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At least 37 records · Page 2

SB10 Frit Recommendation, and Evaluations of the Glass Variability Study and Cs-137 Concentrations in Strip Effluent Based on May 2021 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, and 26F, Alternate Feed Stock-2 (AFS-2) and Sodium Reactor Experiment (SRE) material from H-Canyon. In support of SB10 qualification, frit development using 2020 Tank 40 blend projections and experimental work for the glass variability study were previously conducted. Frit 473 and Frit 209 were identified as candidate frits and both were included in the development of the variability study test matrix; however, a final frit recommendation was postponed until more information could be determined about the composition of SB10 after washing. In May 2021, Savannah River Remediation (SRR) reprojected SB10 based on the analytical results from the Tank 51 qualification sample that was washed in the Savannah River National Laboratory (SRNL) Shielded Cells Facility.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Organomercury Measurements from Sludge Batch 10 Simulant Studies

Researchers at the Savannah River National Laboratory have recently performed testing to evaluate the Sludge Batch 10 flowsheet using simulated sludge waste. In the course of this testing several samples were taken to determine the concentration of organomercury species resulting from sludge batch processing. These samples were submitted to the Savannah River National Laboratory Sensing and Metrology department quantitation using a mercury analyzer. The signal amplifier used to perform organomercury quantitation in the mercury analyzer experienced a malfunction in the course of analysis, leading to uncertainty of organomercury concentrations observed. Seventy-three organomercury samples from six project submissions to the Savannah River National Laboratory Sensing and Metrology department have been critically reviewed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Zirconium Sludge Criticality Calculations in Large Process Tanks

The Savannah River Site’s H-Canyon facility has been tasked with accelerating the disposition of used research reactor fuels. • Future missions will involve dissolution of “Non-Aluminum” clad fuels – not easily dissolved – Nitric acid is not capable of dissolving stainless steel, Zirconium, and Hastelloy, clad fuels by itself • The electrolytic dissolver has been (re) selected as a disposition path for these fuels. 2

Devine, Nathan P.↗

Vitrification Testing of HLW with High Phosphate

Projections of the number of high level waste (HLW) canisters to be produced in the Hanford Tank Waste Treatment and Immobilization Plant (WTP) (e.g., [1]) are based upon the inventory of the tank wastes, the anticipated performance of the sludge treatment processes, and current understanding of the capability of the borosilicate glass waste form. The WTP HLW melter design, unlike earlier Department of Energy (DOE) melter designs, incorporates a glass bubbler system. The bubblers create active glass pool mixing and thereby improve heat and mass transfer and glass melting rate. The WTP HLW melters each have a glass surface area of 3.75 m 2 and depth of ~1.1 m. The two melters in the HLW facility together are designed to produce up to 7.5 MT of glass per day at 100% availability. Further increases in HLW waste processing rates can potentially be achieved by optimization of the feed and glass formulations, increasing the melter operating temperature above 1150⁰C, and by increasing the waste loading in the glass product. Increasing the waste loading also has the added benefit of decreasing the number of canisters for storage.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Zirconium Sludge Criticality Calculations in Large Process Tanks

The Savannah River Site’s (SRS) H-Canyon recently re-activated its 6.3D electrolytic dissolver to dissolve stainless steel clad research reactor fuels from Japan. A potential new mission was identified to dissolve other long-cooled fuel stored at SRS that is not aluminum clad. In the basic process of dissolution, the spent fuel dissolves into nitric acid (bulk solution). The eight ft. high and four ft. radius 6.3D dissolver is unique in that it has a platinum-coated niobium insert to resist corrosion, and the niobium basket forms an anode and cathode arrangement within the charge chute (Fig 1,2). DC current flows from anode to cathode, at up to 10,000 amps at 45 volts, through the potential gradient in the nitric acid solution, which allows the stainless steel (or other non-aluminum cladding) of the fuel to dissolve.

Wade, Brindley↗

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.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Transformation Kinetics of Phosphorus and Nitrogen in Iron-Rich Sewage Sludges during Hydrothermal Treatment and Recovery of Nutrients from Process Water

Hydrothermal treatment (HT) is an emerging technique for sustainable sewage sludge management and resource recovery. Many sludges are rich in iron (Fe) due to the common addition of Fe salts in water resource recovery facilities. To develop guidance for reaction conditions targeting nutrient recovery, this study systematically investigated the influence of HT temperature, treatment time, and sludge source on the dynamic speciation evolution of phosphorus (P) and nitrogen (N) during HT of Fe-rich sewage sludge. Complementary chemical extraction and X-ray spectroscopy analyses were conducted to characterize the treatment products. For the sludge mixture (a blend of primary and waste activated sludges), P speciation did not change significantly within 4.5 h at 125 °C HT, while soluble and labile P was converted into insoluble P over time at 175 and 225 °C HT. Strengite (FePO 4 · 2 H 2 O) preferentially formed in the hydrochars with increasing treatment temperature and/or time, whereas 125 °C HT within 1.5 h favored the formation of vivianite (Fe 3 (PO 4 ) 2 ·8H 2 O). Organic P was completely decomposed into orthophosphate when the HT temperature reached up to 175 °C. Pyrrole-N was enriched in the hydrochars. Similar reaction pathways were observed during HT of anaerobically digested sludge, though some minor differences in Fe-associated P and organic P were observed. Meanwhile, HT of the two sludges released orthophosphate and ammonia into the process waters at 175 and 225 °C, which can be recovered by a sequential process involving struvite (MgNH 4 PO 4 ·6H 2 O) precipitation and air stripping. This study provides new insights into the transformation of P and N during HT of Fe-rich sludges as well as a modular design for maximum P and N recovery from the treatment products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Removal of phosphorus using biochar derived from Fenton sludge: Mechanism and performance insights

Abstract A phosphorus removal biochar adsorbent was prepared from Fenton sludge. The adsorption process was optimized, and its phosphorus adsorption mechanism was discussed. It was found that the phosphorus adsorption performance of biochar prepared from single Fenton sludge (FBC‐400) was better than that of co‐pyrolysis of Fenton sludge and bamboo powder. The optimum condition was that Fenton sludge pyrolyzed at 400°C (FBC‐400). FBC‐400 had a larger specific surface area than that prepared by co‐pyrolysis with bamboo powder. And the high content of iron element could provide a higher surface charge of the biochar, thereby increasing the electrostatic adsorption of phosphorus onto FBC‐400. The phosphorus adsorption was highly pH dependent by FBC‐400, which can enhance electrostatic adsorption and increase adsorption capacity in acidic conditions. The effect of coexisting anion on adsorption performance was mainly affected by CO 3 2− , reducing the adsorption capacity by at least 49%, whereas other anions had no obvious interference. The adsorption process of FBC‐400 accorded with the pseudo‐second‐order kinetic model and the Langmuir model, which indicated that the adsorption process was monolayer adsorption and mainly chemical adsorption, and the maximum saturated phosphorus adsorption capacity was 8.77 mg g −1 . The mechanisms for phosphorus adsorption were electrostatic adsorption and inner‐sphere complexing. 1 M NaOH was used for desorption, and the adsorption capacity remained at 81% in the fifth cycle. Practitioner Points The Fenton sludge biochar usage as an adsorbent could be a win‐win strategy to convert waste biomass to valuable ‐ product. The adsorption process accorded with the Langmuir model, the maximum phosphorus adsorption capacity was 8.77 mg/g at 25°C. The adsorption mechanisms were electrostatic adsorption and inner‐sphere complexing. 1M NaOH was used for desorption, and the adsorption capacity remained at 81% in the fifth cycle.

Liu, Yanfang↗

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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Mercury Testing with Sludge Batch 10 Tank 40 Simulant

Savannah River Mission Completion (SRMC) requested that researchers at Savannah River National Laboratory (SRNL) perform testing designed to examine why the Defense Waste Processing Facility (DWPF) is not collecting elemental mercury in the Mercury Water Wash Tank (MWWT). In order for DWPF to recover mercury, mercuric oxide must first be reduced to elemental mercury. The elemental mercury must then be steam stripped, condense, and coalesce in the Mercury Water Wash Tank (MWWT) during chemical processing in the Sludge Receipt and Adjustment Tank (SRAT). The efficiency of these steps was investigated in a series of laboratory scale SRAT experiments under the nitric-glycolic and nitric-formic flowsheets utilizing Momentive Y-17112 and Antifoam 747. Mercury speciation in the Slurry Mix Evaporator Condensate Tank (SMECT) and condensate streams was also examined. The key conclusions from these experiments are as follows: Mercury II Oxide may not be fully reduced to elemental mercury during acid addition at 93°C. Higher temperatures, i.e., boiling may be necessary to fully reduce Mercury II Oxide. The highest percent mercury recovery (71 %) in the MWWT was observed in the MS-NGA-17112 experiment (nitric-glycolic acid flowsheet with Momentive Y-17112), which is how DWPF is currently operating the SRAT.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Modeling of Chemical Slurry Rheology in DWPF Sludge Batch (SB) 10 Simulants

The Defense Waste Processing Facility (DWPF) treats high-activity radionuclides from sludge through a process called vitrification. This process converts radioactive liquid waste currently stored in tank farms into a solid glass form that is suitable for long-term storage and disposal. Due to the complexities involved in vitrifying this waste within each operation of the Chemical Processing Cell (CPC), waste rheology is studied to characterize the fluid-mechanical properties as it passes through the CPC and into the Melter. To better understand the waste and validate flow behavior, slurry rheology of simulants that represents the waste was studied at various acid stoichiometry percentages and solids concentrations to determine the simulant’s yield stress and viscosity. This research work has been supported by the DOE-FIU Science & Technology Workforce Development Initiative, an innovative program developed by the U.S. Department of Energy’s Office of Environmental Management (DOE-EM) and Florida International University’s Applied Research Center (FIU-ARC). During the spring of 2022, a DOE Fellow intern, Brendon Cintas, spent 10 weeks doing a summer internship at Savannah River National Laboratory (SRS) under the supervision and guidance of Dan Lambert, Chemical Flowsheet Development. The intern’s project was initiated on June 6, 2022, and continued through August 11, 2022 with the objective of assisting scientists at SRNL’s Rheology and Grout Laboratory at Aiken Country Technology Lab (ACTL) better understand the sludge composition on the rheology of a simulant slurry using a HAAKE RheoStress 6000 rheometer and extrapolate the results to the real-waste data.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

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.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Selection of Glasses to Confirm the 0.65 Weight Percent Sulfate Solubility Limit for Sludge Batch 10

In preparation for Sludge Batch 10 (SB10) processing, projections of sulfate (SO 4 2- ) in glass at 36% waste loading (WL) were calculated in May 2020 for Tank 40 blend projections representing 0.7M and 0.85M Na wash endpoints. The projected SO 4 2- ) concentrations for either sludge-only (SO) or coupled processing with the Salt Waste Processing Facility (SWPF) were either near or exceeded the current Sludge Batch 9 (SB9) limit of 0.65 weight percent (wt.%). Four nominal glass compositions were selected based on SO and coupled processing for the 0.85M Na wash endpoint Tank 40 blend projection to conduct an initial evaluation of the SB10 sulfate solubility behavior. A sulfate salt phase was absent from each of the prepared glasses, which provided preliminary results that supported the 0.65 wt.% SO 4 2- ) limit for SB10.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

PERFORMANCE ANALYSIS OF AN ENGINEERING SCALE HYDROTHERMAL LIQUEFACTION SYSTEM

This work evaluates the Modular Hydrothermal Liquefaction System (MHTLS), an engineering-scale, integrated continuous HTL plant operated at the Pacific Northwest National Laboratory (PNNL), for converting realistic wet wastes into energy-dense biocrudes. The production campaigns discussed here processed algae, sewage sludges, lignocellulosic blends, Industrial food waste, and engineered food-waste slurries at 350?°C and around 200?bar, with nominal feed rates of ~12?L?h?¹. We report biocrude yields and composition, establish mass and elemental (C, N) balances, and quantify energy performance via heater duties, heat-exchanger behavior, and system-level efficiencies. Biocrudes contained 76–80?wt?% C (dry, ash-free) with HHVs of 38-41?MJ?kg?¹, substantially higher than feed materials HHVs of 16.6–26.1?MJ?kg?¹ and approaching petroleum fuels. Dry, ash-free biocrude yields of 32–53?wt?% corresponded to 43–71?wt?% carbon yields, with 18–40?wt?% of feed carbon routed to the aqueous phase. Thermal efficiencies were 50-65%, and total energy efficiencies, including reactor heat input, were 35-55%. A counter-current tube-in-tube heat exchanger delivered U values of 200–450?W?m?²?K?¹, with fouling-induced declines impacting heat recovery and heater duty. The analysis highlights three priorities for the process intensification of HTL: robust, fouling-resistant heat recovery, hydrodynamically suitable reactor and heat-exchanger designs, simplified and predictable solids management, and biocrude-water separation.

Biocrude production↗

Chemical Characterization Results for Tank 40 Sludge Batch 10 Waste Acceptance Product Specifications (WAPS) Sample

A 3-L sample (HTF-40-23-24) obtained from Tank 40 following transfer of Tank 51 to achieve the final Sludge Batch 10 processing composition was received by Savannah River National Laboratory (SRNL). SRNL was tasked with characterization of the sample in accordance with requirements for reporting the Waste Acceptance Product Specifications. A representative subsample, approximately 500 mL, was prepared by continuously agitating the 3-L sample via a mixing blade inserted into the bottle. This subsample was then used for the chemical and physical characterization reported here. This characterization includes the following: (1) Supernate and slurry density; (2) Weight percent solids; (3) Mercury Analysis (supernate and slurry); (4) Anions; (5) Total Organic/Inorganic Carbon; (6) Free Hydroxide; (7) Other Base; (8) Elementals; (9) Volatile Organic Analysis and Semi-volatile Organic Analysis; and (10) Fissile Radionuclides and Uranium Enrichment. The results of this physical and chemical characterization of the sample are documented in this report.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Harvesting Energy from Wastewater by Converting Sewage

This project aims were to develop and demonstrate a scalable, integrated process to convert sewage sludge into renewable natural gas (RNG), enabling wastewater treatment plants (WWTPs) to become net energy producers. The system proposal integrates autothermal hydrothermal liquefaction (AT-HTL), supercritical salt precipitation (SCSP), and hydrothermal gasification (HTG), collectively forming the Supercritical Sludge-to-Gas (SC-S2G) platform. Initially, batch hydrothermal liquefaction reactions were used to screen sewage sludge using AT-HTL (later termed RI-HTL) conversion to biocrude, aqueous and char phases compared to hydrothermal liquefaction (HTL). Significant improvement in biocrude yield using peroxide addition at O:C ratio of 0.05 and under conditions of 300°C for 10 minutes gave 57% biocrude yield and 85% fluid carbon yield (biocrude plus aqueous), while minimizing the loss of carbon to char solids (~7%). Hence, RI-HTL was shown to be effective for conversion of real sewage sludge. The corrosion of the alloy reactor tubes or vessels is an important factor when developing a process that includes an oxidant and a chemically complex feed like sewage sludge. We investigated the corrosion rates on metal alloys at 350°C for 240 hours. Corrosion rates of 0.21 and 0.26 mpy for 304L and 316L stainless steel were measured respectively. The corrosion information obtained in this investigation was utilized by PNNL for design, materials sourcing and construction of the pilot scale continuous flow system.

09 BIOMASS FUELS↗

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.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗