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At least 469 records · Page 26

Real Time, In-line Monitoring of Hanford Tank Wastes - Year 1 Report

The team comprised of students, postdocs, early, mid and senior career scientists from Los Alamos National Laboratory, Savanah River National Laboratory, Georgia Tech and Florida International University, with the guidance of H2C, is developing a suite of in-line instruments for the Hanford high level waste (HLW) and low active waste (LAW) processes to provide near-real-time analysis of waste form physical properties and composition. The work builds on results from the recent DOE-ORP, EM Technology Development and other projects that demonstrated promise for the use of real-time in-line monitoring (RTIM) to measure chemical compositions of slurries of up to 20 weight % solids. The goal is for this instrument suite is to substantially reduce the need for sampling for process control. Sample waste, exposure associated with sample analysis, and the demand for an external laboratory facility would be greatly reduced. The throughput of waste treatment systems would be improved by elimination of the downtime caused by waiting for sample results. This translates into reduced process storage as process knowledge will be continuously updated in near-real-time. These breakthrough technologies would significantly reduce the life cycle cost and accelerate the schedule for the Hanford tank waste mission.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Direct Processing of Lithium Chloride Based Waste Salt in a Ceramic Waste Form

Ceramic waste form materials were fabricated with a LiCl based salt mixture to demonstrate the suitability of direct processing of waste salt from an all LiCl pyroprocessing flow sheet on the formation, microstructure, and durability of ceramic waste forms. Materials were successfully synthesized by using the simplified direct processing technique with salt loadings of 5, 7.5, and 10 wt% at the laboratory scale. Materials fabricated with LiCl based salt indicated full conversion of zeolite to sodalite occurred to form products with low open porosity. This indicates that the Na 2 O content of NBS4 glass is suitable for processing salt chemistries which do not contain NaCl. Generated sodalite was microencapsulated by the glass binder, halite occlusions were detected within sodalite domains at all salt loadings, and a Cs-rich phase believed to be Cs-pollucite was detected in the material made with the lowest salt loading (5 wt%). Salt inclusions were encapsulated within the binder glass at all loadings, and found to consist primarily of NaCl with Cs present. A small amount of salt was found at the surface of the wasteform made with the highest salt loading of 10 wt%, which may indicate an upper limit to the amount of salt that can be accommodated or incomplete mechanical mixing of the reagents. Durability testing by using the ASTM C1308 method indicated that initial rapid dissolution of exposed halite inclusion phases was directly correlated to salt loading. Wasteform degradation during all tests occurred primarily due to dissolution of the sodalite phase. Durability of the binder glass was found to increase as the waste salt loading increased. Results for the release of cations from the salt indicate the changes in wasteform durability and halite inclusion chemistry are strongly influenced by ion exchange phenomena between the salt and the glass. This appears to be the result of the relatively stronger affinity for the glass phase of Li, compared to that of other cations such as Na and Cs. The effects from cation exchange were diminished at lower salt loadings.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Panel Session 120: Roundtable: Waste Management - Energy Facilities Contractor Operating Group (EFCOG WM)

This Roundtable focused on the WM EFCOG working group as they met to discuss a variety of issues of importance to US DOE waste management operations. The purpose of the WM EFCOG is to seek out and promote the best management and operating practices, cost effective technologies and disposal options for all waste streams generated at US DOE facilities whether destined for US DOE or commercial facilities. Each site representative provided a radioactive waste management lessons learned briefing. Panelists with presentations: Savannah River Site (SRS) Solid Waste Program Update (Kerri Crawford); Idaho Clean-up Project Status (Frederick Hughes); West Valley Demonstration Project Update - EFCOG Waste Management Working Group (John Rendall); Key Project Challenges and Successes (Kalli Shupe); EFCOG WMWG Challenging Waste Subgroup Update (Tammy Monday); CH TRU Difficult Waste Stream Processing Challenges (Daniel Pancake); Argonne Building 350 Clean-up Success Using Effective Work Control (Daniel Dilday); Problematic Waste Streams on the Oak Ridge Reservation (John Wrapp)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Remote Handled Hot Cell Facility and Other Research Transuranic Waste (Debris)

This acceptable knowledge (AK) Summary Report has been prepared for the Central Characterization Program (CCP) for remote-handled (RH) transuranic (TRU) waste generated and managed by Sandia National Laboratories/New Mexico (SNL/NM) in Albuquerque, New Mexico. The waste described in this report was predominately generated in the SNL/NM Hot Cell Facility (HCF) during the removal and packaging of experimental material and decontamination operations in Building 6580 at Technical Area (TA)-V. The waste stream also includes a very small amount of waste (estimated at less than 1 gram of fuel similar to that used for research at the HCF) originating from classified research at TA-I. In addition, the waste also includes secondary waste termed by SNL/NM as process generated waste (PGW), created during repackaging operations for this waste at the Auxiliary Hot Cell Facility (AHCF). The waste has been stored at the Sandia Pulsed Reactor (SPR) Dense Pack Storage Facility within TA-V or the Manzano Bunkers located at Manzano Base within Kirtland Air Force Base. All of the waste is being repackaged at the AHCF. This report was prepared in accordance with CCP-TP-005, CCP Acceptable Knowledge Documentation (Reference 1), to implement the AK requirements of DOE/WIPP-02-3214, Remote-Handled TRU Waste Characterization Program Implementation Plan (WCPIP) (Reference 2); Waste Isolation Pilot Plant Hazardous Waste Facility Permit, Waste Analysis Plan (WIPP-WAP) (Reference 3); and DOE/WIPP-02-3122, Transuranic Waste Acceptance Criteria for the Waste Isolation Pilot Plant (WIPP-WAC) (Reference 4).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Nuclear Safety [Vol. 37, No. 2, April-June 1996]

Nuclear Safety is a journal that covers significant issues in the field of nuclear safety. Its primary scope is safety in the design, construction, operation, and decommissioning of nuclear power reactors worldwide and the research and analysis activities that promote this goal, but it also encompasses the safety aspects of the entire nuclear fuel cycle, including fuel fabrication, spent-fuel processing and handling, and nuclear waste disposal, the handling of fissionable materials and radioisotopes, and the environmental effects of all these activities. Table of Contents for this issue follows. GENERAL SAFETY CONSIDERATIONS: 97 The Nuclear Community and the Public: Cognitive and Cultural Influences on Thinking About Nuclear Risk, M. A. Meyer; 109 Twenty-Third Water Reactor Safety Information Meeting, D. A. Copinger; ACCIDENT ANALYSIS: 126 Analysis of a PWR LBLOCA Without SCRAM, Trevor N. Tyler, Rafael Macian-Juan and John H. Mahaffy; DESIGN FEATURES: 139 Vulnerability of Multiple-Barrier Systems, N. C. Lind; ENVIRONMENTAL EFFECTS: 149 A Study of Wet Catalytic Oxidation of Radioactive Spent Ion Exchange Resin by Hydrogen Peroxide, Xingchao Jian, Tianbao Wu, and Guichun Yun; 157 A Comparison Study and Resolution of Differences Between Emergency Response and Safety Analysis Codes Used at the Savannah River Site, A. A. Simpkins; OPERATING EXPERIENCES: 164 Reactor Shutdown Experience, Compiled by J. W. Cletcher; RECENT DEVELOPMENTS: 167 Reports, Standards, and Safety Guides, D. S. Queener; 172 Proposed Rule Changes as of Dec. 31,1995; ANNOUNCEMENTS: 178 American Nuclear Society 1997 Annual Meeting; 178 American Nuclear Society Nuclear Criticality and Safety Division Topical Meeting; 176 The Authors.

05 NUCLEAR FUELS↗

Technologies for ECLSS Evolution

Viewgraphs and discussion on technologies for Environmental Control and Life Support System (ECLSS) evolution are presented. Topics covered include: atmosphere revitalization including CO2 removal, CO2 reduction, O2 generation, and trace contaminant control; water recovery and management including urine processing, hygiene water processing, and potable water processing; and waste management. ECLSS technology schematics, process diagrams, and fluid interfaces are included.

Diamant, Bryce L.↗

Advanced collapsible tank for liquid containment

Tanks for bulk liquid containment will be required to support advanced planetary exploration programs. Potential applications include storage of potable, process, and waste water, and fuels and process chemicals. The launch mass and volume penalties inherent in rigid tanks suggest that collapsible tanks may be more efficient. Collapsible tanks are made of lightweight flexible material and can be folded compactly for storage and transport. Although collapsible tanks for terrestrial use are widely available, a new design was developed that has significantly less mass and bulk than existing models. Modelled after the shape of a sessible drop, this design features a dual membrane with a nearly uniform stress distribution and a low surface-to-volume ratio. It can be adapted to store a variety of liquids in nearly any environment with constant acceleration field. Three models of 10L, 50L, and 378L capacity have been constructed and tested. The 378L (100 gallon) model weighed less than 10 percent of a commercially available collapsible tank of equivalent capacity, and required less than 20 percent of the storage space when folded for transport.

Flanagan, David T.↗

Processes in Salt Repositories for Radioactive Waste Disposal

This document summarizes the key processes (thermal, hydrological, mechanical, and chemical; THMC) impacting the features of a deep geological repository for radioactive waste in salt. Some processes are natural and on-going whether the repository is there or not, and other processes are driven by the perturbation associated with the repository. The features considered here include both engineered and natural components of the repository system. The engineered barrier system (EBS) in a salt repository is quite different from those implemented for a repository in clay or crystalline rocks, because it is comprised mostly of granular salt and salt-compatible cements, rather than bentonite. When compared to other rocks (i.e., silicates), salt has unique properties that make it an excellent potential host rock. Openings and fractures in salt creep closed readily. Salt has high thermal conductivity, which can reduce peak temperatures. Additionally, far away from the excavations the porosity of salt is unconnected, which leads to essentially zero advective or diffusive transport. The small amount of hypersaline brine occurring in salt minimizes microbial activity, reduces colloid-assisted transport, and eliminates in-package criticality (i.e., chloride is a neutron poison). At the end of the report, we present a brief outline for a potential salt repository, including considerations avoided in previous repository disposal concepts. We propose considering higher-temperature processes in future disposal concepts, rather than trying to minimize the thermal perturbation of the repository. Since hot salt is drier, a dry repository would limit corrosion, gas generation, and solute transport. Openings and fractures creep shut faster in hot salt. Therefore, higher temperatures could be seen as beneficial, rather than something to minimize, through increased spacing between waste packages (increasing repository costs).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Strontium Speciation in Relevant Tank Waste Components Examined by Electrospray Ionization Mass Spectrometry

The identification of chemical species formed in complex nuclear waste is crucial for the development and employment of advanced separations technologies to remediate the Hanford site by processing tank waste. The current Tank Side Cesium Removal (TSCR) process deployed at Hanford utilizes crystalline silicotitanate (CST) ion exchange (IX) media to aid in the separation of low-activity waste for proper treatment and disposal. The inorganic IX media is highly selective for Cs but has been shown to also remove Sr from caustic simulants and small-scale IX processing of Hanford tank waste.(Fiskum, Rovira et al. 2019, Fiskum, Campbell et al. 2021, Westesen, Campbell et al. 2022) Quantitative Sr removal has not been observed in all tank waste supernates tested; thus, to better understand Sr removal and effectively predict processing behavior through TSCR, it is necessary to first investigate Sr speciation in tank waste. This work utilized electrospray ionization mass spectrometry (ESI-MS) to identify ionic Sr complexes that form in the presence of NO 3 –, NO 2 –, OH–, and Cl–. Although our results show that NO 3 –, NO 2 –, and OH– are competitive for Sr 2+ binding, previous data from IX studies indicate that [SrOH] + is not the dominant species of concern in tank waste processing schemes.(Fiskum, Campbell and Trang-Le 2020) Our results show that the [Sr(NO3)]+ species and the [Sr(NO2)] + species form in considerable abundances, which may affect the ability to separate Sr using CST in nuclear waste separation processes.

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Overview of Upcoming Process Improvement Efforts at the Saltstone Facilities at the Savannah River Site - 20474

The Saltstone Facilities at the Savannah River Site (SRS) process and dispose of low activity salt solution waste generated by other liquid waste facilities. Today in the Liquid Waste System (LWS), approximately 125 million liters of salt waste remain to be processed. The Saltstone Production Facility (SPF) receives the decontaminated salt waste, which is mixed with dry feeds consisting of cement, fly ash and slag to produce the saltstone. The mixed slurry is pumped to the Saltstone Disposal Units (SDUs) for safe disposal in the Saltstone Disposal Facility (SDF). To support continuous Salt Waste Processing Facility (SWPF) operations at annual processing volumes many times higher than present, significant modifications are required to ensure that the SPF has the capacity to support the throughput of salt waste. These changes include several infrastructure upgrades that are being worked through the Enhanced Low Activity Waste Disposal (ELAWD) project. In addition to infrastructure upgrades, Savannah River Remediation (SRR), the Savannah River Site's Liquid Waste Contractor for the U.S. Department of Energy, has identified a flowsheet improvement opportunity of implementing a cement-free saltstone formulation to eliminate cement from the current three component formulation. This two-component formulation would simplify the procurement, transport, off-loading, and storage of the premix materials, and increase the storage capacity for the individual components. This flowsheet, when implemented, will reduce operational risk and improve throughput necessary to achieve disposal rates necessary for SWPF operations. Research has been completed to confirm the feasibility of this formulation, with the new cement-free flowsheet expected to be implemented in the next few years. Improvements have also been identified downstream of the SPF to increase SDU utilization. Specifically, a concentrated effort has taken place to raise the fill height in SDU 6 to the full disposal height, 13 meters, to maximize the usage of each SDU in support of the liquid waste disposal mission. This improvement has been made through additional thermal modeling and improved process understanding to create a SDU flammability model and control strategy more representative of facility operations. This work will allow for the completion of construction and operational readiness for SDU 7 while filling SDU 6 to ensure there is no lapse in available space once SWPF starts up. A summary of these improvements as they relate to increased throughput will be provided along with associated status. (authors)

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Identification and Quantification of Technetium Species in Hanford Waste Tank AN-102

Technetium-99 (Tc) generated from the fission of 235U and 239Pu in high yields is one of the most difficult contaminants to be addressed at the U.S. Department of Energy Hanford Site. In strongly alkaline solutions typifying Hanford tank waste, Tc exists as pertechnetate (TcO4-) (oxidation state VII) as well as in reduced forms (oxidation state < VII) collectively known as non-pertechnetate species. Designing strategies for effective Tc management, including separation and immobilization, necessitates understanding the molecular structure of the non- pertechnetate species and their identification in the actual tank waste samples, which would facilitate development of new treatment technologies effective for dissimilar Tc species. Toward this objective, a spectroscopic library of the Tc(I) [fac-Tc(CO)3]+ and Tc(IV, VII) compounds was generated using a range of techniques and applied to the characterization of the actual tank waste supernatant collected from the tank 241-AN-102 at Hanford, WA. A sample of the 241-AN-102 tank waste supernatant was processed to adjust Na concentration to about 5.6 M and remove 137Cs by spherical resorcinol-formaldehyde (sRF) ion exchange resin. Cesium-loaded sRF column was eluted with 0.5 M HNO3. As received AN-102, Cs-depleted AN-102 effluent, and sRF eluate fractions were comprehensively characterized for chemical composition and speciation of Tc using 99Tc nuclear magnetic resonance spectroscopy and X-ray absorption spectroscopy. It was demonstrated for the first time that non-pertechnetate Tc present in the 241-AN-102 tank waste is composed of several low-valent Tc species, including the Tc(I) [fac-Tc(CO)3]+ and Tc(IV) compounds. This is the second experimental observation of the [fac-Tc(CO)3]+ species in the Hanford tank waste and the first demonstration of multiple forms of non-pertechnetate species existing simultaneously in the waste, cumulatively highlighting their importance for the waste processing.

Low Activity Waste (LAW), High Level Waste, nuclea↗

Glass formulation and lab-scale testing of glasses designed for in-can Melter and in-container Vitrification of high-assay low-enriched uranium aqueous polishing Raffinate waste

Glasses were designed for processing a nuclear waste from aqueous polishing of high-assay low-enriched uranium using either In-Can Melter (ICM) or GeoMelt® In-Container Vitrification™ (ICV) technologies, which operate at temperatures of T p ≤ 1100 °C and T p ≤ 1450 °C, respectively. Due to the different operating conditions, the melt and glass properties were optimized differently for each technology. Each glass was designed to optimize for maximum waste loading while simultaneously satisfying processing (e.g., crystallization, viscosity, and conductivity) and product quality (e.g., durability, hazard characteristic, and crystal content) constraints. Here, the raffinate waste contains high nitric acid (4 M) and low total solids (9 g·L -1 ) concentrations. Feed preparation processes were tested to facilitate concentration and nitrate destruction/removal while controlling redox of the melter feed. A successful feed process including sugar addition and spray-drying was performed to generate an adequate melter feed for ICV processing.

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Chapter 6: Recycling Plastic Waste to Produce Chemicals - A Techno-Economic Analysis and Life-Cycle Assessment

This study presents the results of a preliminary assessment on the technology, economics, and sustainability of using waste plastics as a feedstock to produce low molecular weight olefins via pyrolysis and gasification pathways. We also studied the formation of formaldehyde - an important polymer precursor - via the gasification of waste plastics. Process pathways for recovery of ethylene and propylene and production of formaldehyde from a simulated mixed plastic waste were constructed based on literature data. They included direct and indirect pathways based on either gasification or pyrolysis as the primary conversion step. Results of these studies have shown that significant economic challenges exist of producing olefins via pyrolysis and gasification, with the latter pathway especially difficult. Base costs of pyrolysis naphtha from waste plastics are higher when compared to the same material produced from fossil feedstocks. Base olefin costs for one direct route are two times higher than comparable costs from steam cracking of fossil naphtha. These costs are driven primarily by feedstock costs; some pyrolysis scenarios become more economically feasible when very low feedstock costs are used. Similarly, for gasification, the cost of methanol - the central intermediate - was found to be noticeable higher when produced by gasification of waste plastics compared to current selling prices, which negatively impacts all pathways that go through methanol as the central intermediate. Life-cycle assessment indicates that the production of pyrolysis naphtha from plastics is a carbon intensive operation; no major advantages were found in terms of greenhouse gas emissions for any of the pathways producing C2 and C3 olefins. The results of this study can serve as the baseline for future comparison to other plastic waste valorization processes.

BIOMASS FUELS,ENERGY PLANNING, POLICY, AND ECONOMY↗

Process Feasibility Analysis of Waste Biomass Valorization to Biochar and Bio-Oil via Slow and Fast Pyrolysis

The United States has abundant biomass and waste feedstock to support the nation's energy addition and affordability targets. Pyrolysis, a thermochemical conversion process, decomposes lignocellulosic feedstocks into liquid, solid, and gaseous fuels that can contribute to the domestic production of biofuels, biopower, and bioproducts. Growing private sector interest in this technology is a key motivation for this comprehensive techno-economic process modeling analysis of a respective biorefinery that includes feedstock preprocessing, slow and fast pyrolysis, and product separation to bio-oil, biochar, and syngas hydrocarbons. Results show that biochar from slow pyrolysis could achieve minimum selling prices (MSPs) of $\$$188-$\$$260/t, competitive with reported market values, while bio-oil from fast pyrolysis is estimated to yield MSPs of $\$$6.49-$\$$9.68/GGE, approximately twice conventional fuel benchmarks. Sensitivity analysis identifies feedstock cost, product yield, and scale as primary cost drivers, while scenarios involving biochar carbon credits and high value applications may substantially improve economics. Overall, these results suggest that continued innovation in feedstock logistics, process integration, and market development will be critical to achieving economically viable and scalable bioproducts.

09 BIOMASS FUELS↗

Process Scale-Up of an Energy-Efficient Membrane Solvent Extraction Process for Rare Earth Recycling from Electronic Wastes

This study reports the process scale-up and long-term performance of an energy-efficient and cost-effective membrane solvent extraction (MSX) process for separation and recovery of high purity rare earth oxides (REOs) from scrap permanent magnets (SPMs). Here, the rare earth elements (REEs), including dysprosium, neodymium, and praseodymium, are recovered from SPMs using a neutral extractant, tetraoctyl diglycolamide (TODGA) embedded in a microporous polypropylene hollow fiber membrane module. The MSX process performance is demonstrated with bench scale module with membrane surface area of 1.4 m 2 to industrial scale modules with membrane surface area of up to 20 m2 to enable the processing of up to 1 ton month –1 of SPMs. The purity and the yield of the recovered REOs are >99.5 wt% and >95%, respectively. The average extraction rate of REOs is >10 g m –2 hr –1 . A skid of MSX system is assembled with a membrane area of 40 m 2 . The MSX skid successfully recovers REOs with a capacity of 300 kg REOs/month. Finally, it is determined that the organic phase containing the extractant maintains its performance up to 250 h. The results suggest that the MSX process is an economically viable and environmentally friendly process for separation and recovery of REOs from electronic wastes.

36 MATERIALS SCIENCE↗

Waste Management Options for Long-Duration Space Missions: When to Reject, Reuse, or Recycle

The amount of waste generated on long-duration space missions away from Earth orbit creates the daunting challenge of how to manage the waste through reuse, rejection, or recycle. The option to merely dispose of the solid waste through an airlock to space was studied for both Earth-moon libration point missions and crewed Mars missions. Although the unique dynamic characteristics of an orbit around L2 might allow some discarded waste to intersect the lunar surface before re-impacting the spacecraft, the large amount of waste needed to be managed and potential hazards associated with volatiles recondensing on the spacecraft surfaces make this option problematic. A second option evaluated is to process the waste into useful gases to be either vented to space or used in various propulsion systems. These propellants could then be used to provide the yearly station-keeping needs at an L2 orbit, or if processed into oxygen and methane propellants, could be used to augment science exploration by enabling lunar mini landers to the far side of the moon.

Space processing↗