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At least 559 records · Page 31

Process optimization of caustic scrubber and iodine-129 immobilization in sodalite-based waste forms

Caustic scrubbers are proposed to remove vaporized iodine from nuclear fuel reprocessing plants. Resulting caustic slurries of radioactive iodine ( 129 I) and other anions can be captured and immobilized into the cage structures of sodalite-type minerals. Here, mixed anion sodalites were hydrothermally synthesized from a simulated caustic scrubber solution containing hydroxide/water, carbonate, chlorine, bromine, iodine, nitrate, and nitrite ions with added kaolinite. Experiments were conducted with twenty-five different sets of process conditions. Resulting powders were characterized by quantitative X-ray diffraction (XRD) and multi-functional thermal analysis, including gravimetry, calorimetry, and mass spectrometry. Using statistical analysis, process variables were tailored to maximize conversion of kaolinite into cage silicates, immobilize caustic scrubber anions, and minimize amorphous content. Further, chemical analysis showed the incorporation of all the targeted ions into the solids. Detailed investigation of a batch characterized after washing (creating secondary waste) and one without washing but subsequent calcination is given. This work contributes to defining the constraints required for subsequent consolidation process steps of the waste form to avoid volatilization.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Morphological controls on flow conductivity and viscosity of bentonite–polymer composites

In this study, the authors investigate the morphological organisation of polymers in bentonite–polymer composites (BPCs) used in geosynthetic clay liners and controls on hydraulic conductivity and viscosity. A limited understanding of the relationship between the microstructure of BPCs and their macroscopic engineering behaviour motivates this study. The polymer resides in the inter-granular pores of bentonite based on synchrotron-based small-angle X-ray scattering measurements, scanning electron microscopy imaging and pore size analyses. On wetting, the polymer swells to produce a swollen hydrogel residing in the inter-granular pores. Enhanced tortuosity arising from hydrogel formation reduces the hydraulic conductivity of BPCs. The higher viscosity of the BPC slurry is attributed to the higher shear resistance emerging from swelling of the polymer fraction on wetting. These findings link the morphological features of BPCs to the observed hydraulic conductivity and viscosity of these materials.

Engineering↗

CT_Data_of_Gas_Migration_in_Setting_Cement

Computed tomography experimental data associated with the submitted manuscript "Migration of air bubbles in a column of cement slurry" by N’dri Arthur Konan, Eilis Rosenbaum, Dustin Crandall, Mehrdad Massoudi. Full description with citation to be updated when manuscript is accepted.

Computed Tomography↗

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↗

Advanced sorbents for modular oxygen production for REMS gasifiers

Under a DOE funded effort, Thermosolv LLC has been developing a sorbent-based oxygen production technology for gasification and oxy-combustion applications. The sorbents utilize oxygen-storage properties of certain perovskites to (1) selectively adsorb oxygen at moderate temperature from compressed air and (2) release the adsorbed oxygen into a vacuum or a sweep gas such as CO2 and/or steam. Through cyclic operations of multiple sorbent beds such a process can be made continuous. Pressure drop across the sorbent bed and other similar design considerations dictate that the sorbent be in the form of a high surface-area-to-volume pellet and yet still possess sufficient crush strength and integrity. Process efficiency is determined by the sorption and desorption kinetics and sorbent capacity. Typical process involves cycle times in the order of 100 seconds, a time too short to fully utilize the full volume of the sorbent and the sorption capacity of the sorbent pellets. As a part of this project, Thermosolv LLC undertook the development of oxygen sorbents as a high-surface area supported sorbent on a light-weight inert support to (1) reduce the cost, (2) increase the productivity, and (3) reduce the overall weight of the reactor. Using a previously developed perovskite (LSCF 1991) with its well-characterized performance, composite sorbent pellets each consisting of an inert core coated by a thin layer of the functional perovskite material were produced. Several low-density, inexpensive inert solids supports in the 1/8”-1/4” size were selected to keep the pressure drop across the sorbent bed in the acceptable range. A number of commercial technologies including spray coating, dip coating, incipient impregnation of porous substrate followed by thermal annealing at various temperatures and duration were employed and tested to produce robust composite supported sorbent pellets. A sense of optimum coating thickness was developed by testing sorbent pellets of various increasing diameter pellets. LSCF-1991extrudates ranging in size from 1/32” to 3/16” were tested in a TGA and in a fixed-bed pressure swing test set-up for sorption/desorption cycles of interest. The data show that for the operational conditions of interest the coating thickness for a supported sorbent pellet needs to be approximately 1/32” (about 0.8 mm). Subsequent work thereby concentrated on developing composite pellets of various substrates, shapes and sizes with coating layer of about this size range. Candidate support materials were chosen based on cost, inertness, mechanical strength, thermal expansion and chemical stability with sorbent material, and in a size range to give an acceptable pressure drop in fixed-bad reactor configurations. Coating application methods used for application of the sorbent onto the support included precipitation, spray coating and dip coating from sorbent slurries and sol gels. For all coated supports where we could successfully apply a uniform coating of desired thickness with an acceptable handling performance in terms of exfoliation, TGA-based cyclic sorption/desorption testing was performed to determine cycling capacity of oxygen. Among nearly twenty different support materials tested, best adhesion performance was obtained from stainless saddle supports. In the bench-scale fixed-bad tests stainless steel saddle support composite pellets with a coating thickness in the 0.6 mm or so range, the composite sorbent pellet performance approached up to 95% of that of the 2 mm parent material pellets. In a parallel approach to reducing the cost of the sorbent, alternate sorbent formulations replacing/reducing the amount of cobalt in the LSCF family were also investigated. Successful formulations that could match the performance of LSCF 1991 were identified based on TGA cyclic tests as LSCF 1919 and LSF 1910. In the range of operational envelop of cycle times and other relevant process operating conditions, the reduced Co formulations showed comparable performance in the bench-scale fixed-bad cyclic operations. As a part of this project, we also attempted substitution of La and Sr with Ca and Ba, and Co with Mn, Ni and Cu with little success, but the overall project goal of reducing sorbent cost in terms of raw material and manufacturing expenses was successful.

01 COAL, LIGNITE, AND PEAT↗

Roll-to-Roll Advanced Materials Manufacturing DOE Laboratory Collaboration (FY2019 Final Report)

R2R processing is used to manufacture a wide range of products for various applications which span many industrial business sectors. The overall R2R methodology has been in use for decades and this continuous technique traditionally involves deposition of material(s) onto moving webs, carriers or other continuous belt-fed or conveyor-based processes that enable successive steps to build a final version which serves to support the deposited materials. Established methods that typify R2R include tape casting, silk-screen printing, reel-to-reel vacuum deposition/coating and R2R lithography. Products supported by R2R manufacturing include micro-electronics, electro-chromic window films, PVs, fuel cells for energy conversion, battery electrodes for energy storage, and barrier and membrane materials. Due to innovation in materials and process equipment, high-quality yet very low-cost multilayer technologies have the potential to be manufactured on a very cost-competitive basis. To move energy-related products from high-cost niche applications to the commercial sector, a means must be available to enable manufacture of these products in a cost-competitive manner that is affordable. Fortunately, products such as fuel cells, thin- and mid-film PVs, batteries, electrochromic and piezoelectric films, water separation membranes, and other energy saving technologies readily lend themselves to manufacture using R2R approaches. However, more early-stage research is needed to solve the challenge of linking the materials (particles, polymers, solvents, additives) used in ink and slurry formulations, though the ink processing, coating and drying processes, to the ultimate performance of the final R2R product, especially for a process that uses multiple layers of deposition to achieve the end product.

42 ENGINEERING↗

Technology Demonstration of a High-Pressure Swirl Oxy-Coal Combustor

This technical report presents the exploration of the design and prototyping of a High-Pressure Swirl Oxy-coal Combustor. Pressurized oxy-coal combustion systems have the potential to improve efficiency along with an increased carbon capture rate. Reduction of flue gas at higher pressure, smaller system size, and capital cost reductions render high-pressure oxy-coal systems particularly attractive as next-generation energy-producing systems. High-pressure oxy-coal combustion systems are a recent concept, and thus operability issues of combustor designs for such systems are not fully understood. Significant challenges exist to maintain oxy-coal combustion stability at elevated pressure and a high CO 2 diluent environment. Although a body of knowledge exists for high-pressure oxygen combustion in rocket engines (or similar applications), it is yet to be strategized how these fundamental concepts can be translated to low-temperature CO 2 diluent combustion regimes. The realization of the pressurized oxy-coal based systems requires combustor components to be designed and demonstrated for an operating pressure over 10 bar. However, pressurized oxy-coal combustor design information at this pressure range and scale relevant to validate those proposed systems is currently limited. Experimental data from MWth scale oxy-coal combustors are needed to identify the optimal trade-off between net efficiency and systems size. The proposed effort is aimed at demonstrating a 1 MWth down-fired swirl Oxy-Coal combustor and investigate the interrelation between combustor operating conditions (pressure; flame stability; flue gas recirculation ratio) and conversion efficiencies to minimize oxygen requirements. One of the key challenges is to configure burner design (i.e., swirl number and injector) and operating conditions for high-pressure oxy-coal combustion systems. These experiments differ from current systems partly due to the high theoretical flame temperature and related burner operability issues associated with oxy-combustion. An ASPEN PLUS® model study for 550 MWe TIPS and ENEL pressurized oxy-coal systems with CO 2 recirculation was performed to evaluate system design, subsystems sizing, and operating condition determination. The system analysis effort included TRL and technology gap determination of subsystems and critical components. This information was scaled to develop design requirements (design pressure and flue gas recirculation: RR Flue Gas = $\frac{m_{flue}}{m_{total}}$) for the 1 MWth combustor. The effects of a wide range of carbon dioxide recirculation ratios on the thermal efficiency of ENEL and TIPS cycles are studied. The pressure of 10 bar and 80 bar are used for ENEL and TIPS cycles, respectively. The thermal efficiency of ENEL is significantly higher than the efficiency of TIPS at a pressure of less than 10 bar. The insights from system analysis were then used to design a 1 MWth swirl oxy-coal combustor. Flame temperature analysis and material strength analysis was performed to determine the combustor thickness. The structural integrity of the combustor was validated by finite element analysis using Abacus® and Hypermesh®. Feasibility of igniters and secondary burners are investigated in successful high-pressure oxy-methane combustion. The secondary burners are designed in such a way that it can operate between 100 to 500 kW firing input. Three generations of the pintle injector were designed based on swirl numbers (S=0, 0.9, and 1.2). Key pintle injector parameters such as pintle size, pintle orifice size, spray pattern were investigated by cold flow tests. Information from these tests was used to modify injector design for smooth and successful operation. A 5 mm pintle orifice size was decided upon as the optimum size for oxy-coal operation for the combustor. Shadow sizing experiments were performed to identify the atomization rate of each injector. Different coal water slurry mixtures (30 – 50% coal by wt% in the mixture) at various total momentum ratios (TMR) were investigated for this purpose. These experiments provided decisive information to choose the best design of the injector. The injector with 1.2 swirl provided higher atomization in all cases than other designs. The mean equivalent droplet size of the jet was similar at different TMR and mixture ratios using this injector, thus making it suitable for use in most cases. Therefore, the 1.2 swirl-pintle injector was chosen for the shakedown test. The combustor and other sub-systems, including feed systems and control and data acquisition, have been manufactured, assembled, and integrated. The total system integration and installation began on July 1, 2020. The shake-down tests and initial operational capability demonstration are expected to be completed by September 30, 2020.

01 COAL, LIGNITE, AND PEAT↗

Tank 50H Mixing Pump Run Time Reassessment

Tank 50H is required to operate a single rotating standard slurry pump for 4.5 hours prior to transfers to the Salt Solution Receipt Tanks (SSRTs) in the Saltstone Production Facility (SPF). This mixing time is required to adequately mix miscible and immiscible liquids within Tank 50H and meet the Saltstone Waste Acceptance Criteria (WAC). The miscible liquids are aqueous solutions of dissolved salts, while the immiscible liquids include organic droplets such as Isopar® L. To support the accelerated salt processing rates from the Salt Waste Processing Facility (SWPF), a desire to reduce the transfer time of Decontaminated Salt Solution (DSS) downstream of SWPF was identified. This document describes the analysis performed to reassess the technical basis for the 4.5 hour mixing requirement for Tank 50H.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Removal of High Specific Activity Fission Products from Uranyl Sulfate Waste Solutions

The Savannah River National Laboratory (SRNL) is currently providing support to SHINE Medical Technologies (SHINE) which plans to deploy a low energy, accelerator-based neutron source to fission low enriched U in a uranyl sulfate target solution for 99 Mo production. The 99 Mo is initially separated from the fission products and target solution by an extraction column. Subsequent washing of the column will generate waste solutions containing residual U and fission product activity. A small number of high specific activity fission products (e.g., 90 Sr, 137 Cs, and 144 Ce) in these streams will likely control the classification of the low level waste (LLW). If a sufficient amount of the high specific activity isotopes are separated from the SHINE waste streams and concentrated into a waste form, it would be possible to treat a majority of the wash solutions from the column operations as a lower class of LLW (Class A versus Class B or C or Class B versus Class C). The high specific activity fission product elements could then be dispositioned as a much smaller volume of waste rather than requiring the disposal of the entire waste stream at the higher waste classification. The Savannah River Site (SRS) has experience with using monosodium titanate (MST) and crystalline silicotitanate (CST) to remove Cs and Sr from high salt content waste solutions generated during the reprocessing of nuclear fuels and targets. Both of these materials have worked very well for their intended purposes at the SRS where the fission product elements are removed from highly alkaline waste. On the other hand, SHINE waste streams from the extraction column contain H 2 SO 4 which makes the solution acidic. Additionally, the SRS waste streams do not contain other fission product elements such as transition metals or lanthanides because they precipitate upon neutralization of the SRS waste and are not present in the supernate which is dispositioned as LLW following treatment. As such, there are inherent differences between SHINE and SRS waste treatment strategies. Savannah River National Laboratory was tasked with performing scoping studies to see if MST and CST would remove Sr, Cs, and Ce from an acidic mixed metal simulant solution. Batch contact experiments were performed using MST and two CST type materials. The MST material is a 15 wt % powder in 0.15 M NaOH slurry. The MST showed low adsorption for elements of interest from acidic solution. Furthermore, the powder size makes MST non-ideal for column operations. A CST IE-911 ion exchange material had high Cs adsorption, moderate Sr, and marginal Ce adsorption. Based on adsorption of all species, the ion exchange capacity was found to be 0.032 meq/mL. A bench-top column experiment to measure elemental breakthrough curves was performed using CST IE-911 where chromatographic separations of the mixed simulant were expected to occur. While most elements behaved as expected, the lanthanide series, containing Ce, broke though the column earlier than expected. The second CST material, CST R9120, displayed high adsorption for all elements in the acidic mixed simulant solutions in a batch contact study, and had a calculated loading capacity of 0.091 meq/mL. Future studies to develop a waste treatment flowsheet should focus on CST R9120 to treat SHINE waste solutions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Additive Manufacturing of Energy Harvesting Material System for Active Wireless MEMS Sensors

Combustion systems make up a large sum of the world’s yearly energy production despite advances in renewable energy sources. Precise control of pressure and temperature in combustion chambers allows for lower carbon emissions, and overall higher efficiency. Wireless temperature and pressure sensors are critical for the operation of combustion chambers. Energy harvesters have emerged as a viable way to power wireless sensors when heat and mechanical energy are available. Lithium niobate (LNB), barium titanate (BTO), and lead zirconate titanate (PZT) pyroelectric ceramics were studied and fabricated through additive manufacturing (AM) for use as energy harvesting structures in combustion environments. The electric power generation potential of LNB and PZT ceramics was studied by varying the temperature from 50 to 60 °C and by introducing cyclic compression loads of 2000 N amplitude. It was found that thermal energy conversion had the highest output of 500 nW and that combined thermal and mechanical conversion did not increase the harvesting potential because of the competing contributions of both effects. Powder bed and slurry extrusion AM methods were used to fabricate BTO and PZT ceramic structures. Optimization of the powder-based binder jetting method produced BTO ceramics with a relative density of 36.77% a piezoelectric coefficient of 153 pC/N. The density of the ceramics increased up to 56% when increasing the saturation of binder in the powder to because of liquid phase sintering. Finally, PZT structures were manufactured through AM and fin features were added to the design to enhance the heat transfer along the material. The harvested power density of the flat samples was 3.643 μW/cm 3 and of the finned samples was 3.034 μW/cm3. This research paves the ways for the development of self-powered wireless sensors in critical areas of operation such as combustion.

01 COAL, LIGNITE, AND PEAT↗

DPC Cement Filler Development (Progress Report)

The fillers research and development (R&D) program, mostly experimental, is part of a broader R&D program that includes new process modeling and performance assessment of criticality effects and the overall importance of criticality to repository performance (consequence screening). A literature research and consultation effort with experts by Hardin and Brady (2018) identified several potentially effective and workable filler materials including cements (primarily phosphate based), moltenmetal alloys, and low-temperature glasses. Filler attributes were defined, and the preliminary lists were compared qualitatively. Further comparative analysis will be done (e.g., cost estimates) after experimental screening has narrowed the list of alternatives. The following cement filler compositions were selected for experimental development work and accelerated testing in FY20: Aluminum phosphate cements (APCs); more specifically aluminum oxide / aluminum phosphate (Al 2 O 3 / AlPO 4 ) cements in which Al 2 O 3 serves as the filler material bound by an AlPO 4 binder formed by the reaction of Al 2 O 3 with H 3 PO 4 ; Calcium phosphate cements (CPCs); more specifically composed of pure or nearly pure hydroxyapatite or HAP (Ca 5 (PO 4 ) 3 (OH)); Wollastonite phosphate cements (WPC), specifically wollastonite and aluminum or calcium aluminum phosphates in which CaSiO 3 serves as the filler material and the phosphate serves as the binder. The FY20 effort focused on the optimization of compositions and subsequent processing of these three materials to achieve dense and well-consolidated monolithic samples with 30 to 40% porosity and permeabilities of 1 millidarcy. At the close of this progress report the aluminum phosphate cements (APCs) and the wollastonite phosphate cements (WPCs) appear to show the most promise for continued development. Less progress has been made with the calcium phosphate cements (CPCs); their slurry viscosities are high (and difficult to measure) and they exhibit relatively short cure times of 2 to 3 hours with concomitant and excessive volatile (e.g. CO 2 ) generation.

36 MATERIALS SCIENCE↗

Modeling DWPF Hydrogen Gas Retention and Release

Savannah River Remediation (SRR) currently manages the risk for retained hydrogen in the Defense Waste Processing Facility (DWPF) vessels by implementing a Retained Hydrogen Program. The current program conservatively relies on bounding assumptions concerning gas release and retention to develop allowable vessel Q-times. SRR would like to establish more realistic inputs to the Retained Hydrogen Program. To address this need, SRNL conducted a literature search on work investigating the retention and release of gas from DWPF type slurries. The search revealed that the retained hydrogen is not released instantaneously upon the start of agitation, and that hydrogen gas could be released under quiescent, non-agitated, conditions. The literature search also identified a Lattice-Boltzmann computational fluid dynamics (CFD) software that could model and predict hydrogen release from DWPF vessels. SRR requested that Savannah River National Laboratory (SRNL) personnel pursue this software and focus the model for hydrogen gas retention and release to justify relaxing these conservative assumptions. This report documents the refinement of the CFD software model and application to show its ability to describe retained hydrogen release from DWPF vessels and relax the conservativisms in the Retained Hydrogen Program.

08 HYDROGEN↗

Novel Algae Technology for CO2 Utilization

The United States, the world’s largest energy user and second largest CO2 emitter, is heavily dependent on fossil energy. In 2014, U.S. coal burning utilities emitted ~1562 million (MM) tons/year (TPY) of CO2 into the atmosphere, accounting for 76% of the total US power sector emissions1. Hence, reducing the CO2 emission footprint from coal plants is widely viewed as a key element in mitigating global warming. Despite significant interest, implementation of CO2 capture technologies has been constrained by the high capture cost which significantly increases the total cost of electricity. Not only is capturing CO2 with traditional technologies expensive, but generally the CO2 has little value and additional expense must be incurred for sequestration. This project funded by a SBIR grant from the U.S. D.O.E. to Helios-NRG in collaboration with the State University of New York at Buffalo (UB) and Membrane Technology and Research Inc. (MTR) aimed to develop a novel, algae based technology to capture CO2 from the effluent of coal-based power plants and convert it to renewable bio-fuels and higher value co-products such as animal feed and nutraceuticals with the potential to enable a substantial reduction in the net cost of carbon capture. The Phase 2 project was aimed at further demonstrating the technical feasibility of the proposed multi-stage continuous (MSC) flow CO2 capture system and the generation of high-value co-products to offset the CO2 capture cost. The project was completed and the project objectives were met and exceeded. A first-of-a-kind integrated, laboratory scale MSC process unit was fabricated and tested in a greenhouse. The tests were conducted with the preferred algae species identified in Phase I and simulated flue gas containing contaminants at levels typically present in the post flue gas desulfurization (FGD) stream, including ~12% CO2, acid gas (SOX, NOX), and a large number of heavy metals. The tests were successful and demonstrated a 25g/m2/day seasonal average algae productivity and an 80% CO2 capture efficiency. Two new algae species were identified for high-value nutraceutical production. Studies to improve growth rate and nutraceutical content of these algae species were performed and a pathway for further improvements was identified. A new dewatering technology called DeAqua was further advanced. Significant improvement in the performance index was achieved. The anti-fouling membrane was developed and fabricated into a module. The fabricated membrane module was tested with algae slurry and demonstrated improved fouling resistant properties, that can potentially reduce the cost and energy of the critical dewatering step. Test data were used to simulate operation of the overall process. The preliminary economic analysis was updated and modelled based on a 5000-acre algae farm. To the extent possible, the financial and operating assumptions used were the same as those used in the DOE’s 2022 projections for algae technology for CO2 capture and utilization. The results showed the proposed technology’s potential to significantly reduce the cost of CO2 capture compared to current options and that the high value products generated from the CO2 captured can make a step change in the cost of carbon capture. Plans to advance the technology to Phase 2B were developed and potential end-user partners were identified.

Maloney, James↗

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.

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↗

Staged OMB for Modular Gasifier/Burner

The goal of this final project report is to comprehensively summarize the work conducted on project DE-FE0031506. In accordance with the Statement of Project Objectives (SOPO), the University of Kentucky Center for Applied Energy Research (UK CAER) (Recipient) has developed a staged opposed multi-burner (OMB) gasifier, scaled down from a commercial gasification technology to utilize coal slurry as feed for the high-temperature gasification. The project involved the design, fabrication, commissioning, parametric testing, and performance validation of the entrained gasifier with multiple burners to narrow the major near-term technical gaps that impede the application of small-size gasification by modularizing the system. Project results verified the UK CAER approach to address the major technical challenges on the gasification modularization for a distributed application at a small scale of 1-5 MWe, while maintaining advantages in cost and flexibility, which include: 1) a cost-effective burner configuration to provide high flexibility in both load and fuel feed; 2) the modularized staged-OMB to provide better gasification performance such as a desired temperature profile, better fuel conversion, better gasification efficiency, and long lifetimes of the refractory wall and burners; and 3) load control simply through changing the number of burners firing. UK CAER’s staged gasifier configuration, fuel blend performance, and economic evaluation shows promise, as summarized in this report, as an effective means for improved gasification efficiency with reduced operation cost and process complexity.

01 COAL, LIGNITE, AND PEAT↗

Sludge Batch 10 Flowsheet Testing with Non-radioactive Simulants

Fourteen Chemical Processing Cell (CPC) simulations were performed with nonradioactive sludge simulants at the Aiken County Technology Laboratory in Aiken, SC. Four of these experiments were performed with Tank 51 sludge simulant. The remaining ten were performed with Tank 40 sludge simulant. The purpose of these experiments was to elucidate the chemistry and characteristics of Sludge Batch (SB) 10 as anticipated in the Defense Waste Processing Facility (DWPF). Experiments were performed at acid stoichiometries between 76% and 138% of the Koopman Minimum Acid requirement (85% - 144% of the Hsu acid requirement) and at REDuction/OXidation (REDOX) targets between 0.1 and 0.3. Testing examined the impact of coupled operations and sludge-only operations during Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) processing at both design basis and nominal boilup rates. This report shares conclusions made as a result of this testing.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Increased Fissile Loading Flowsheet Review

A request was made by H-Canyon Process Engineering to assess the impact of blending dissolved, neutralized Spent Nuclear Fuel (SNF) with future sludge batches and their impact on downstream processing facilities including the Concentration, Storage and Transfer Facilities (CSTF), the Salt Waste Processing Facility (SWPF), the Defense Waste Processing Facility (DWPF), Saltstone, and the Effluent Treatment Facility (ETF). The purpose of this change is to accelerate the deinventory of SNF which is currently stored in the L-Area Disassembly Basin. The addition of SNF increases the mass of fissiles in each future sludge batch, due to their high enrichment. This high enrichment has the potential to complicate the programs to eliminate criticality events in the downstream processing facilities and will increase the number of canisters produced by DWPF because of the SNF mass increase. A separate report addressed the impacts to glass. The review and subsequent calculations were based on average predicted compositions of Accelerated Basin Deinventory (ABD) slurry, average compositions for predicted future sludge batches, average past salt batches and average past recycle batches to predict the feeds that will be processed in SWPF, DWPF, Saltstone, the 2H evaporator and ETF. Each of the processes was evaluated for potential issues.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗