performance of heavy-duty FCEVs. Here, we studied the effect of dispenser pressure ramp rate and precooling temperature, initial tank temperature and pressure, ambient temperature, and onboard storage design parameters, such as onboard storage pipe diameter and length, on the fueling rate and final vehicle state-of-charge, while observing prescribed tank pressure and temperature safety limits. An important finding was the sensitivity of the temporal fueling rate profile and the final tank state of charge to the design factors impacting pressure drop between the dispenser and vehicle tank, including onboard storage pipe diameter selection, and flow coefficients of nozzle, valves, and fittings. The fueling rate profile impacts the design and cost of the hydrogen precooling unit upstream of the dispenser.

08 HYDROGEN↗

Hydrogen Mitigation Process Installation at Nevada Solar One

The National Renewable Energy Laboratory (NREL) and Acciona Solar Power (ASP) have developed and are implementing a process that addresses the issue of hydrogen buildup in parabolic trough power plants. Our method selectively removes hydrogen from the expansion tanks of the power plant to control hydrogen levels in the circulating heat-transfer fluid (HTF). During previous work, we developed a sensor that measures hydrogen partial pressure in the expansion-tank headspace gas. We demonstrated that our sensor measures hydrogen levels over a wide range of partial pressure—from 1.33 mbar down to 0.003 mbar. More recently, we conceived and developed an integrated process module that performs both hydrogen sensing and separating functions. The sensor/separator measures hydrogen partial pressure in the headspace gas in the same way as our original sensor design. Additionally, the integrated module separates hydrogen from the headspace gas to reduce hydrogen to the level needed to maintain the performance of receivers in the collector field. We demonstrated the performance of a laboratory-scale version of this module. Testing showed that the module performed as expected: the accuracy of the sensing function was ±7%, and the hydrogen extraction rate for the separating mode was consistent with our modeling predictions. The primary benefit of this module is its simple design, both in terms of function and incorporation into the HTF subsystem of the power plant. Most recently, NREL and ASP planned, specified, and designed a mitigation process that is based on the integrated module. We are currently completing installation of this process at ASP's Nevada Solar One power plant in Boulder City, Nevada, USA. The mitigation process is being installed at ground level below the HTF expansion tanks, where it draws headspace gas from the tanks, removes hydrogen, and returns the treated gas back to the tanks. In this paper, we report progress on the installation and describe some of the many design details and challenges that we addressed during the past year. We will generate initial performance data from the Nevada Solar One mitigation process in early 2020.

41 EE - Solar Energy Technologies Office (EE-4S)↗

Assessment of Methane Generation from the Thermolysis of Organics in Caustic Waste

Methane generation has been detected during thermolytic Hydrogen Generation Rate (HGR) testing of SRS tank waste and in simulant samples. Simulant testing has shown methane generation in the presence of trimethylsilanol (TMS) and radioactive sample testing has shown methane generation in presence of methylmercury, both of which are found within SRS waste tanks. The 2019 report Evaluation of the Current State of Knowledge for Thermolysis of Organics within SRS Waste Forming Volatile Organic Compounds (VOCs) reviewed historical data and assessed literature pertaining to thermolytic methane generation. That review recommended undertaking thermolysis studies on simulated waste to detect and quantify VOCs. The purpose of this assessment is to review chemistry and current knowledge of organics in SRS waste to recommend which organics in SRS waste tanks, if any, should be tested for thermolytic methane generation. An evaluation of observed methane generation rates has been performed to assess the implication for current CSTF controls. Based on the inputs used in this report, it was concluded that no methane generation data observed to date has challenged the existing 5% organic contribution to the Composite Lower Flammability Limit (CLFL) assumption in the CSTF tank farm at temperatures below 100 °C. Evidence shows that thermolytic pathways to methane generation become significant at temperatures >100 °C in caustic waste. Currently, the influences of thermolytic methane production on the flammability of vessels at >100 °C (e.g., evaporators) is unclear. It is recommended that testing should be undertaken using the HGR experimental approach for methane generation. The initial simulant testing should obtain quantitative methane generation rates at elevated temperatures for methylated siloxanes/silanes and methylmercury with the goal of determining the current mechanism for thermolytic methane generation seen in SRS tank waste. The results of this testing should then be compiled and analyzed to ascertain the risk of challenging the current projected organic contribution of 5% to the CLFL at elevated temperatures. Following this testing, an evaluation of possible flammable gas generation in the 2H and 3H Evaporators should be performed to assess the risk of methane generation at the high temperatures employed by the evaporators.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

FIU Project1: Chemical Process Alternatives for Radioactive Waste [Slides]

"The U.S. DOE Hanford Site has the largest number of high-level waste (HLW) storage tanks and the largest volume of HLW in the United States. The safe storage, retrieval, treatment, and disposal of approximately 53 million gallons of highly toxic, high-level radioactive waste stored in Hanford’s 177 underground tanks are a national priority. Retrieval and treatment of waste from these tanks pose a considerable challenge. Florida International University has been conducting research on several promising alternative processes and technologies that can be applied to address several technology gaps in the current waste retrieval and conditioning plans. Specifically, FIU has been involved in: the evaluation of non-metallic materials in the waste transfer system, evaluation of alternative HLW instrumentation for in-tank applications and the development of technologies to assist in the inspection of tank bottoms at Hanford."

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Spent Crystalline Silicotitanate Storage Study—Post AP-105DF Processing

A Tank-Side Cesium Removal (TSCR) system is under development by Washington River Protection Solutions to support initial production of immobilized low-activity waste (LAW) by feeding Hanford tank supernate from tank farms to the Hanford Waste Treatment and Immobilization Plant (WTP) LAW Facility. Tank waste supernate will be filtered to remove suspended solids and then Cs will be removed by processing it through crystalline silicotitanate (CST) ion exchange media manufactured by Honeywell UOP, LLC. The Cs-loaded CST columns will be stored indefinitely, with a goal of eventual CST removal and treatment. Thus, the spent CST needs to be recoverable after undetermined storage time. Previous testing with AP-105 simulant showed that rinsing the CST bed with 3 bed volumes (1.4 apparatus volumes [AVs]) of 0.1 M NaOH resulted in a dried bed that maintained flow characteristics indicative of ease of recovery. This study explored the intermediate conditions (between feed dried in place and the 1.4 AVs of 0.1 M NaOH rinse) to evaluate CST bed properties after: 1) stoppage with feed in place; 2) stoppage after draining feed; 3) stoppage after 0.7 AV of 0.1 M NaOH rinse through column; 4) stoppage after 1.5 AVs of 0.1 M NaOH rinse through column. Post processing, each column was heated at 50 °C for 19 days under pseudo-storage conditions to simulate the expected dried and stored CST bed conditions. Testing was conducted at the small scale (12-mL bed volume); actual, Cs-depleted, AP-105 tank waste was used as the feed. Post-dried CST bed physical properties (angle of repose and penetration depth) were measured to evaluate how CST moved and flowed. All process stop-conditions resulted in a solidified CST bed except for the final condition, 1.5 AVs of 0.1 M NaOH rinse. At this small scale, the three CST beds presented an issue for retrievability after the short storage period (19 days at 50 °C). The latter case confirmed the results from simulant testing. The testing was intended to provide a preliminary assessment of issues that may arise from desiccation of CST during storage with the indicated salt solutions in place. Since these were small-scale tests, the processing system did not scale to full scale conditions exactly; however, the tests did provide insight into the impact on the dried and stored CST bed after stopping processing at an earlier step (upset condition) than normal. These results indicate that if an upset condition occurs at TSCR, a dilute hydroxide rinse should be considered before the CST dries from internal heating.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗