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At least 37 records · Page 2

Impact of Permanganate Oxidation of Glycolate on Corrosion of the Defense Waste Processing Facility (DWPF) Recycle Collection Tank (RCT), Transfer-line and Waste Tank Materials of Construction (MoC)

Savannah River Remediation (SRR) is evaluating the use of glycolic acid to replace formic acid as an alternate reductant for the Defense Waste Processing Facility (DWPF) at Savannah River Site (SRS). The replacement is aimed at reducing facility hazards, improving pH stability and rheological control, and lowering off gas production. Glycolate, which is the product that may remain, can also be carried downstream to High-Level Waste and Low-Level Waste facilities. Complete oxidation of glycolate and other organic species from the Sludge Receipt and Adjustment Tank (SRAT) may be necessary to minimize thermolytic hydrogen generation that can cause flammability issues. The glycolate oxidation may be performed in the Recycle Collection Tank (RCT). The RCT heel would be adjusted with sodium hydroxide to maintain the solution caustic and sodium nitrite as corrosion inhibitor prior to the addition of condensate that can be from the contents of the Slurry Mix Evaporator Condensate Tank (SMECT) or Offgas Condensate Tank (OGCT). The RCT tank collects the waste to be transferred via the Low Point Pump Pit – Recycle Pump Tank (LPPP-RPT) through a jacketed transfer-line to the Tank Farm facility. Scoping studies were performed to evaluate an oxidizing agent and sodium permanganate was selected as the best option for glycolate destruction. Testing was recommended to determine the impact on the Materials of Construction (MoC) due to the addition of sodium permanganate. The targeted concentration of sodium permanganate used equated to a 7:1 molar permanganate to glycolate ratio (nominally 0.002 M permanganate). However, to conservatively maximize the permanganate corrosivity, in some cases no glycolate was added.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Analysis of Defense Waste Processing Facility (DWPF) Condensate Samples and Evaluation of the Glycolate Destruction Process during Nitric-Glycolic flowsheet Transition

Glycolate concentrations were measured by the Savannah River National Laboratory (SRNL) in Slurry Mix Evaporator Condensate Tank (SMECT) and Recycle Collection Tank (RCT) samples retrieved after implementation of the Nitric-Glycolic Acid flowsheet at the Defense Waste Processing Facility (DWPF). No glycolate has been detected in any sample using Ion Chromatography (IC) with a detection limit of 8 mg/L, and no glycolate has been detected using either IC or Proton Nuclear Magnetic Resonance Spectroscopy ( 1 HNMR) after a permanganate strike was performed in the RCT.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Evaluation of the Impact of Additional Manganese from the Recycle Collection Tank (RCT) Glycolate Destruction Process on Glass Properties

The Defense Waste Processing Facility (DWPF) is planning to implement glycolic acid as a reductant within the waste processing flowsheet. An assessment of the glycolic acid flowsheet has revealed the potential for thermolytic production of hydrogen in the Concentration, Storage and Transfer Facilities (CSTF) from glycolate entrained in the DWPF recycle stream. To mitigate this potential scenario, a glycolate destruction process utilizing sodium permanganate (NaMnO 4 ) is being developed for use in the DWPF Recycle Collection Tank (RCT). The RCT is fed by the Slurry Mix Evaporator Condensate Tank (SMECT) and the Off-Gas Condensate Tank (OGCT). The SMECT could receive glycolate via a foamover from the Sludge Receipt and Adjustment Tank (SRAT) or the Slurry Mix Evaporator (SME), and the OGCT could receive glycolate via carryover of sludge particles in the purge from the melter during surge conditions. The use of NaMnO 4 additions in the RCT will result in additional manganese (Mn) in the waste stream and needs to be evaluated.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Drastically different restructuring of airborne and surface-anchored soot aggregates

Combustion soot particles are fractal aggregates of hydrophobic spherules. Mixing of soot particles with other chemicals during atmospheric processing may partially offset their hydrophobicity, promoting water uptake and structural compaction. Here, we investigated morphological changes in fractal soot particles coated by sulfuric acid and then humidified, both in airborne and surface-bound states. Airborne soot was probed by tandem differential mobility analysis. Surface-bound soot was studied in a controlled microenvironment of a closed cell, using environmental transmission electron microscopy. After humidification, the airborne particles became fully compact, but the deposited particles showed only minor morphological changes despite significant water uptake. Although minor, those changes were detected during both water condensation and evaporation, indicating that condensation-evaporation cycles play an important role in atmospheric soot compaction. Lesser restructuring of deposited aggregates was caused by surface anchoring and coating loss, making anchoring an indispensable tool for preserving morphology of aggregates against changing experimental environment.

54 ENVIRONMENTAL SCIENCES↗

Analysis of Defense Waste Processing Facility Sample: Off-Gas Condensate Tank Sample Batch 27862

The Savannah River National Laboratory (SRNL) was requested by Savannah River Remediation (now Savannah River Mission Completion (SRMC)), through a Technical Task Request (X-TTR-H-00107), to characterize the “as-received” Off-Gas Condensate Tank (OGCT) Sample identified as sample batch 27862, which was delivered to SRNL Shielded Cells on April 30, 2021. This OGCT report is the third of three sample characterization reports dealing with this Defense Waste Processing Facility (DWPF) Recycle Diversion Project. The other two recycling stream characterization reports are the Recycle Collection Tank (RCT) and the Slurry Mix Evaporator Condensate Tank (SMECT) sample report.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

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↗

From Langmuir isotherm to Brunauer–Emmett–Teller isotherm

Abstract Developed for multilayer adsorption, the Brunauer–Emmett–Teller ( BET) isotherm considers the adsorption of the first layer as an equilibrium chemical reaction between adsorbate molecules and adsorption sites and the adsorption of the second and subsequent layers as a condensation–evaporation process. Following the recent development of an activity‐based formulation for the Langmuir isotherm for monolayer adsorption, we present an activity‐based formulation for the BET isotherm in which species concentrations are replaced with species activities. Capturing the adsorbent surface heterogeneity for the adsorption of the first layer, the resulting thermodynamic BET isotherm is shown to accurately represent pure component adsorption isotherms over the relative pressure range of zero to unity or prior to the onset of capillary condensation. The thermodynamic BET isotherm should facilitate accurate estimation of monolayer adsorption capacity and the corresponding adsorbent surface area.

Vyawahare, Pradeep↗

Review of Experimental Decontamination Factors (DF) of Iodine in the Pilot-Scale Law Melter Off-Gas Systems

The Low Activity Waste (LAW) melters at the Hanford Tank Waste Treatment and Immobilization Plant (WTP) will convert low-activity tank wastes containing high concentrations of sodium salts into glass for onsite disposal. Much of the airborne particulates during the calcination/fusion of the feed solids will be removed by condensation and scrubbing of the melter exhaust in the Submerged Bed Scrubber (SBS) and Wet Electrostatic Precipitator (WESP)of the primary off-gas treatment system. The gases exiting the WESP enter a secondary off-gas treatment system, which includes a High-Efficiency Particulate Air (HEPA) filter, an activated carbon absorber, a Thermal Catalytic Oxidizer (TCO), a Selective Catalytic Reduction (SCR) unit, a caustic scrubber, and an exhauster. Much of the volatile organics and NOx will be removed in the TCO and SCR, respectively. Under WTP Direct Feed LAW (DFLAW) configuration, the liquid effluents from the SBS and WESP will be collected and evaporated under vacuum with the evaporator concentrate recycled back to the LAW melter, while the evaporator condensate will be merged with the caustic scrubber solution and sent to the Effluent Treatment Facility (ETF).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Modeling of Glycolate Destruction in the Recycle Collection Tank

The Savannah River Site’s DWPF is being upgraded with the introduction of the NG flowsheet. Glycolic acid has been shown to be a superior alternative to formic acid for sludge processing. The new flowsheet improves or maintains necessary parameters such as 1) reduction of mercury, 2) adjustment of feed rheology, 3) pH stability, and 4) adjustment of melter oxidation/reduction potential. Further, the use of glycolic acid virtually eliminates the potential for catalytic hydrogen generation in DWPF processing DWPF process condensates are collected and returned to the Savannah River Site (SRS) CSTF. The RCT collects off-gas condensate during chemical processing, vitrification, and other unit operations performed in DWPF and is the singular return vessel delivering recycle effluent back to CSTF. Each batch of recycle will have a small amount of glycolate from chemical processing and melter off-gas condensates. To avoid potential flammability issues due to thermolysis of glycolate in the CSTF, Savannah River National Laboratory (SRNL) provided to Savannah River Remediation (SRR) at their request a Task Technical and Quality Assurance Plan (TTQAP) to quantify and mitigate glycolate returns via DWPF’s recycle stream. The request included testing of a process to oxidize glycolate and other organic species that are responsible for hydrogen generation from thermolysis. Following that work SRR provided a Task Technical Request (TTR) that requested process modeling. In 2021 a TTQAP was issued to cover the modeling work. Modeling draws data from laboratory scale studies using chemical simulants and radioactive waste samples. Chemical kinetic modeling was performed to evaluate the feasibility of using sodium permanganate to destroy glycolate in the RCT. The results from the laboratory studies were summarized in a series of reports. Reference 9 is a report of lab scale processing of actual DWPF Slurry Mix Evaporate Condensate Tank (SMECT) and Offgas Condensate Tank (OGCT) samples in the SRNL Shielded Cells. Tests at caustic conditions demonstrated sodium permanganate was effective in converting glycolate to oxalate, and permanganate (Mn 7+ ) is reduced to manganate (Mn 6+ ) with no significant formation of carbon dioxide or carbonate. Equation (1) was found to best describe the observed reaction of glycolate with permanganate under nominal (60 to 145 mg/L in RCT) glycolate entrainment conditions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Underwater thermomagnetic generator for remote marine thermal energy harvesting and sensing

Thermomagnetic generators offer a promising approach for sustainable power generation in remote marine environments. Here, this study presents the design, thermal modeling, and experimental validation of a passively driven underwater thermomagnetic generator developed for powering ocean observation and monitoring sensors. The generator was evaluated under varying working fluids, thermal boundary conditions, and extended operation to assess real-world applicability. Two fluids, deionized water and silicone-based Thermal C5, were tested under simulated shallow- and deep-ocean conditions. Deionized water outperformed Thermal C5, especially in colder environments (~5°C), achieving a peak output of 2.7 mW due to larger temperature gradients and enhanced convective-evaporative heat transfer. Long-duration tests revealed a transient evaporation-condensation cycle that temporarily reduced rotor immersion and performance before stabilizing. The generator powered commercial marine sensors for over 6 h without external batteries, demonstrating the viability of compact, passively cooled thermomagnetic systems for autonomous, off-grid marine sensing.

13 HYDRO ENERGY↗

Liquid lithium divertor analysis using coupled plasma material interaction model

A liquid lithium divertor can improve performance of future fusion devices by creating efficient power exhaust and improving the energy confinement via pumping of the hydrogen isotopes. In addition, significantly higher heat fluxes can be handled if controlled vapor shielding is used to redistribute the divertor heat flux over a wider area. Design and optimization of such a system calls for an analysis model which includes a strong two-way coupling between the plasma and divertor material. The incoming plasma heat and particle flux will affect the divertor surface temperature, which is a defining factor of the lithium evaporative and sputtered flux going into the plasma. Results of the coupled model based on the plasma edge code SOLPS-ITER and the computational fluid dynamics (CFD) code ANSYS-CFX will be presented for different configurations. An analytical slab flow model is used as a heat transfer boundary condition for SOLPS, defining particle flux from the wall via calculation of the surface temperature. At the final step, results of the SOLPS analysis are verified using a 3D CFD magnetohydrodynamics (MHD) analysis which uses heat and particle flux from SOLPS as a boundary condition. In addition to plasma heat flux, both analytical and CFD temperature models include several plasma material interaction effects, such as lithium evaporation, condensation and sputtering based on deuterium target flux. New adatom sputtering model based on the available experimental data is presented. Analytical model is expanded to include free surface axisymmetric configurations. Results of parametric studies of the divertor configurations with different lithium inlet temperature and velocity will be presented leading to the optimal design resulting in the lowest possible lithium contamination in the core.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Generalized Brunauer–Emmett–Teller Isotherm for Mixed-Gas Multilayer Adsorption Equilibria

Here, this work presents a rigorous thermodynamic framework to calculate mixed-gas multilayer adsorption equilibria from single-component isotherms and vapor–liquid equilibria. Named the generalized Brunauer–Emmett–Teller (gBET) isotherm, the newly formulated isotherm considers adsorbent surface heterogeneity, competitive adsorption on the monolayer, condensation–evaporation on the subsequent layers, and adsorbed phase nonideality for the monolayer and the subsequent layers. The monolayer adsorbed phase nonideality is tracked by using an area-based adsorption nonrandom two-liquid activity coefficient model. The adsorbed phase composition and corresponding nonideality in the subsequent layers are calculated at the dew point condition of the mixed gas with either an equation of state or an activity coefficient model for the vapor–liquid equilibria. The proposed model is validated with six single and three binary multilayer adsorption equilibrium systems, and the model results are compared against those from the classical BET isotherm for single-component adsorption and ideal adsorbed solution theory for mixed-gas adsorption equilibria.

09 BIOMASS FUELS↗

Nonequilibrium statistical thermodynamics of multicomponent interfaces

Nonequilibrium interfacial thermodynamics has important implications for crucial biological, physical, and industrial-scale transport processes. Here, we discuss a theory of local equilibrium for multiphase multicomponent interfaces that builds upon the “sharp” interface concept first introduced by Gibbs, allowing for a description of nonequilibrium interfacial processes such as those arising in evaporation, condensation, adsorption, etc. By requiring that the thermodynamics be insensitive to the precise location of the dividing surface, one can identify conditions for local equilibrium and develop methods for measuring the values of intensive variables at the interface. We then use extensive, high-precision nonequilibrium molecular dynamics (NEMD) simulations to verify the theory and establish the validity of the local equilibrium hypothesis. In particular, we demonstrate that equilibrium equations of state are also valid out of equilibrium, and can be used to determine interfacial temperature and chemical potential(s) that are consistent with nonequilibrium generalizations of the Clapeyron and Gibbs adsorption equations. We also show, for example, that, far from equilibrium, temperature or chemical potential differences need not be uniform across an interface and may instead exhibit pronounced discontinuities. However, even in these circumstances, we demonstrate that the local equilibrium hypothesis and its implications remain valid. These results provide a thermodynamic foundation and computational tools for studying or revisiting a wide variety of interfacial transport phenomena.

36 MATERIALS SCIENCE↗

Results of the Analyses of SMECT Mercury Sample Collected During Mercury Pump (MB1) Functional Check

A pump added to remove mercury from the sump of the Slurry Mix Evaporator Condensate Tank (SMECT) in DWPF was successfully tested in 2020, resulting in a sample of contaminated mercury obtained from the Mercury Purification Process (MPP) cell. The mercury in the sump of the SMECT was present as a result of steam stripping of sludge slurry in the Sludge Receipt and Adjustment Tank (SRAT) at DWPF. A schematic of the MPP system provided by DWPF personnel is shown in Appendix A. DWPF personnel supplied the following detailed description of the Hg sampling: “The sample provided is the result of DWPF extraction of mercury by means of the Mercury Pump-Water Cart. The Mercury Pump extracted the sample from the SMECT mercury sump. The pump uses pressurized water to transfer a small amount of mercury to a leachate bucket located at the Lab Mercury cell. The mercury and water were allowed to be self separated, and mercury was gravity decanted from the leachate bucket.” DWPF personnel indicate that the leachate bucket is equipped with both a top stopcock/drain and a lower/bottom stopcock/drain from which the mercury was decanted or drained out, while the separated water layer remained above the mercury during draining. The DWPF customer requested SRNL to analyze the sample for the following: gross alpha/nonvolatile beta analysis and perform a Toxicity Characteristic Leaching Procedure (TCLP) per the Environmental Protection Agency's Test Methods for Evaluating Solid Waste: Physical/Chemical Methods, SW-846. While the TCLP was preferred, a Total Metals analysis of the eight Resource Conservation and Recovery Act (RCRA) metals was deemed acceptable.2 The analytical data collected on this mercury sample will be used in planning for sample disposition as well to start a profile for future Hg disposition of Hg collected from steam stripping.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Evaluation of Technologies to Mitigate the Presence of Gaseous Elemental Mercury in Waste Disposal Containers

A study was conducted to evaluate sorbent technologies that can mitigate the presence of elemental mercury (Hg⁰) in waste containers for mercury-contaminated debris (MCD). Decontamination and demolition (D&D) activities at the Y-12 National Security Complex (Y-12) and other U.S. Department of Energy (DOE) Oak Ridge Reservation (ORR) facilities generate MCD requiring offsite disposal. The debris is packaged in appropriate waste containers and may be temporarily stored onsite prior to transport for treatment and/or disposal. During transportation of loads that had no visible liquid Hg at the point of origin, temperature changes can cause Hg⁰ to evaporate, condense, and form droplets on container walls. Furthermore, vibration during transportation could cause beads of Hg to be released from the debris, container walls, and ceiling, resulting in pools of liquid Hg⁰ on the container floor. Waste acceptance criteria (WAC) limitations for commercial disposal facilities, the Nevada National Security Site (NNSS), and ORR mixed low-level waste landfills prohibit the presence of any free liquids in containers identified as a solid waste form. Potential solutions to mitigate the presence of residual liquids that could be formed through vapor condensation include the use of sorbents or similar materials to capture and stabilize volatile Hg⁰ vapors and thus ensure compliance with landfill WAC requirements. This report summarizes data from small-scale laboratory experiments conducted to evaluate sorbent materials for Hg⁰ vapor suppression and sorption of liquid Hg⁰ that could form under relevant transportation and disposal conditions. A series of experiments was conducted to evaluate commercial sorbent materials and their effectiveness for Hg⁰ sorption across a temperature range from 19.4°C to 60°C. The impact of residual moisture on sorption was investigated under relevant conditions, and leaching tests were performed to assess the stability of Hg⁰ captured sorbent materials. The results provide estimates for sorbent quantities needed for a given Hg⁰ mass loading based on experimental results exposing sorbents to gaseous and liquid Hg⁰ at various mass ratios. Overall, sorbents that were most effective for Hg⁰ vapor suppression were brominated activated carbons, mackinawite-based sorbents coated on vermiculite, and sulfur-modified granular activated carbon. Elevated temperatures and moisture conditions did not result in significant increases of Hg⁰ headspace concentrations, and the materials also demonstrated high sorption capacities for the sorption of liquid Hg⁰.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Two-Phase Cooling for High Packaging Density Planar Inverter: Cooperative Research and Development Final Report, CRADA Number CRD-15-00592

The project objective was to utilize two-phase heat transfer to enable compact and power-dense inverters. The high heat transfer capacity and near isothermal characteristics of two-phase cooling can enable higher power densities, reducing the size and cost of the power electronics system. This project focused on developing efficient, passive (no pump or compressor) two-phase cooling strategies that consist of an air-cooled condenser and evaporator. This report describes the modeling work conducted to design the evaporator and air-cooled condenser for a prototype inverter development work underway in the John Deere. Prototypes of the final evaporator and condenser designs were then fabricated via 3D printing for testing. Experiments on the evaporator confirmed that this component can meet the heat load and junction temperatures requirements for Si IGBT (insulated-gate bipolar transistor) inverter. Experiments with the air-cooled condenser were not possible due to leaks through the condenser walls.

33 ADVANCED PROPULSION SYSTEMS↗

Loss and Isotopic Fractionation of Alkali Elements during Diffusion-Limited Evaporation from Molten Silicate: Theory and Experiments

Moderately volatile elements (MVEs) are variably depleted in planetary bodies, reflecting the imprints of nebular and planetary processes. Among MVEs, Na, K, and Rb are excellent tracers for unraveling the history of MVE depletion in planetary bodies because they have similar geochemical behaviors but can be chemically fractionated by evaporation and condensation processes. Furthermore, K and Rb are amenable to high-precision isotopic analyses, which can help constrain the conditions of evaporation and condensation. To quantitatively understand why Na, K, and Rb are depleted in planetary bodies, we have carried out vacuum evaporation experiments from basaltic melt at 1200 and 1400 °C to study their evaporation kinetics and isotopic fractionations. We chose this composition because it is relevant to evaporation from small differentiated planetesimals. The Rb isotopic compositions of the evaporation residues were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS), and the K isotopic compositions were measured along profiles across the residues by secondary ion mass spectrometry (SIMS). In the 1400 °C run products, we found that the concentrations of both K and Rb in the run products decreased from core to rim, which was accompanied by a heavy K isotope enrichment near the surface. This indicates that, in this run, evaporation was limited by diffusion. To use those data quantitatively, we derive analytical equations that describe the evaporation rate and isotopic fractionation associated with diffusion-limited evaporation from a sphere, slab, and cylinder in transient and quasi-steady state regimes. This model is used to tease out the roles that diffusive transport in the melt and evaporation at the melt/gas interface play in setting the elemental depletion and isotopic composition of the residue. Under our experimental conditions, volatility decreases in the order of Na, Rb, and K. Using our experimental results in a thermodynamic model, we have estimated the product γΓ of activity coefficients × evaporation coefficients of Na, Rb, and K. The measured isotopic compositions of the residues are well explained using Rayleigh distillations, whereby the relative volatilities of K and Rb isotopes are given by the square root of their masses. We use our results and previously published data to predict how K and Rb could have been lost as a function of temperature, melt composition, oxygen fugacity, and saturation degree relevant to Vesta’s building blocks. We find that the K and Rb depletions, K/Rb elemental fractionation, and δ 41 K and δ 87 Rb isotopic fractionations of Vesta (as sampled by howardite-eucrite-diogenite (HED) meteorites) are best explained by evaporation of submillimeter size objects for 0.1-10 years at moderate temperatures (~1050 °C) in a medium ~98.8% saturated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗