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At least 73 records · Page 4

Evaluation of Sludge Solids Returns Impacts on Sludge Batch 10 Flammability, Glass Quality, and Glass Processability

The Savannah River National Laboratory (SRNL) is currently preparing to return ≤ 20 kgs of sludge solids collected over time from Tank Farm characterization activities and demonstrations of the Defense Waste Processing Facility (DWPF) flowsheets (nitric-formic and nitric-glycolic). These sludge solids will be transported and added to Tank 51 which is currently preparing Sludge Batch (SB) 10. DWPF plans to operate the under the nitric-glycolic flowsheet for the processing of SB10. The hydrogen generation rate for the nitric-glycolic flowsheet is 0.024 lb h -1 . The addition of ≤20 kg of sludge solids returns to SB 10 does not have an impact on flammability in the DWPF Chemical Process Cell (CPC) or glass quality and processability. The relatively low mass of the addition (≤20 kg) is insufficient to detect a significant analytical change to the expected SB 10 compositions.

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Measurement Acceptance Region (MAR) Assessment Results Based on Confirmation Sample Sludge Batch 10 Projections

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, 26F, 40H (heel only), and Alternate Feed Stock-2 and Sodium Reactor Experiment material from H-Canyon. Frit 473 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. 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 October 2022, SRMC System Planning provided an updated SB10 Tank 40H blend baseline projection based on the Tank 51 confirmation sample results. Due to the reduced Na concentration relative to previous SB10 projections, two additional projections based on the addition of 7,000 gallons of caustic were provided in November 2022.

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Evaluation of the 0.65 Weight Percent Sulfate Solubility Limit for Sludge Batch 10 Based on November 2022 Projections

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, 26F, 40H (heel only), and Alternate Feed Stock-2 and Sodium Reactor Experiment material from H-Canyon. Frit 473 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 glass property models and their associated Measurement Acceptance Region constraints. 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 October 2022, SRMC System Planning provided an updated SB10 Tank 40H blend baseline projection based on the Tank 51 confirmation sample results. Due to the reduced Na concentration relative to previous SB10 projections, two additional projections based on the addition of 7,000 gallons of caustic were provided in November 2022.

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Chemical and Radiological Compatibility Testing of 3D Printed Materials

To dramatically increase the adaptability, performance, and safety of processes in support of the Defense Waste Processing Facility (DWPF), Savannah River National Lab (SRNL) plans to perform chemical and radiological compatibility testing on a wide variety of 3D printed materials of interest. The 3D printing process provides numerous strategic operational benefits such as rapid prototyping of complex designs and geometry specific to the needs of the nuclear waste disposition process, as well as on-demand rapid prototyping and iteration with materials that aren’t as accessible through traditional manufacturing methods. Reaction chemistry in simulated waste batches can be matched closely to its radioactive counterpart, but glass reactor vessels have limitations. Vessel geometry can play a big factor in mixing transport limitations, process chemistry, and degradation reaction kinetics. In addition, additive manufacturing allows for much more detailed vessel design than traditional alternatives. Waste processing techniques in DWPF also encounter extreme chemical environments including high pH, strong acids, abrasive slurries, and significant irradiation. To meet these challenges, a matrix of various polymer, ceramic, and metal additive manufacturing materials have been exposed to a suite of chemical environments of interest as well as radioactive dose (such as gamma radiation from 60 Co) to properly test their durability under these conditions. Mass change has been monitored over a period of up to a week in these conditions, as well as added characterization for surface modification through Scanning Electron Microscopy/Electron Dispersive X-ray analysis (SEM/EDX). Further chemical characterization has been monitored through Fourier-Transform InfraRed Spectroscopy (FTIR), with planned investigation via thermal and tensile strength degradation. While the direct product of this research is identification of material(s) that can withstand specific hazardous environments encountered by the mercury water wash tank in DWPF process simulation experiments, the reference base of materials will be used for many other nuclear processes in the pursuit of rapidly developed, cost-efficient, and highly specific devices for environmental remediation and much more.

Wilson, Nathan W. [Savannah River National Laborat↗

Composition-Based Density Model for High Level Waste Glasses

In this report, the Savannah River National Laboratory (SRNL) provides a first-principles model capable of predicting the density of high-level waste (HLW) glass based on the glass composition. The model relies on the additivity of the specific volume of bound glass oxides to obtain a quantitative evaluation of the approximate glass density. A database of glass densities and compositions was compiled from various sources including previous Defense Waste Processing Facility (DWPF) variability study glasses, HLW studies from other institutions, and literature references. There are a total of 1104 glass compositions in the database with densities ranging from 2.224 g/cm 3 to 3.997 g/cm 3 . The breadth of the compositional coverage space is reported as well. A predictive method was investigated in which the glass density was calculated as a function of the weighted partial molar volumes of the individual glass oxides and the molar mass of the glass. This method yielded a high correlation between the predicted density and the measured density. In addition, a linear regression of these predictions indicated that the predicted value was equal to the measured within the bounds of analytical uncertainty. The following conclusions were drawn from the results of these analyses: 1. Measured glass density is highly correlated with glass composition (R 2 ≈ 0.95). 2. The correlation between glass density and glass composition can be expressed as either: a. A weighted sum of the individual oxide glass-component densities, or b. A weighted sum of the individual oxide glass-component partial molar volumes. 3. A linear regression of the predicted density via partial molar volume method to the measured density yields a slope of 0.9975 and an intercept of -0.0007 – the uncertainty interval associated with these coefficients contain one and zero, respectively. 4. The fitted coefficients and associated uncertainty intervals of the linear regression of the predicted density via the partial molar volume method to the measured density suggest that the predicted theoretical density is, within analysis uncertainty, equal to the measured density of the glass. It is recommended that glass density measurements included with the variability study for each sludge batch be discontinued. In their place, SRNL will calculate a bounding glass density value for the frit/sludge system using the model. It is also recommended that DWPF implement the density model as part of the fissile loading determination portion of the SME acceptability process. Details for implementation are provided in this report.

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White Paper to Justify the Use of Strip Effluent in the Defense Waste Processing Facility During Slurry Mix Evaporator Processing

At the request of Savannah River Remediation (SRR), a white paper was written to assess whether it would be acceptable to process Strip Effluent (SE) in both the Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) in the Defense Waste Processing Facility (DWPF) for the nitric-glycolic acid flowsheet. Savannah River National Laboratory (SRNL) experimental data and DWPF Sludge Batch 9 (SB9) process data was reviewed, looking at batches which included Precipitate Reactor Feed Tank (PRFT) and/or Strip Effluent Feed Tank (SEFT) feeds that led to long processing times. These batches were reviewed looking for processing problems such as melter feed trips, foamovers, heating rod or steam coil fouling, missed Reduction/Oxidation (REDOX) targets, and other process anomalies.

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An Evaluation of the Impact of Glycolate and Glycolate Mitigation on the Defense Waste Processing Facility Recycle Diversion Project Flowsheet

The Savannah River Site (SRS) Defense Waste Processing Facility (DWPF) processes radioactive High Level Waste (HLW) sludge solids from the Concentration, Storage, and Transfer Facilities (CSTF); which includes the SRS Tank Farm and Evaporator facilities, and a concentrated Cs-137 laden stream and a Monosodium Titanate (MST) and sludge solids stream from the SRS Salt Waste Processing Facility (SWPF). The waste is chemically adjusted with acids and reductant (currently with 50 wt.% nitric acid and ~90 wt.% formic acid, but eventually formic acid will be substituted with ~70 wt.% glycolic acid), and frit is added so that a durable, borosilicate glass waste form can be produced when the material is vitrified in the melter. As a result of the evaporation of water during both the melter feed preparation and the melter feed vitrification steps in DWPF, a recycle waste stream is generated, neutralized, and sent back to the CSTF. The recycle waste is a dilute aqueous stream originating from the collection of condensate liquids containing some minor sludge, MST, and frit solids and other waste components resulting from melter feed entrainment during foamover events and transfer of volatile species into the condensate. The recycle stream volume is significant and is expected to approach 3 million gallons per year once SWPF reaches full operation, requiring the use of multiple large CSTF tanks for storage. The recycle waste is currently collected in the SRS Tank Farm and periodically evaporated in the 242-16H (2H) Evaporator to conserve storage space.

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Ion Chromatography (IC) Round Robin Analyses of Low Glycolate Concentrations in Recycle Collection Tank (RCT) Post Permanganate Treatment Simulant

This work is a demonstration of Ion Chromatography (IC) analysis of low concentrations of glycolate in chemical simulant designed to mimic the matrix in the Recycle Collection Tank (RCT) at the Defense Waste Processing Facility (DWPF) after sodium permanganate oxidation treatment. The IC method was previously developed [1] and this report covers the results of round robin testing with three analytical laboratories located at the Savannah River Site (SRS). The laboratories are termed the Sensing & Metrology (S&M) laboratory at the Savannah River National Laboratory (SRNL), the Processing Science Analytical Laboratory (PSAL) at SRNL, and the DWPF laboratory at SRS. Each laboratory received four samples: (1) 200 mL of 21.3 mg/L glycolate in RCT post permanganate strike sulfite quenched simulant, (2) 200 mL of 38.0 mg/L glycolate in RCT post permanganate strike sulfite quenched simulant, (3) 200 mL of 54.9 mg/L glycolate in RCT post permanganate strike sulfite quenched simulant, and (4) 600 mL of RCT post permanganate strike sulfite quenched simulant to use for matrix matched blanks.

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Characterization of the SRNL-Washed Tank 51 Sludge Batch 10 Qualification Sample

Savannah River National Laboratory (SRNL) personnel have been requested to qualify the next sludge batch (Sludge Batch 10 – SB10) for processing at the Defense Waste Processing Facility (DWPF). To accomplish this task, Savannah River Remediation (SRR) sent SRNL two 3-L samples of Tank 51H slurry to be characterized, washed, and then used in a lab-scale demonstration of the DWPF flowsheet. Sample HTF-51-19-114 was received on January 28, 2020, and HTF-51-20-15 was received on February 4, 2020. SRNL washed the Tank 51H sample per the Tank Farm washing strategy. During washing, material from H Canyon Tanks 16.3 and 16.4 was also added to the Tank 51 samples to simulate canyon discharges subsequent to sampling. A part of the qualification process is extensive radionuclide and chemical characterization of the SRNL-washed Tank 51H slurry. This report documents the chemical characterization of the washed slurry; radiological characterization will be documented in a separate report. The major supernatant components, elements on a weight percent calcined basis, and the weight percent solids of the SRNL-washed sample were comparable to the Tank Farm projections, with the exception of free hydroxide and carbonate. Therefore, this SRNL-washed sample is suitable for further SB10 qualification activities and SRR planning for SB10.

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SRNL Sludge Batch 10 Qualification SRAT and SME Off-Gas Results

Savannah River National Laboratory (SRNL) completed a small-scale demonstration of the Defense Waste Processing Facility (DWPF) Chemical Process Cell (CPC) utilizing the nitric-glycolic acid (NGA) flowsheet to support Sludge Batch 10 (SB10) qualification. The demonstration utilized a Tank 51 slurry sample washed by SRNL (with added H-canyon material). The purpose of this document is to report the observed off-gas results from the demonstration. With the NGA flowsheet, DWPF has a CPC hydrogen generation limit of 2.4×10 -2 lb/h. The peak observed rate was nearly 90 times less than that limit during SRNL testing.

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Radioactive Waste Sludge Washing and Demonstration of the Nitric-Glycolic Acid Flowsheet for Sludge Batch 10 Qualification

For each sludge batch that is processed in the Defense Waste Processing Facility (DWPF), the Savannah River National Laboratory (SRNL) performs qualification testing to demonstrate that the sludge batch (SB) is processible. During processing of SB9, DWPF will be transitioning from the Nitric-Formic Acid (NFA) flowsheet to the Nitric-Glycolic Acid (NGA) flowsheet. Thus, the qualification of SB10 was requested to only be performed using the NGA flowsheet. In order to qualify the batch for the NGA flowsheet, Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) cycles, designated SC-19, were performed using SB10 Tank 51 sample material. SRNL received Tank 51 material in the midst of Tank Farm washing. SRNL continued the washing in the SRNL Shielded Cells. The SRNL process included the addition of Sodium Reactor Experiment (SRE) material from H Canyon, simulating the transfer of SRE from H Canyon to Tank 51 during Tank Farm washing. The washed SB10 Tank 51 material, with SRE, was characterized prior to flowsheet qualification testing.

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Technical Evaluation of Accelerated Basin De-Inventory Material Addition to Sludge Batch 11

Savannah River Nuclear Solutions has a need to discard spent nuclear fuel (SNF), currently stored in L Basin, to the Defense Waste Processing Facility (DWPF) for vitrification. The Department of Energy (DOE) has approved the Accelerated Basin De-inventory (ABD) Program for discarding SNF via transfers from H-Canyon to the Savannah River Site (SRS) Liquid Waste (LW) system. The first ABD discards will occur during the preparation of Sludge Batch (SB) 11. An initial impact evaluation of the LW flowsheet was performed by the Savannah River National Laboratory (SRNL) prior to the approval of the ABD Program. This evaluation addressed the LW downstream facilities based on the current H-Canyon flowsheet sequence for the average ABD discard. The flowsheet evaluation only included aluminum-clad SNF, specifically Materials Test Reactor (MTR) fuel and High Flux Isotope Reactor (HFIR) fuel similar to the planned SB11 discard. Following this evaluation, the flowsheet has been slightly altered to address (i) new nuclear criticality safety controls for DWPF that credit a higher amount of gadolinium as a neutron poison for all of the enriched uranium contained in a SB and (ii) potential additions of the H-Canyon neutralized fuel stream prior to the Low Temperature Aluminum Dissolution (LTAD) process in Tank 51. The early introduction of ABD material into the SB assembly process is being investigated to provide flexibility regarding transfer opportunities for H-Canyon to Tank 51 for SB11 and future sludge batches.

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Washing Study with SRS Tank 26 Samples FTF-26-19-12 and -13

A recent analysis of Tank 26, one of the feed tanks for the Defense Waste Processing Facility (DWPF) Sludge Batch 10 (SB10), determined a higher than anticipated sulfur concentration in the supernatant and a significant amount of insoluble sulfur, which could negatively impact the DWPF glass waste form. Savannah River Remediation Engineering (SRR-E) requested that the Savannah River National Laboratory (SRNL) perform a washing study with Tank 26 material to determine amount of sulfur removed during washing tests. SRNL decanted supernate from a sample of Tank 26 until it was at 12 wt% insoluble solids. Subsequently, SRNL performed washing experiments from the 8 M sodium initial concentration to targeted endpoints of 4 M, 2 M and 1 M sodium concentration (assuming no sodium dissolution). Results show that over 80% of the sulfur was removed and nearly all the sulfur was in the aqueous phase at the end of washing, demonstrating effective removal of sulfur during washing. Additional washing is likely to decrease the sulfur concentration further since most of the sulfur was in the aqueous phase.

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Calculation of Glycolate Concentration Factors Across the 242-25H (3H) Evaporator System

Two models were developed to predict glycolate concentration factors across the 242-25H (3H) Evaporator system. The first model, identified as the Unrestricted Evaporation Model, was designed to evaluate concentration of typical 3H feed material to relatively high densities in order to calculate the concentration factor of glycolate in a given feed stream. This model may be used to understand the potential of glycolate to concentrate from a generic feed material through the 3H system. The second model, identified as the Holistic Evaporation Model, was designed to evaluate the evaporation of dilute, glycolate-containing Defense Waste Processing Facility (DWPF) waste with the requirement that high silicon concentrations typical of recycle material require dilution to adhere to current technical safety requirements. This model may be used to understand the potential of glycolate from DWPF recycle material to concentrate as a result of feeding through the 3H system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Examining Thermolytic Production of Hydrogen from Lubrication Oil

Savannah River National Laboratory (SRNL) was requested by Savannah River Remediation (SRR) to conduct testing via Technical Task Request (HR) to determine the thermolytic HGR of Mobil SHC™ 630, a lubrication oil. Currently, 35 gallons of contaminated Mobil SHC 630 is proposed for release into the recycle stream from the Defense Waste Processing Facility (DWPF) to Tank 22 and then to the 242-16H (2H) Evaporator system. Inhibited recycle waste in the Recycle Collection Tank (RCT) is transferred to Recycle Pump Tank (RPT) in the Low Point Pump Pit (LPPP) and then to the Concentration, Storage and Transfer Facilities (CSTF) H-area. The lubrication oil would be added directly to the RPT, bypassing the RCT. The current DWPF waste compliance plan for liquid transfers from the RCT to the CSTF limits the concentration of Mobil SHC 630 to <1,100 ppm which is equal to <9.3 gallons of Mobil SHC 630 when considering a 7,500 gal RCT batch with an initial Mobil SHC 630 concentration of 42 mg/L. Mobil SHC 630 is expected to be largely immiscible in the caustic aqueous waste stream. It is a blend of base oils including polyalphaolefin (PAO) base oil and additives such as triphenylphosphate and cresyl diphenyl phosphate at various concentrations (<0.25 wt%). While the base oils are expected to be largely unreactive in CSTF waste, the triarylphosphates additives would be expected to hydrolyze in the caustic waste, forming diarylphosphates and phenol. The tests described herein were governed by a single Run Plan and will determine thermolytic HGR from the caustic aqueous solution, as well as from any organic phases present.

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An Assessment of the Materials of Construction for the Transfer Lines and Unit Operations Equipment Associated with the Recycle Diversion Process

The Defense Waste Processing Facility (DWPF) processes and vitrifies radioactive waste that it receives from the Concentration, Storage, and Transfer Facility (CSTF) and Salt Waste Processing Facility (SWPF). As a result of the evaporation of water during both the melter feed preparation and the melter feed vitrification steps in DWPF, a recycle waste stream is generated, neutralized, and sent back to the CSTF. The recycle waste is a dilute water stream originating from the collection of condensate liquids containing some minor sludge and frit solids and other waste components primarily resulting from entrainment into the condensate during foam-over events. The recycle stream volume is significant and is expected to approach 3 million gallons per year once the SWPF reaches full operation. Diverting the bulk of the recycle waste stream from the CSTF is essential for the eventual closure of the waste tanks, and hence the completion of the SRS liquid waste mission.

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Evaluation Of Glass Density to Support the Estimation of Fissile Mass Loadings in Sludge Batch 10 Glasses

Per a directive from the Department of Energy Savannah River Operations Office (DOE-SR) in 2008, the fissile mass loading concentration must remain below 897 g/m 3 in each high-level waste (HLW) glass canister produced by the Defense Waste Processing Facility (DWPF). To support Sludge Batch 5 (SB5) processing, the Savannah River National Laboratory (SRNL) developed a technical basis that facilitates the evaluation of fissile mass loading of the glass product. The calculation is based on the iron (Fe) concentration in the glass as determined by measurements from the Slurry Mix Evaporator acceptability analysis as well as the glass density. In April 2022, a subsequent DOE-SR directive increased the fissile mass loading limit to 2500 g/m 3 beginning with Sludge Batch 11. Thus, the 897 g/m 3 limit still applies to Sludge Batch 10 (SB10) processing. For SB5 through initial Sludge Batch 9 (SB9) processing prior to coupled operation with the Salt Waste Processing Facility (SWPF), SRNL provided DWPF a bounding glass density value that was based on a statistical evaluation of density measurements. To eliminate the need for experimental work, a composition-based density model for HLW glasses was developed at SRNL in 2019. The objective of this report is to present the bounding glass density determined with the composition-based density model for SB10 sludge-only (SO) and coupled processing.

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M-Star ® Software Test and Verification

Savannah River Mission Completion (SRMC) currently manages the risk for retained hydrogen in the Defense Waste Processing Facility (DWPF) vessels by implementing a Retained Hydrogen Program. The current program relies on Sludge Batch (SB) 8 Gas Chromatograph data and on conservative assumptions concerning gas release and retention to determine allowable vessel Quiescent time (Q-time). The authors identified M-Star ® CFD as a software that could simulate processes such as fluid flow, heat transfer, species transport, chemical reactions, particle transport, and retained hydrogen gas release. Preliminary simulation results suggest that more realistic assumptions on gas retention and release may be feasible for the DWPF retained hydrogen program. Because of the desire to use the M-Star ® software to perform analyses that support nuclear safety, SRMC has requested Savannah River National Laboratory (SRNL) to upgrade the software classification level of M-Star ® CFD from level D to level A to perform analyses that support nuclear safety.

08 HYDROGEN↗