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At least 127 records · Page 7

Analysis of Defense Waste Processing Facility Sample: Recycle Collection Tank Sample Batch 4945

The Savannah River National Laboratory (SRNL) was requested by Savannah River Remediation (now Savannah River Mission Completion (SRMC)), through a Technical Task Request, to characterization the “as-received” Recycle Collection Tank (RCT) Sample identified as sample batch 4945 [Sludge Receipt and Adjustment Tank (SRAT) batch 796)], which was delivered to SRNL Shielded Cells on January 28, 2021. The RCT characterization data will be used as input to the Defense Waste Processing Facility (DWPF) Recycle Diversion Project. This RCT report is the first of three sample characterization reports that will be used for this DWPF Project. The other DWPF reports will involve the characterization of the Off-Gas Condensate Tank (OGCT) and the Slurry Mix Evaporator Condensate Tank (SMECT) samples.

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Physical Properties of the Salt Waste Processing Next Generation Solvent Formulation

In 2020, a review team examined the risks associated with the implementation of a new solvent formulation, similar to what was used in Modular Caustic-Side Solvent Extraction Unit (MCU). The team identified a number of risks associated with the change and pathways to mitigate some of the risks. SRNL has been tasked with examination and testing of a Salt Waste Processing Facility (SWPF) formulation for a Next Generation Solvent (NGS) intended for use at that facility. This formulation is known as the “$NGS\tiny{OPTIMUM}$”. This formulation consists of: 50 mM MAXCalix; 3 mM TiDG•HCl; 0.65 M Modifier; Remainder Isopar-L™. SRNL examined several physical aspects of this solvent in order to confirm its suitability for use at SWPF, such as viscosity, dispersion, surface tension, and third phase formation. Results indicate no unusual properties of this solvent when compared to the current “BOBCalix” solvent in use at SWPF.

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Investigation of Undissolved Solids from Salt Waste Processing Facility (SWPF) Salt Batches Collected via Filtration

SRNL researchers performed six experiments wherein 0.1 μm-grade stainless steel filters were used to filter samples pulled from salt batches 6, 9B, and 11B, without the addition of monosodium titanate. Three of these experiments were performed to collect filterable solids from each salt batch and characterize trapped solids via scanning electron microscopy. The remaining three experiments were performed to collect and then dissolve the same solids using 3.5 M nitric acid (similar to that employed in the Salt Waste Processing Facility) for characterization via Inductively-coupled plasma atomic emission spectroscopy.

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Analysis of NuCycle® Process Waste Streams and Identification of Candidate Waste Forms (CRADA 719) Abstract

The objective of this project is to support collaboration between PNNL and Curio to address technical gaps in the immobilization of waste streams generated by the NuCycle® process, thereby improving the overall viability of the technology. This work will be carried out in two phases, described below. Phase 1 – Waste Management Study The first phase consists of a comprehensive waste management study focused on the waste streams produced during the NuCycle® process, including those containing long lived fission products (LLFPs, e.g., I 129) and transuranic elements (TRUs). This phase involves compiling waste compositions and characteristics based on recently completed NuCycle® testing and modeling efforts. Established waste forms and processing methods will be identified for streams where they are applicable.

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Evaluation of Material Balance Approaches for Hanford Direct-Feed Low Activity Waste Processing - 20022

The Hanford Site has accumulated millions of gallons of tank waste from reprocessing spent fuel to recover plutonium, uranium, cesium, and strontium. The supernatant from the accumulated tank waste will be treated using a Direct Feed Low-Activity Waste approach. The supernatant will be treated to remove solids and cesium in the Tank-Side Cesium Removal process in the Hanford tank farm, then vitrified in a semi-batch process in the Hanford Waste Treatment and Immobilization Plant (WTP). Currently, each batch of feed is sampled at three locations prior to being fed to the melter: the feed qualification tank in the Hanford tank farm as well as the concentrate receipt vessel (CRV) and melter feed preparation vessel (MFPV) in the WTP. The feed qualification sample is taken from a large batch of accumulated feed, only two to three samples are expected each year. Approximately 275 samples from the CRVs and 1100 samples from the MFPV are expected each year. An evaluation was performed to determine if a material balance based on the feed qualification sample could replace most of the sampling in the CRVs and MFPVs. The evaluation consisted of three elements: (1) determination of the practicality of using a material balance to estimate the stream composition of the CRV and MFPV contents, (2) evaluation of whether the material balance could be automated using the existing process control system, and (3) determination of the uncertainty in glass composition using the material balance approach. It is assumed that periodic sampling at the CRV and MFPV would be performed periodically to re-baseline the material balance, evaluations are in progress to determine the frequency of this periodic sampling. Process sample locations downstream of the melter were reviewed as well, but the partitioning of semi-volatile species in the melter was determined to preclude extending the material balance approach past the melter. It was determined that replacement of the CRV sample location was feasible and did not increase process uncertainty or significantly impact waste loading. Replacement of the MFPV sample was also determined to be feasible, but that measurement of the glass former chemical addition may be needed prior to addition of these chemicals to the MFPV. This measurement could be performed by an in situ laser-induced breakdown spectroscopy (LIBS) system. Limited tests were performed to evaluate LIBS for direct measurements of the low-activity waste melter feed. The use of a material balance would eliminate over 1200 samples each year if only 10% of the CRV and MFPV batches are sampled and could likely allow the WTP laboratory to operate on days only versus 24/7 operation. (authors)

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Development and testing of a wet oxidation waste processing system

The wet oxidation process is considered as a potential treatment method for wastes aboard manned spacecraft for these reasons: (1) Fecal and urine wastes are processed to sterile water and CO2 gas. However, the water requires post-treatment to remove salts and odor; (2) the residual ash is negligible in quantity, sterile and easily collected; and (3) the product CO2 gas can be processed through a reduction step to aid in material balance if needed. Reaction of waste materials with oxygen at elevated temperature and pressure also produces some nitrous oxide, as well as trace amounts of a few other gases.

Weitzmann, A. L.↗

New Tank Mapping Method Improves Waste Removal Process

Waste Tank Mapping Overview • Camera inspections are performed within available tank top risers and used to create waste tank maps – Several camera inspections are performed during waste removal transfers to verify the elevation of the visible salt/sludge mounds against the known elevation of the liquid surface • Tank mappings are used to evaluate the volume and distribution of saltcake or sludge that is present within the waste tank – Allows for refined operating strategies and process safety controls • New tank mapping process creates a standardized approach for accurately defining waste distribution within a waste tank while minimizing the required camera inspection footage – First utilized during the 2023 Tank 22 Sludge Removal Campaign

Mini, Melany [Savannah River Mission Completion (S↗

Implementation of Glycolic Acid Flowsheet in the Defense Waste Processing Facility (DWPF) - 17348

The disposition of high level waste (HLW) into canistered waste forms began at Savannah River Site (SRS) in 1996. For its entire processing history, DWPF has added formic acid as a pretreatment step in producing acceptable melter feed from incoming waste sludges sent from the HLW Tank Farms. While this process has been used to successfully produce more than 4,000 radioactive canisters, the addition of formic acid and its tendency to catalytically decompose in the presence of trace quantities of noble metals adds substantial process complexity in order to safely accommodate hydrogen generation and pH shifting during batch operations. Research efforts have been in progress for several years to identify a chemical surrogate for formic acid which performs the essential process functions without the associated negative consequences. The final analytical work to demonstrate the effectiveness of glycolic acid in the DWPF is nearly complete and a project team has been created to safely integrate the new acid into the chemical process. The project team is currently executing an implementation schedule which addresses safety basis development, revision to operations procedures and training, facility modifications, chemical procurement, and updated process monitoring. Introduction of glycolic acid into DWPF is currently scheduled to take place in early 2017, beginning with a blended flowsheet of glycolic and formic acid and ultimately transitioning to glycolic-only processing. This paper provides an overview of planned glycolic acid flowsheet implementation in the DWPF. This paper discusses several issues related to implementing such a significant change to the chemical process including: 1) Process chemistry differences between the two flowsheets with quantitative comparison for several properties of interest; 2) Technical approach to hazards analysis and safety basis development strategy; 3) Status of project execution for major deliverables; and 4) Path forward for facility modifications related to legacy formic acid support equipment. (authors)

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Permanganate Oxidation of Defense Waste Processing Facility (DWPF) Recycle Collection Tank (RCT) Simulants Larger Scale Protocol Runs - Chemical Process Cell (CPC) Nominal and Foamover Conditions

Testing to develop a process to oxidize glycolate and other organic species in non-radioactive waste simulants was requested by Savannah River Remediation (SRR). A Task Technical and Quality Assurance Plan (TTQAP) was written to describe the testing requested by SRR in the development of a process to oxidize glycolate and other organic species that are responsible for hydrogen generation from thermolysis. Scoping studies have been completed as requested by a Technical Assistance Request (TAR) to evaluate the feasibility of using sodium permanganate and Fenton's Reagent (iron catalyzed hydrogen peroxide) for destroying glycolate. The results from these scoping studies were summarized in a report. Six phases of tests with simulants have been planned in developing an oxidation flowsheet for the Recycle Collection Tank (RCT), as shown in Table 1. The first three phases have been completed. The first phase comprised of scoping tests of permanganate and Fenton's reagent. The second phase was a matrix of 23 tests completed to inform a down-select decision by SRR and to complete testing needed to understand the influence of various factors in defining the optimum processing conditions for oxidation of organics. From the results of this testing, oxidation by permanganate was chosen over Fenton's reagent with hydrogen peroxide. The third phase of testing was to demonstrate nominal operation of the permanganate oxidation process under protocols similar to those used in the Defense Waste Processing Facility (DWPF).

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Evaluating the feasibility of biological waste processing for long term space missions

Recycling waste products during orbital (e.g., International Space Station) and planetary missions (e.g., lunar base, Mars transit mission, Martian base) will reduce storage and resupply costs. Wastes streams on the space station will include human hygiene water, urine, faeces, and trash. Longer term missions will contain human waste and inedible plant material from plant growth systems used for atmospheric regeneration, food production, and water recycling. The feasibility of biological and physical-chemical waste recycling is being investigated as part of National Aeronautics and Space Administration's (NASA) Advanced Life Support (ALS) Program. In-vessel composting has lower manpower requirements, lower water and volume requirements, and greater potential for sanitization of human waste compared to alternative bioreactor designs such as continuously stirred tank reactors (CSTR). Residual solids from the process (i.e. compost) could be used a biological air filter, a plant nutrient source, and a carbon sink. Potential in-vessel composting designs for both near- and long-term space missions are presented and discussed with respect to the unique aspects of space-based systems.

NASA Discipline Life Support Systems↗

Water recovery and solid waste processing for aerospace and domestic applications

The work is described accomplished in compiling information needed to establish the current water supply and waste water processing requirements for dwellings, and for developing a preliminary design for a waste water to potable water management system. Data generated was used in formulation of design criteria for the preliminary design of the waste water to potable water recycling system. The system as defined was sized for a group of 500 dwelling units. Study tasks summarized include: water consumption, nature of domestic water, consumer appliances for low water consumption, water quality monitoring, baseline concept, and current and projected costs.

Murawczyk, C.↗

Development and Testing of a High Level Waste Slurry Sampling Technique to Support Hanford Waste Processing - 17164

The Hanford Tank Operations Contractor must demonstrate the capability to adequately sample staged high-level waste feed. The sampler employed must have accuracy and precision performance that allow the Tank Operations Contractor (TOC) to meet the Waste Treatment and Immobilization Plant (WTP) Waste Acceptance Criteria Data Quality Objectives (DQO). A full-scale sampling loop was used at a test facility to develop and demonstrate sampler capability. This paper will discuss the modifications to a sampler configuration previously tested - modifications focused on the improvement of the accuracy of test results. This work targets one of the remaining technical issues with the high-level waste treatment mission at Hanford. The sampling method employed must support both Tank Operations and Waste Treatment and Immobilization Plant requirements. To facilitate information transfer between the two facilities the mixing and sampling demonstrations are led by the TOC's Chief Technology Office in conjunction with the One System Integrated Project Team. Results of the testing showed that performance of the Isolok{sup R} sampler, chosen for implementation, can be greatly improved by modifying the systems configuration to provide accurate, repeatable results for Hanford's simulated high level waste. (authors)

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Solid Waste Processing: An Essential Technology for the Early Phases of Mars Exploration and Colonization

Terraforming of Mars is the long-term goal of colonization of Mars. However, this process is likely to be a very slow process and conservative estimates involving a synergic, technocentric approach estimate that it may take around 10,000 years before the planet can be parallel to that of Earth and where humans can live in open systems. Hence, any early missions will require the presence of a closed life support system where all wastes, both solids and liquids, will need to be recycled or where all consumables will need to be supplied. The economics of both are often a matter of speculation and conjecture, but some attempt is made here to evaluate the choice. If a choice is made to completely resupply and eject the waste mass, a number of unknown issues are at hand. On the other hand, processing of the wastes, will enable predictability and reliability of the ecosystem. Solid wastes though smaller in volume and mass than the liquid wastes contains more than 90% of the essential elements required by humans and plants. Further, if left unprocessed they present a serious risk to human health. This paper presents the use of well established technology in processing solid wastes, ensuring that the biogeochemical cycles of ecosystems are maintained, reliability of the closed life support system maintained and the establishment of the early processes necessary for the permanent presence of humans on Mars.

Wignarajah, Kanapathipillai↗

Adapting Waste Processing for Space Applications

It has been estimated that on a 1-year mission, a four-astronaut crew will produce approximately 2,600 kg of waste materials. The current International Space Station practice for waste management is a stow and jettison model in which the trash is simply ejected. The immediate challenge waste poses for long duration space flight is that it represents unproductive mass. Longer term, waste accumulation on planetary surfaces will also pose challenges. A waste management/disposal solution is greatly needed. Simultaneously, significant research and development efforts are being made to enable in-situ resource extraction and recovery for lunar and Mars surface operations. A waste management solution could free up volume, reduce mass and thereby propellant needs, as well as contribute to resource recovery for spacecraft, and eventually, surface operations. The adaptation of many chemical engineering unit operations to the microgravity environment is critical to achieve this goal. An ideal spacecraft waste treatment system would convert waste into useful gases. It should be largely self-sustaining in that it should have the ability to recycle commodities to avoid imposing mass penalties associated with transporting feedstock on the spacecraft at launch. At NASA KSC, a model of what such a system would look like is being developed. In addition, the team has recently completed a suborbital flight campaign with a combustion reactor to demonstrate rudimentary conversion in a microgravity environment and identify challenges for future design. This presentation will discuss what a full waste treatment system could look like, point out challenges relating to various unit operations involved in such a system, and highlight recent progress in space waste management research and development.

Waste Processing↗

Nitric-glycolic flowsheet reduction/oxidation (redox) model for the defense waste processing facility (DWPF)

Control of the REDuction/OXidation (REDOX) state of glasses containing high concentrations of transition metals, such as High Level Waste (HLW) glasses, is critical in order to eliminate processing difficulties caused by overly reduced or overly oxidized melts. Operation of a HLW melter at Fe +2 /ΣFe ratios of between 0.09 and 0.33, retains radionuclides in the melt and thus the final glass. Specifically, long-lived radioactive 99 Tc species are less volatile in the reduced Tc 4+ state as TcO 2 than as NaTcO 4 or Tc 2 O 7 , and ruthenium radionuclides in the reduced Ru 4+ state are insoluble RuO 2 in the melt which are not as volatile as NaRuO 4 where the Ru is in the +7 oxidation state. Similarly, hazardous volatile Cr 6+ occurs in oxidized melt pools as Na 2 CrO 4 or Na 2 Cr 2 O 7 , while the Cr +3 state is less volatile and remains in the melt as NaCrO 2 or precipitates as chrome rich spinels. The melter REDOX control balances the oxidants and reductants from the feed and from processing additives such as antifoam.

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Predictive modeling of crystal accumulation in high-level waste glass melters processing radioactive waste

The effectiveness of HLW vitrification is limited by precipitation/accumulation of spinel crystals [(Fe, Ni, Mn, Zn)(Fe, Cr)2O4] in the glass discharge riser of Joule-heated ceramic melters during idling. These crystals do not affect glass durability; however, if accumulated in thick layer, they can clog the melter and prevent discharge of molten glass into canisters. To address this problem, an empirical model was developed that can predict thicknesses of accumulated layers as a function of glass composition. This model predicts well the accumulation of single crystals and/or small-scale agglomerates, but, excessive agglomeration observed in high-Ni-Fe glass resulted in an under-prediction of accumulated layers, which gradually worsen over time as an increased number of agglomerates formed. Accumulation rate of ~53.8 ± 3.7 µm/h determined for this glass will result in ~26 mm thick layer in 20 days of melter idling.

Crystal accumulation↗

Trisodium Phosphate Phases and Solubility in Alkaline Solutions Relevant to Radioactive Waste Processing

The U.S. Department of Energy’s Hanford Site faces significant challenges in managing millions of gallons of legacy radioactive waste, where phosphate precipitation can obstruct pipelines during retrieval and processing. To resolve long-standing inconsistencies in reported solubility and clarify factors governing trisodium phosphate hydrates, we examined the Na3PO4:NaOH:H2O system. Powder and single-crystal X-ray diffraction revealed that commercial precursors undergo transformations that produce multiple hydrates, including three previously unreported phases comprising an ordered polymorph of Na3(PO4)·12H2O·1/6NaOH, Na3PO4·5H2O, and Na3PO4·9H2O. Computational modeling indicated that the ordered dodecahydrate is more stable than its disordered counterpart, suggesting kinetic persistence of structural disorder. Solubility measurements were conducted with solutions prepared either from anhydrous Na3PO4 or from Na3(PO4)·12H2O·1/6NaOH and revealed that release of interstitial NaOH from the hydrate precursor elevated solution alkalinity, thereby significantly reducing phosphate solubility relative to solutions prepared with anhydrous Na3PO4 across 20–44 °C. These results begin to reconcile inconsistencies in prior solubility data and clarify how phase composition dictates phosphate precipitation under alkaline conditions.

Graham, Trenton R. (ORCID:0000000189078004)↗