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At least 127 records · Page 7

Hanford Low-Activity Waste Processing: Demonstration of the Off-Gas Recycle Flowsheet - 13443

Vitrification of Hanford Low-Activity Waste (LAW) is nominally the thermal conversion and incorporation of sodium salts and radionuclides into borosilicate glass. One key radionuclide present in LAW is technetium-99. Technetium-99 is a low energy, long-lived beta emitting radionuclide present in the waste feed in concentrations on the order of 1-10 ppm. The long half-life combined with a high solubility in groundwater results in technetium-99 having considerable impact on performance modeling (as potential release to the environment) of both the waste glass and associated secondary waste products. The current Hanford Tank Waste Treatment and Immobilization Plant (WTP) process flowsheet calls for the recycle of vitrification process off-gas condensates to maximize the portion of technetium ultimately immobilized in the waste glass. This is required as technetium acts as a semi-volatile specie, i.e. considerable loss of the radionuclide to the process off-gas stream can occur during the vitrification process. To test the process flowsheet assumptions, a prototypic off-gas system with recycle capability was added to a laboratory melter (on the order of 1/200 scale) and testing performed. Key test goals included determination of the process mass balance for technetium, a non-radioactive surrogate (rhenium), and other soluble species (sulfate, halides, etc.) which are concentrated by recycling off-gas condensates. The studies performed are the initial demonstrations of process recycle for this type of liquid-fed melter system. This paper describes the process recycle system, the waste feeds processed, and experimental results. Comparisons between data gathered using process recycle and previous single pass melter testing as well as mathematical modeling simulations are also provided. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Removal of Trace Amounts of Co-60 from NPP Waste Water Using UV-C Irradiation, TiO{sub 2} and Co-Treat Inorganic Ion Exchange Media - 16025

The removal of Co-60 from an aqueous nuclear liquid waste obtained from a BWR NPP was tested using a two-step process. In the first phase the liquid waste was oxidized with ultraviolet irradiation at 254 nm (UV-C irradiation) together with a photo-catalyst, TiO{sub 2} P25 AEROXIDE, to degrade the organic complexing agents present in the solution. During some of the experiments it was noticed that TiO{sub 2} P25 AEROXIDE also removed Co-60 from the solution. In the second phase the UV-C irradiated solution was mixed with inorganic ion exchange media, Co-Treat, to remove the rest of Co-60 from the solution. The effect of pH and contact time with UV-C irradiation were evaluated and both had a noticeable effect on the results. Best results were attained when pH of the initial test solution was lowered to 3.5 ± 0.2 before the UV-C irradiation. From the initial Co-60 activity, 2.2 Bq/ml, the activity decreased to 0.03 ± 0.01 Bq/ml after 24 hours of UV-C irradiation together with the photo-catalyst and mixing with Co-Treat. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Results Of Hg Speciation Testing On DWPF SMECT-1, SMECT-3, And SMECT-5 Samples

The Savannah River National Laboratory (SRNL) was tasked with preparing and shipping samples for Hg speciation by Eurofins Frontier Global Sciences, Inc. in Seattle, WA on behalf of the Savannah River Remediation (SRR) Mercury Task Team. The thirteenth shipment of samples was designated to include Defense Waste Processing Facility (DWPF) Slurry Mix Evaporator Condensate Tank (SMECT) from Sludge Receipt and Adjustment Tank (SRAT) Batch 736 and 738 samples. Triplicate samples of each material were prepared for this shipment. Each replicate was analyzed for seven Hg species: total Hg, total soluble (dissolved) Hg, elemental Hg [Hg(0)], ionic (inorganic) Hg [Hg(I) and Hg(II)], methyl Hg [CH 3 Hg-X, where X is a counter anion], ethyl Hg [CH 3 CH 2 -Hg-X, where X is a counter anion], and dimethyl Hg [(CH 3 ) 2 Hg]. The difference between the total Hg and total soluble Hg measurements gives the particulate Hg concentration, i.e. Hg adsorbed to the surface of particulate matter in the sample but without resolution of the specific adsorbed species. The average concentrations of Hg species in the aqueous samples derived from Eurofins reported data corrected for dilutions performed by SRNL are tabulated.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Solids Erosion Patterns Developed by Pulse Jet Mixers

Millions of gallons of radioactive waste are stored in underground storage tanks at the Hanford Site in Washington State. This waste will be vitrified at the Waste Treatment and Immobilization Plant that is under construction. Vessels in the pretreatment portion of the plant are being configured for processing waste slurries with challenging physical and rheological properties that range from Newtonian slurries to non-Newtonian sludge. Pulse jet mixing technology has been selected for mobilizing and mixing this waste. In the pulse jet mixing process, slurry is expelled from pulse tube nozzles directed towards the vessel floor. The expelled fluid forms a radial jet that erodes the settled layer of solids. The pulse tubes are configured in a ring or multiple rings and operate concurrently. The expelled fluid and mobilized solids traverse toward the center of the tank. At the tank center the jets from pulse tubes in the ring collide and lift solids upward in a central plume. At the end of the pulse, when the desired fluid volume is expelled from the pulse tube, the applied pressure switches to suction and the pulse tube is refilled. This cycle is used to mobilize and mix the tank contents. An initial step of the process is the erosion of solids from the vessel floor by the radial jets that form on the vessel flow beneath each pulse tube. Experiments have been conducted using simulants to evaluate the ability of the pulse jet mixing system radial jets to combine to develop the central upwell and lift solids into the vessel. These experiments have been conducted at three scales using a range of granular simulants over a range of concentrations. The vessels have elliptical, spherical, or flanged and dished bottoms. Process parameters evaluated include the velocity of fluid expelled from the pulse tube, the duration of the pulse and the duty cycle, the ratio of pulse duration to cycle time. Videos taken from beneath the vessel show the growth of the cleared area from each pulse tube as a function of time. All solids are lifted from the vessel bottom when the system is operating at the critical suspension velocity. The focus of this paper is to compare and contrast erosion patterns developed from different simulants and pulse tube configurations. The cases are evaluated to determine how changes in process parameters affects the PJM ability to mobilize solids from the vessel floor.

erosion↗

Scaling Theory for Pulsed Jet Mixed Vessels, Sparging, and Cyclic Feed Transport Systems for Slurries

This document is a previously unpublished work based on a draft report prepared by Pacific Northwest National Laboratory (PNNL) for the Hanford Waste Treatment and Immobilization Plant (WTP) in 2012. Work on the report stopped when WTP’s approach to testing changed. PNNL is issuing a modified version of the document a year later to preserve and disseminate the valuable technical work that was completed. This document establishes technical bases for evaluating the mixing performance of Waste Treatment Plant (WTP) pretreatment process tanks based on data from less-than-full-scale testing, relative to specified mixing requirements. The technical bases include the fluid mechanics affecting mixing for specified vessel configurations, operating parameters, and simulant properties. They address scaling vessel physical performance, simulant physical performance, and “scaling down” the operating conditions at full scale to define test conditions at reduced scale and “scaling up” the test results at reduced scale to predict the performance at full scale. Essentially, this document addresses the following questions: • Why and how can the mixing behaviors in a smaller vessel represent those in a larger vessel? • What information is needed to address the first question? • How should the information be used to predict mixing performance in WTP? The design of Large Scale Integrated Testing (LSIT) is being addressed in other, complementary documents.

non-Newtonian↗

Concentration of HLLW from Future SNF Recycling for Efficient Immobilization in a CCIM

Sponsored by the Department of Energy Nuclear Energy’s Fuel Cycle Research and Development Program, the Cold Crucible Induction Melter is being developed as the next generation of melter technology for High Level Liquid Waste’s efficient immobilization in highly durable glass ceramic and ceramic forms. Concentration of the radioactive High Level Liquid Waste generated from the proposed future recycling of spent nuclear fuel, after the fuel’s dissolution in nitric acid, is necessary to take advantage of the inherent attributes of Cold Crucible Induction Melting technology. Based on a provided range of commercial spent nuclear fuel fission product composition data and its expected High Level Liquid Waste raffinate composition data as provided in oxide form, an analysis was completed to concentrate the waste. The analysis involved using nitric acid vapor liquid equilibrium data over a range of boiling temperatures and performing spreadsheet calculations to concentrate the High Level Liquid Waste through evaporation. The calculation results will provide a concentrated nonradioactive surrogate High Level Liquid Waste melter feed recipe for testing in Idaho National Laboratory’s Cold Crucible Induction Melter Pilot Plant. This testing will provide a quantifiable verification of the relatively high feed rates of Cold Crucible Induction Melters compared to those achievable with the current ceramic lined Joule Heated Melters.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Rationale for evaluating a closed food chain for space habitats

Closed food cycles for long duration space flight and space habitation are examined. Wash water for a crew of six is economically recyclable after a week, while a total closed loop water system is effective only if the stay exceeds six months' length. The stoichiometry of net plant growth is calculated and it is shown that the return of urine, feces, and inedible plant parts to the food chain, along with the addition of photosynthesis, closes the food chain loop. Scenarios are presented to explore the technical feasibility of achieving a closed loop system. An optimal choice of plants is followed by processing, waste conversion, equipment specifications, and control requirements, and finally, cost-effectiveness.

Modell, M.↗

Place Based STEM: Leveraging Local Resources to Engage K-12 Teachers in Teaching Integrated STEM and for Addressing the Local STEM Pipeline

Business, industry, parks, nature settings, government infrastructure, and people, can be invaluable resources for connecting STEM curriculum within context which results in conditions ideal for promoting purposeful learning of authentic STEM content. Thus, community-based STEM resources offer ideal context for teaching STEM content. A benefit of focusing teacher attention on these contextual, content aligned resources is that they are in every community; making place-based STEM education a possibility, regardless of the location of STEM teaching and learning. Further, associating STEM teaching and learning with local resources addresses workforce development and the STEM pipeline by exposing students to STEM careers and applications in their local communities. The desire to align STEM teaching and learning with local STEM related resources guided the design of our week-long integrated STEM K-12 teacher professional development (PD) program, i-STEM. We have completed four years of our i-STEM PD program and have made place-based STEM a major emphasis of our curriculum. This report focuses on the data collected in the fourth year of our program. Our week-long i-STEM PD served over 425 educators last summer (2013), providing them with in depth theme-based integrated STEM short courses which were limited to an average of 15 participants and whole group plenary sessions focused around placed based integrated STEM, inquiry, engineering design, standards and practices of Common Core and 21st Century skills. This state wide PD was distributed in five Idaho community colleges and took place over two weeks. The STEM short courses included topics on engineering for sustainability, using engineering to spark interest in STEM, municipal water systems, health, agriculture, food safety, mining, forestry, energy, and others. Integral to these short courses were field trips designed to connect the K-12 educators to the resources in their local communities that could be leveraged for teaching integrated STEM and provide a relevant context for teaching STEM content. Workplace presentations made by place-based STEM experts and provided teachers field trips to place-base STEM industries and business such as manufacturing plants, waste water treatment systems, mines, nature parks, food processing plants, research, hospitals, and laboratory facilities. We researched the 425 participants’ conceptions of place-based STEM prior to and after their taking part in the summer institutes, which included fieldtrips. Our findings revealed substantial increase in our participants’ knowledge, interest, and plans to use place-based resources for teaching integrated STEM. We detail the data analysis and provide a theoretical foundation and justification for the importance of place-based STEM to address the STEM pipeline for the future workforce.

99 GENERAL AND MISCELLANEOUS↗

Comparative Evaluation of Cutting Methods of Activated Concrete from Nuclear Power Plant Decommissioning - 13548

The amount of radioactive wastes from decommissioning of a nuclear power plant varies greatly depending on factors such as type and size of the plant, operation history, decommissioning options, and waste treatment and volume reduction methods. There are many methods to decrease the amount of decommissioning radioactive wastes including minimization of waste generation, waste reclassification through decontamination and cutting methods to remove the contaminated areas. According to OECD/NEA, it is known that the radioactive waste treatment and disposal cost accounts for about 40 percentage of the total decommissioning cost. In Korea, it is needed to reduce amount of decommissioning radioactive waste due to high disposal cost, about $7,000 (as of 2010) per a 200 liter drum for the low- and intermediate-level radioactive waste (LILW). In this paper, cutting methods to minimize the radioactive waste of activated concrete were investigated and associated decommissioning cost impact was assessed. The cutting methods considered are cylindrical and volume reductive cuttings. The study showed that the volume reductive cutting is more cost-effective than the cylindrical cutting. Therefore, the volume reductive cutting method can be effectively applied to the activated bio-shield concrete. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Does the Perfect Waste Package Exist? Development of a Decisional Tool Addressing this Challenge - 17053

The definition of a safe, technically, economically and societally acceptable waste management strategy is highly dependent on the Waste Acceptance Criteria in each country and on the already available disposal routes. It is the reason why there is not a single solution but a combination of optimized solutions depending on the type of waste and on each country's considerations. In fact, when operating a nuclear plant or performing its decommissioning or legacy waste management, one has to consider a large waste diversity in term of natures, types, volumes and radioactivity spectra. All nuclear operators have to take-up the challenge of implementing solutions for conditioning its waste in packages suitable for transport short to long term interim storage and final disposal of it (or prepare for final disposal if the repository is not yet available). Operators have then to answer the following dilemma: either define a complete strategy packaging the waste for final disposal, or 'containerising' it temporarily, pending final disposal. The strategy is highly country dependent; in the first case, one has to take into account the available information and future orientations relative to acceptability of the packages in order to define a robust solution. The approach implemented in France requires a close dialogue between the Operators, the Safety Authority, the Administration and the stakeholders. Moreover it pushes forward whenever possible standardization, contributing to cost minimization. If the second approach has the advantage of leaving the options open, and reducing the initial investments, it inevitably requires future retrieval and re-packaging with potential evolutions/degradation of the initial waste form. It also induces the potential risk to produce additional secondary waste. As an additional drawback, it introduces uncertainties and unknowns related to the future waste management criteria and to the costs. The general idea is that, depending on context, a given route (i.e., treatment, conditioning, and transport), could be considered as efficient or not. Assessing a waste package is certainly highly context dependent. However it should be possible to recognize and to lead an evaluation based on a number of fixed criteria, whatever the context, to be addressed when assessing the development of a final waste package in connection to the overall management route. A waste package is always a combination of a waste container and a waste form and will have to be transported one day from the production site to the final repository or to off-site interim storage facilities. AREVA's approach consists in defining an evaluation grid based on a set of criteria which aim (i) to evaluate whether the different waste treatments, conditionings, transport and packages deserve to be considered within different national contexts, and (ii) to evaluate R and D actions to be performed for improving existing solutions or developing new ones. One of the key lessons to be drawn from AREVA's experience in developing waste packages is that the perfect waste doesn't exist even though the vitrified canister is probably the most efficient one. The performance of a package resulting from a compromise depends on context and is a strength combination between the waste container and the waste form. The approach is to evaluate a waste package development against different set of criteria and to draw optimization diagrams. In such diagram, a given waste package is assessed with respect to selected criteria such as waste form and waste container, stability, level of waste incorporation, integrity lifetime, secondary waste generation, transport, long term behavior, and economical effectiveness, etc. Addressing a waste form is a very key point. This evaluation grid and comparative approach will be presented through examples and comparison providing from AREVA feedback on waste package development related to complex waste management such as problematic waste or legacy waste. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Selective separation of Sr by potassium titanates from solution of nitrate - 15248

The radioactive waste treatment is planned in LWTF (Low-level radioactive Waste Treatment Facility, JAEA) for the low-level liquid wastes generated from Tokai-reprocessing facility [1]. The target liquid wastes mainly consist of highly concentrated sodium nitrate (4.7 M NaNO{sub 3}) containing low level radioactive {sup 137}Cs and {sup 90}Sr, while the conventional adsorbent (Titanic acid-PAN) has some problems in the adsorption performance and irradiation resistance. In this study, the adsorption properties of Sr{sup 2+} ions, leaching properties of Sr{sup 2+} and irradiation properties were clarified by using the novel adsorbent of potassium titanates (KT-1). Relatively large uptake percentage (99%) and maximum uptake capacity (0.37 mmol/g) were obtained for the KT-1 compared to that of Titanic acid-PAN. As for the breakthrough properties, KT-1 had the smoother breakthrough carve and larger 5% breakthrough capacity compared to Titanic acid-PAN. From the results of batch and column experiments, KT-1 was effective for the uptake of Sr{sup 2+} ions in the presence of highly concentrated Na{sup +} ions. The leached percentages of Sr{sup 2+} ions form calcined products of Sr-KT-1 in pure water and 0.1 M NaOH were less than the detection limit of ICP-AES, and those in 0.1 M HCl tended to markedly decrease with calcining temperature; the formation of SrTiO{sub 3} phase above 800 deg. deg. C was effective for the lowering of leachability. The irradiation stability of the adsorbent was examined by instrumental analyses and the evaluation for the uptake percentage of Sr{sup 2+} ions by batch method. The growth of surface crystal was observed by SEM, but no significant change in X-ray diffraction peak was observed, and Sr{sup 2+} uptake (%) was almost constant. The novel adsorbent of KT-1 had excellent characteristics for Sr selectivity, uptake capacity, leachability and irradiation resistance. KT-1 is thus effective for the treatment and disposal in LWTF. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Radionuclide Inventory Calculations for the Calcined Solid Storage Facility Performance Assessment - 19292

Originally named the Idaho Chemical Processing Plant when it was constructed in the early 1950's, the Idaho Nuclear Technology and Engineering Center reprocessed SNF to recover highly enriched uranium and other nuclear-related products for the U.S. DOE. Reprocessing SNF generated millions of gallons of aqueous radioactive waste. Calcination was a process developed at the INL Site to convert liquid waste into a solid, granular form from 1963 to 2000. The calcination process produced a safer product for storage while reducing the volume of stored liquid waste by an average factor of seven. Calcine is currently stored in the Calcined Solids Storage Facility (CSSF). The CSSFs are often called 'bin sets' because each CSSF (CSSFs 1 through 6) contains several stainless-steel storage bins housed in a concrete vault. The CSSF is an interim waste storage facility. In the future, calcine will be retrieved, treated (if necessary), and sent to an off-Site facility for storage or disposal. To close the CSSF, the bulk of the calcine will be removed and stored or disposed of elsewhere. The bins and vaults will then be placed in a configuration that is protective of human health and the environment. For purposes of the performance assessment, the depth of the residual calcine at closure was assumed to be 5-cm in each bin. The 5-cm of residual calcine in each bin is assumed to be mixed in grout during closure. The activities of the residual radionuclides are the inventory used for the dose assessment calculations for the CSSF performance assessment. The objective of this analysis was to calculate the radionuclide activity in the residual calcine remaining in the CSSF after closure. The purpose of this paper is to present the approach used to calculate the radionuclide inventory of the calcine currently stored in CSSF and the residual calcine in the CSSF after closure using data from the calcined waste Historical Processing Model (HPM). Limited sampling and analysis of the calcine in the CSSF bins was conducted in the past. Future similar calcine sampling and analysis efforts would be costly, generate additional mixed waste, and may not provide the desired detailed calcine composition data. However, during the later years of calcining, an alternative to calcine sampling and analysis was developed and the information was captured in the HPM. The HPM uses multiple sources to provide definitive calcine volume, mass, and composition, including: compositions and volumes of the liquid wastes that were calcined, ORIGEN2 - and ORIGEN-ARP-based radioactivity calculations, calciner and CSSF operating data, and process knowledge of INTEC fuel and waste-processing systems. HPM calcine composition was used to develop an inventory of radionuclides for use in the performance assessment evaluation for closure of CSSF. There are 43 bins that contain calcine, with six to twelve segments in each bin for a total of 337 bin segments for which the HPM calculates the average calcine composition. The HPM calculates the composition of each of the nearly 7,000 batches of material (startup bed, nonradioactive material, and radioactive waste) charged to the calciners. The calculations use the CSSF dimensions, including the CSSF number of bins, heights, outside diameters, annular air space diameter (if necessary), and volume of calcine currently in the bins. For each of the CSSFs, for a 5-cm residual, the percent of total calcine was calculated along with the residual activity for the radionuclides. Residual activity was estimated for 148 different radionuclides. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Applications of CELSS technology to controlled environment agriculture

Controlled environment agriculture (CEA) is defined as the use of environmental manipulation for the commercial production of organisms, whether plants or animals. While many of the technologies necessary for aquaculture systems in North America is nevertheless doubling approximately every five years. Economic, cultural, and environmental pressures all favor CEA over field production for many non-commodity agricultural crops. Many countries around the world are already dependent on CEA for much of their fresh food. Controlled ecological life support systems (CELSS), under development at ARC, KSC, and JSC expand the concept of CEA to the extent that all human requirements for food, oxygen, and water will be provided regenerated by processing of waste streams to supply plant inputs. The CELSS will likely contain plants, humans, possibly other animals, microorganisms and physically and chemical processors. In effect, NASA will create engineered ecosystems. In the process of developing the technology for CELSS, NASA will develop information and technology which will be applied to improving the efficiency, reliability, and cost effectiveness for CEA, improving its resources recycling capabilities, and lessening its environmental impact to negligible levels.

Bates, Maynard E.↗

Low Activity Waste Feed Solids Characterization and Filterability Tests

The primary treatment of the tank waste at the DOE Hanford site will be done in the Waste Treatment and Immobilization Plant (WTP) that is currently under construction. The baseline plan for the WTP Pretreatment facility is to treat the waste, splitting it into High Level Waste (HLW) feed and Low Activity Waste (LAW) feed. Both waste streams are then separately vitrified as glass and sealed in canisters. The LAW glass will be disposed onsite in the Integrated Disposal Facility (IDF). There are currently no plans to treat the waste to remove technetium in the WTP Pretreatment facility, so its disposition path is the LAW glass. Options are being explored to immobilize the LAW portion of the tank waste, i.e., the LAW feed from the WTP Pretreatment facility. Removal of 99 Tc from the LAW Feed, followed by off-site disposal of the 99 Tc, would eliminate a key risk contributor for the IDF Performance Assessment (PA) for supplemental waste forms, and has potential to reduce treatment and disposal costs. Washington River Protection Solutions (WRPS) is developing some conceptual flow sheets for LAW treatment and disposal that could benefit from technetium removal. One of these flow-sheets will specifically examine removing 99 Tc from the LAW feed stream to supplemental immobilization. The conceptual flow sheet of the 99 Tc removal process includes a filter to remove insoluble solids prior to processing the stream in an ion exchange column, but the characteristics and behavior of the liquid and solid phases has not previously been investigated. This report contains results of testing of a simulant that represents the projected composition of the feed to the Supplemental LAW process. This feed composition is not identical to the aqueous tank waste fed to the Waste Treatment Plant because it has been processed through WTP Pretreatment facility and therefore contains internal changes and recycle streams that will be generated within the WTP process. Although a Supplemental LAW feed simulant has previously been prepared, this feed composition differs from that simulant because those tests examined only the fully soluble aqueous solution at room temperature, not the composition formed after evaporation, including the insoluble solids that precipitate after it cools. The conceptual flow sheet for Supplemental LAW immobilization has an option for removal of 99 Tc from the feed stream, if needed. Elutable ion exchange has been selected for that process. If implemented, the stream would need filtration to remove the insoluble solids prior to processing in an ion exchange column. The characteristics, chemical speciation, physical properties, and filterability of the solids are important to judge the feasibility of the concept, and to estimate the size and cost of a facility.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Initial Testing of Off-Gas Recycle Condensate Liquid from the WTP Low Activity Waste Vitrification Process - 16432

The Waste Treatment and Immobilization Plant (WTP) under construction at the Hanford site is designed to treat and immobilize the inventory of High-Level Waste stored in the 177 underground storage tanks. The WTP process flow was designed to pre-treat this waste, separating it into High Level Waste (HLW) and Low Activity Waste (LAW) fractions for vitrification. Vitrification of the waste generates a condensate stream from the off-gas processes originating from two off-gas treatment unit operations, the Submerged Bed Scrubber (SBS) and the Wet Electrostatic Precipitator (WESP). The baseline plan for disposition of the stream from the LAW melter is to recycle it to the Pretreatment facility where it gets evaporated and processed through the LAW melter again. If the Pretreatment facility is unavailable, this baseline disposition pathway is not viable. Additionally, chloride, fluoride, and sulfate are partially volatile in the melter, accumulating to high concentrations while recycling and impacting the glass waste loading and facility throughput. The primary radionuclide that volatizes and accumulates is {sup 99}Tc. The long half-life and environmental mobility of {sup 99}Tc complicates disposal options for this secondary aqueous waste stream. This task is investigating {sup 99}Tc removal to examine the potential for diverting this stream to an alternate disposition path and avoiding impacting the glass waste loading. Separation methods for {sup 99}Tc have focused on using inorganic precipitation agents that can remove it by reducing it from soluble pertechnetate ion, with a +7 oxidation state, to insoluble technetium dioxide in the +4 oxidation state. Stannous chloride (SnCl{sub 2}) has been found highly effective at causing the reduction and precipitating {sup 99}Tc for removal, but it also precipitates other components. The primary competitor that precipitates is chromium, which consumes the redox activity of the Sn(II), causing addition of more of the SnCl{sub 2}. Research has examined the optimum quantity of SnCl{sub 2}, mixing time, and the impact of other redox-active species. It is also important to know the stability of the precipitated {sup 99}Tc in process conditions, since it is expected it will eventually be re-oxidized by oxygen and dissolve. This work is expected to determine if a {sup 99}Tc removal step could be used to decontaminate the bulk of this stream, and make it suitable for other disposal paths so that the chloride, fluoride, and sulfate can be diverted away from the glass melter. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Integrated Waste Treatment Unit (IWTU) Input Coal Analyses and Off-Gass Filter (OGF) Content Analyses

A full engineering scale Fluidized Bed Steam Reformer (FBSR) system is being used at the Idaho Nuclear Technology and Engineering Center (INTEC) to stabilize acidic Low Activity Waste (LAW) known as Sodium Bearing Waste (SBW). The INTEC facility, known as the Integrated Waste Treatment Unit (IWTU), underwent an Operational Readiness Review (ORR) and a Technology Readiness Assessment (TRA) in March 2014. The IWTU began non-radioactive simulant processing in late 2014 and by January, 2015 ; the IWTU had processed 62,000 gallons of simulant. The facility is currently in a planned outage for inspection of the equipment and will resume processing simulated waste feed before commencing to process 900,000 gallons of radioactive SBW. The SBW acidic waste will be made into a granular FBSR product (carbonate based) for disposal in the Waste Isolation Pilot Plant (WIPP). In the FBSR process calcined coal is used to create a CO2 fugacity to force the waste species to convert to carbonate species. The quality of the coal, which is a feed input, is important because the reactivity, moisture, and volatiles (C,H,N,O, and S) in the coal impact the reactions and control of the mineralizing process in the primary steam reforming vessel, the Denitration and Mineralizing Reformer (DMR). Too much moisture in the coal can require that additional coal be used. However since moisture in the coal is only a small fraction of the moisture from the fluidizing steam this can be self-correcting. If the coal reactivity or heating value is too low then the coal feed-rate needs to be adjusted to achieve the desired heat generation. Too little coal and autothermal heat generation in the DMR cannot be sustained and/or the carbon dioxide fugacity will be too low to create the desired carbonate mineral species. Too much coal and excess S and hydroxide species can form. Excess sulfur from coal that (1) is too rich in sulfur or (2) from overfeeding coal can promote wall scale and contribute to corrosion in process piping and materials, in excessive off-gas absorbent loading, and in undesired process emissions. The ash content of the coal is important as the ash adds to the DMR and other vessel products which affect the final waste product mass and composition. The amount and composition of the ash also affects the reaction kinetics. Thus ash content and composition contributes to the mass balance. In addition, sodium, potassium, calcium, sulfur, and maybe silica and alumina in the ash may contribute to wall-scale formation. Sodium, potassium, and alumina in the ash will be overwhelmed by the sodium, potassium, and alumina from the feed but the impact from the other ash components needs to be quantified. A maximum coal particle size is specified so the feed system does not plug and a minimum particle size is specified to prevent excess elutriation from the DMR to the Process Gas Filter (PGF). A vendor specification was used to procure the calcined coal for IWTU processing. While the vendor supplied a composite analysis for the 22 tons of coal (Appendix A), this study compares independent analyses of the coal performed at the Savannah River National Laboratory (SRNL) and at the National Energy Technology Laboratory (NETL). Three supersacks a were sampled at three different heights within the sack in order to determine within bag variability and between bag variability of the coal. These analyses were also compared to the vendor’s composite analyses and to the coal specification. These analyses were also compared to historic data on Bestac coal analyses that had been performed at Hazen Research Inc. (HRI) between 2004-2011.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Decomposition of Select Volatile Organic Compounds by Caustic Hydrolysis for Effluent Management Facility (Rev. 0)

Hydrolysis is a proposed treatment method for organic constituents at the Effluent Management Facility during the Direct-Feed Low-Activity Waste process at the Waste Treatment and Immobilization Plant. Four compounds, acetonitrile, acrylonitrile, acetone, and methylene chloride, comprise a significant portion of the organic constituents identified in the Waste Treatment and Immobilization Plant Effluent Composition Estimate. In support of the Direct-Feed Low-Activity Waste process, the Washington River Protection Solutions Organic Studies Group at the 222-S Laboratory completed a laboratory test of caustic hydrolysis reactions of these four compounds.

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Degradation of Dome Cutting Minerals in Hanford Waste - 13100

At the Hanford Tank Farms, recent changes in retrieval technology require cutting new risers in several single-shell tanks. The Hanford Tank Farm Operator is using water jet technology with abrasive silicate minerals such as garnet or olivine to cut through the concrete and rebar dome. The abrasiveness of these minerals, which become part of the high-level waste stream, may enhance the erosion of waste processing equipment. However, garnet and olivine are not thermodynamically stable in Hanford waste, slowly degrading over time. How likely these materials are to dissolve completely in the waste before the waste is processed in the Waste Treatment and Immobilization Plant can be evaluated using theoretical analysis for olivine and collected direct experimental evidence for garnet. Based on an extensive literature study, a large number of primary silicates decompose into sodalite and cancrinite when exposed to Hanford waste. Given sufficient time, the sodalite also degrades into cancrinite. Even though cancrinite has not been directly added to any Hanford tanks during process times, it is the most common silicate observed in current Hanford waste. By analogy, olivine and garnet are expected to ultimately also decompose into cancrinite. Garnet used in a concrete cutting demonstration was immersed in a simulated supernate representing the estimated composition of the liquid retrieving waste from Hanford tank 241-C-107 at both ambient and elevated temperatures. This simulant was amended with extra NaOH to determine if adding caustic would help enhance the degradation rate of garnet. The results showed that the garnet degradation rate was highest at the highest NaOH concentration and temperature. At the end of 12 weeks, however, the garnet grains were mostly intact, even when immersed in 2 molar NaOH at 80 deg. C. Cancrinite was identified as the degradation product on the surface of the garnet grains. In the case of olivine, the rate of degradation in the high-pH regimes of a waste tank is expected to depend on two main parameters: carbonate is expected to slow olivine degradation rates, whereas hydroxide is expected to enhance olivine dissolution rates. Which of these two competing dissolution drivers will have a larger impact on the dissolution rate in the specific environment of a waste tank is currently not identifiable. In general, cancrinite is much smaller and less hard than either olivine or garnet, so would be expected to be less erosive to processing equipment. Complete degradation of either garnet or olivine prior to being processed at the Waste Treatment and Immobilization Plant cannot be confirmed, however. (authors)

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