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DEVELOPING AN OPTIMIZED PROCESS STRATEGY FOR ACID CLEANING OF THE SAVANNAH RIVERSITE HLW TANKS

Description: At the Savannah River Site (SRS), there remains approximately 35 million gallons of High Level Waste (HLW) that was mostly created from Purex and SRS H-Area Modified (HM) nuclear fuel cycles. The waste is contained in approximately forty-nine tanks fabricated from commercially available carbon steel. In order to minimize general corrosion, the waste is maintained as very-alkaline solution. The very-alkaline chemistry has caused hydrated metal oxides to precipitate and form a sludge heel. Over the years, the sludge waste has aged, with some forming a hardened crust. To aid in the removal of the sludge heels from select tanks for closure the use of oxalic acid to dissolve the sludge is being investigated. Developing an optimized process strategy based on laboratory analyses would be prohibitively costly. This research, therefore, demonstrates that a chemical equilibrium based software program can be used to develop an optimized process strategy for oxalic acid cleaning of the HLW tanks based on estimating resultant chemistries, minimizing resultant oxalates sent to the evaporator, and minimizing resultant solids sent to the Defense Waste Processing Facility (DWPF).
Date: December 4, 2006
Creator: Ketusky, E
Partner: UNT Libraries Government Documents Department

EFFECTIVENESS OF USING DILUTE OXALIC ACID TO DISSOLVEHIGH LEVEL WASTE IRON BASED SLUDGE SIMULANT

Description: At the Savannah River Site (SRS), near Aiken South Carolina, there is a crucial need to remove residual quantities of highly radioactive iron-based sludge from large select underground storage tanks (e.g., 19,000 liters of sludge per tank), in order to support tank closure. The use of oxalic acid is planned to dissolve the residual sludge, hence, helping in the removal. Based on rigorous testing, primarily using 4 and 8 wt% oxalic acid solutions, it was concluded that the more concentrated the acid, the greater the amount of residual sludge that would be dissolved; hence, a baseline technology on using 8 wt% oxalic acid was developed. In stark contrast to the baseline technology, reports from other industries suggest that the dissolution will most effectively occur at 1 wt% oxalic acid (i.e., maintaining the pH near 2). The driver for using less oxalic acid is that less (i.e., moles) would decrease the severity of the downstream impacts (i.e., required oxalate solids removal efforts). To determine the initial feasibility of using 1 wt% acid to dissolve > 90% of the sludge solids, about 19,000 liters of representative sludge was modeled using about 530,000 liters of 0 to 8 wt% oxalic acid solutions. With the chemical thermodynamic equilibrium based software results showing that 1 wt% oxalic acid could theoretically work, simulant dissolution testing was initiated. For the dissolution testing, existing simulant was obtained, and an approximate 20 liter test rig was built. Multiple batch dissolutions of both wet and air-dried simulant were performed. Overall, the testing showed that dilute oxalic acid dissolved a greater fraction of the stimulant and resulted in a significantly larger acid effectiveness (i.e., grams of sludge dissolved/mole of acid) than the baseline technology. With the potential effectiveness confirmed via simulant testing, additional testing, including radioactive sludge testing, is planned.
Date: July 11, 2008
Creator: Ketusky, E
Partner: UNT Libraries Government Documents Department

REINVESTIGATING THE PROCESS IMPACTS FROM OXALIC ACIDHIGH LEVEL WASTE TANK CLEANING

Description: The impacts and acceptability of using oxalic acid to clean the Savannah River Site, High Level Waste Tanks 1-8, were re-investigated using a two-phased approach. For the first phase, using a representative Tank 1-8 sludge, the chemical equilibrium based software, OLI ESP{copyright} and Savannah River Site laboratory test results were used to develop a chemically speciated material balance and a general oxalate mass balance. Using 8 wt% oxalic acid with a 100% molar excess, for every 1 kg of sludge solid that was dissolved, about 3.4 kg of resultant solids would form for eventual vitrification, while about 0.6 kg of soluble oxalate would precipitate in the evaporator system, and form a salt heel. Using available analyses, a list of potential safety and process impacts were developed, screened, and evaluated for acceptability. The results showed that the use of oxalic acid had two distinct types of impacts, those which were safety based and required potential upgrades or additional studies. Assuming such were performed and adequate, no further actions were required. The second type of impacts were also acceptable, but were long-term, and as such, would need to be managed. These impacts were directly caused by the solubility characteristics of oxalate in a concentrated sodium solution and, occurred after pH restoration. Since oxalate destruction methods are commonly available, their use should be considered. Using an oxalate destruction method could enable the benefits of oxalic to applied, while eliminating the long-term impacts that must be managed, and hence should be considered.
Date: January 22, 2008
Creator: Ketusky, E
Partner: UNT Libraries Government Documents Department

COMPARISON OF OXALIC ACID CLEANING RESULTS AT SRS AND HANFORD AND THE IMPACT ON ENHANCED CHEMICAL CLEANING DEPLOYMENT

Description: Waste tanks must be rendered clean enough to satisfy very rigorous tank closure requirements. During bulk waste removal, most of the radioactive sludge and salt waste is removed from the waste tank. The waste residue on the tank walls and interior components and the waste heel at the bottom of the tank must be removed prior to tank closure to render the tank clean enough to meet the regulatory requirement for tank closure. Oxalic acid has been used within the DOE complex to clean residual materials from carbon steel tanks with varying degrees of success. Oxalic acid cleaning will be implemented at both the Savannah River Site and Hanford to clean tanks and serves as the core cleaning technology in the process known as Enhanced Chemical Cleaning. Enhanced Chemical Cleaning also employs a process that decomposes the spent oxalic acid solutions. The oxalic acid cleaning campaigns that have been performed at the two sites dating back to the 1980's are compared. The differences in the waste characteristics, oxalic acid concentrations, flushing, available infrastructure and execution of the campaigns are discussed along with the impact on the effectiveness of the process. The lessons learned from these campaigns that are being incorporated into the project for Enhanced Chemical Cleaning are also explored.
Date: January 5, 2010
Creator: Spires, R. & Ketusky, E.
Partner: UNT Libraries Government Documents Department

ACTUAL-WASTE TESTING OF ULTRAVIOLET LIGHT TO AUGMENT THE ENHANCED CHEMICAL CLEANING OF SRS SLUDGE

Description: In support of Savannah River Site (SRS) tank closure efforts, the Savannah River National Laboratory (SRNL) conducted Real Waste Testing (RWT) to evaluate Enhanced Chemical Cleaning (ECC), an alternative to the baseline 8 wt% oxalic acid (OA) chemical cleaning technology for tank sludge heel removal. ECC utilizes a more dilute OA solution (2 wt%) and an oxalate destruction technology using ozonolysis with or without the application of ultraviolet (UV) light. SRNL conducted tests of the ECC process using actual SRS waste material from Tanks 5F and 12H. The previous phase of testing involved testing of all phases of the ECC process (sludge dissolution, OA decomposition, product evaporation, and deposition tank storage) but did not involve the use of UV light in OA decomposition. The new phase of testing documented in this report focused on the use of UV light to assist OA decomposition, but involved only the OA decomposition and deposition tank portions of the process. Compared with the previous testing at analogous conditions without UV light, OA decomposition with the use of UV light generally reduced time required to reach the target of <100 mg/L oxalate. This effect was the most pronounced during the initial part of the decomposition batches, when pH was <4. For the later stages of each OA decomposition batch, the increase in OA decomposition rate with use of the UV light appeared to be minimal. Testing of the deposition tank storage of the ECC product resulted in analogous soluble concentrations regardless of the use or non-use of UV light in the ECC reactor.
Date: July 10, 2012
Creator: Martino, C.; King, W. & Ketusky, E.
Partner: UNT Libraries Government Documents Department

ACTUAL-WASTE TESTS OF ENHANCED CHEMICAL CLEANING FOR RETRIEVAL OF SRS HLW SLUDGE TANK HEELS AND DECOMPOSITION OF OXALIC ACID

Description: Savannah River National Laboratory conducted a series of tests on the Enhanced Chemical Cleaning (ECC) process using actual Savannah River Site waste material from Tanks 5F and 12H. Testing involved sludge dissolution with 2 wt% oxalic acid, the decomposition of the oxalates by ozonolysis (with and without the aid of ultraviolet light), the evaporation of water from the product, and tracking the concentrations of key components throughout the process. During ECC actual waste testing, the process was successful in decomposing oxalate to below the target levels without causing substantial physical or chemical changes in the product sludge.
Date: January 12, 2012
Creator: Martino, C.; King, W. & Ketusky, E.
Partner: UNT Libraries Government Documents Department

ADVANCED OXIDATION: OXALATE DECOMPOSITION TESTING WITH OZONE

Description: At the Savannah River Site (SRS), oxalic acid is currently considered the preferred agent for chemically cleaning the large underground Liquid Radioactive Waste Tanks. It is applied only in the final stages of emptying a tank when generally less than 5,000 kg of waste solids remain, and slurrying based removal methods are no-longer effective. The use of oxalic acid is preferred because of its combined dissolution and chelating properties, as well as the fact that corrosion to the carbon steel tank walls can be controlled. Although oxalic acid is the preferred agent, there are significant potential downstream impacts. Impacts include: (1) Degraded evaporator operation; (2) Resultant oxalate precipitates taking away critically needed operating volume; and (3) Eventual creation of significant volumes of additional feed to salt processing. As an alternative to dealing with the downstream impacts, oxalate decomposition using variations of ozone based Advanced Oxidation Process (AOP) were investigated. In general AOPs use ozone or peroxide and a catalyst to create hydroxyl radicals. Hydroxyl radicals have among the highest oxidation potentials, and are commonly used to decompose organics. Although oxalate is considered among the most difficult organic to decompose, the ability of hydroxyl radicals to decompose oxalate is considered to be well demonstrated. In addition, as AOPs are considered to be 'green' their use enables any net chemical additions to the waste to be minimized. In order to test the ability to decompose the oxalate and determine the decomposition rates, a test rig was designed, where 10 vol% ozone would be educted into a spent oxalic acid decomposition loop, with the loop maintained at 70 C and recirculated at 40L/min. Each of the spent oxalic acid streams would be created from three oxalic acid strikes of an F-area simulant (i.e., Purex = high Fe/Al concentration) and H-area simulant (i.e., H ...
Date: February 29, 2012
Creator: Ketusky, E. & Subramanian, K.
Partner: UNT Libraries Government Documents Department

SAVANNAH RIVER SITE TANK CLEANING: CORROSION RATE FOR ONE VERSUS EIGHT PERCENT OXALIC ACID SOLUTION

Description: Until recently, the use of oxalic acid for chemically cleaning the Savannah River Site (SRS) radioactive waste tanks focused on using concentrated 4 and 8-wt% solutions. Recent testing and research on applicable dissolution mechanisms have concluded that under appropriate conditions, dilute solutions of oxalic acid (i.e., 1-wt%) may be more effective. Based on the need to maximize cleaning effectiveness, coupled with the need to minimize downstream impacts, SRS is now developing plans for using a 1-wt% oxalic acid solution. A technology gap associated with using a 1-wt% oxalic acid solution was a dearth of suitable corrosion data. Assuming oxalic acid's passivation of carbon steel was proportional to the free oxalate concentration, the general corrosion rate (CR) from a 1-wt% solution may not be bound by those from 8-wt%. Therefore, after developing the test strategy and plan, the corrosion testing was performed. Starting with the envisioned process specific baseline solvent, a 1-wt% oxalic acid solution, with sludge (limited to Purex type sludge-simulant for this initial effort) at 75 C and agitated, the corrosion rate (CR) was determined from the measured weight loss of the exposed coupon. Environmental variations tested were: (a) Inclusion of sludge in the test vessel or assuming a pure oxalic acid solution; (b) acid solution temperature maintained at 75 or 45 C; and (c) agitation of the acid solution or stagnant. Application of select electrochemical testing (EC) explored the impact of each variation on the passivation mechanisms and confirmed the CR. The 1-wt% results were then compared to those from the 8-wt%. The immersion coupons showed that the maximum time averaged CR for a 1-wt% solution with sludge was less than 25-mils/yr for all conditions. For an agitated 8-wt% solution with sludge, the maximum time averaged CR was about 30-mils/yr at 50 C, and 86-mils/yr at 75 C. ...
Date: January 20, 2011
Creator: Ketusky, E. & Subramanian, K.
Partner: UNT Libraries Government Documents Department

CORROSION TESTING OF CARBON STEEL IN OXALIC ACID CHEMICAL CLEANING SOLUTIONS

Description: Radioactive liquid waste has been stored in underground carbon steel tanks for nearly 60 years at the Savannah River Site. The site is currently in the process of removing the waste from these tanks in order to place it into vitrified, stable state for longer term storage. The last stage in the removal sequence is a chemical cleaning step that breaks up and dissolves metal oxide solids that cannot be easily pumped out of the tank. Oxalic acid has been selected for this purpose because it is an effective chelating agent for the solids and is not as corrosive as other acids. Electrochemical and immersion studies were conducted to investigate the corrosion behavior of carbon steel in simulated chemical cleaning environments. The effects of temperature, agitation, and the presence of sludge solids in the oxalic acid on the corrosion rate and the likelihood of hydrogen evolution were determined. The testing showed that the corrosion rates decreased significantly in the presence of the sludge solids. Corrosion rates increased with agitation, however, the changes were less noticeable.
Date: October 14, 2011
Creator: Wiersma, B.; Mickalonis, J.; Subramanian, K. & Ketusky, E.
Partner: UNT Libraries Government Documents Department

ENHANCED CHEMICAL CLEANING: A NEW PROCESS FOR CHEMICALLY CLEANING SAVANNAH RIVER WASTE TANKS

Description: The Savannah River Site (SRS) has 49 high level waste (HLW) tanks that must be emptied, cleaned, and closed as required by the Federal Facilities Agreement. The current method of chemical cleaning uses several hundred thousand gallons per tank of 8 weight percent (wt%) oxalic acid to partially dissolve and suspend residual waste and corrosion products such that the waste can be pumped out of the tank. This adds a significant quantity of sodium oxalate to the tanks and, if multiple tanks are cleaned, renders the waste incompatible with the downstream processing. Tank space is also insufficient to store this stream given the large number of tanks to be cleaned. Therefore, a search for a new cleaning process was initiated utilizing the TRIZ literature search approach, and Chemical Oxidation Reduction Decontamination--Ultraviolet (CORD-UV), a mature technology currently used for decontamination and cleaning of commercial nuclear reactor primary cooling water loops, was identified. CORD-UV utilizes oxalic acid for sludge dissolution, but then decomposes the oxalic acid to carbon dioxide and water by UV treatment outside the system being treated. This allows reprecipitation and subsequent deposition of the sludge into a selected container without adding significant volume to that container, and without adding any new chemicals that would impact downstream treatment processes. Bench top and demonstration loop measurements on SRS tank sludge stimulant demonstrated the feasibility of applying CORD-UV for enhanced chemical cleaning of SRS HLW tanks.
Date: January 17, 2008
Creator: Ketusky, E; Neil Davis, N & Renee Spires, R
Partner: UNT Libraries Government Documents Department

Computed isotopic inventory and dose assessment for SRS fuel and target assemblies

Description: Past studies have identified and evaluated important radionuclide contributors to dose from reprocessed spent fuel sent to waste for Mark 16B and 22 fuel assemblies and for Mark 31 A and 31B target assemblies. Fission-product distributions after a 5- and 15-year decay time were calculated for a ``representative`` set of irradiation conditions (i.e., reactor power, irradiation time, and exposure) for each type of assembly. The numerical calculations were performed using the SHIELD/GLASS system of codes. The sludge and supernate source terms for dose were studied separately with the significant radionuclide contributors for each identified and evaluated. Dose analysis considered both inhalation and ingestion pathways: The inhalation pathway was analyzed for both evaporative and volatile releases. Analysis of evaporative releases utilized release fractions for the individual radionuclides as defined in the ICRP-30 by DOE guidance. A release fraction of unity was assumed for each radionuclide under volatile-type releases, which would encompass internally initiated events (e.g., fires, explosions), process-initiated events, and externally initiated events. Radionuclides which contributed at least 1% to the overall dose were designated as significant contributors. The present analysis extends and complements the past analyses through considering a broader spectrum of fuel types and a wider range of irradiation conditions. The results provide for a more thorough understanding of the influences of fuel composition and irradiation parameters on fission product distributions (at 2 years or more). Additionally, the present work allows for a more comprehensive evaluation of radionuclide contributions to dose and an estimation of the variability in the radionuclide composition of the dose source term that results from the spent fuel sent to waste encompassing a broad spectrum of fuel compositions and irradiation conditions.
Date: June 19, 1995
Creator: Chandler, M.C.; Ketusky, E.T. & Thoman, D.C.
Partner: UNT Libraries Government Documents Department

Single Stage Contactor Testing Of The Next Generation Solvent Blend

Description: The Modular Caustic Side Solvent Extraction (CSSX) Unit (MCU) facility at the Savannah River Site (SRS) is actively pursuing the transition from the current BOBCalixC6 based solvent to the Next Generation Solvent (NGS)-MCU solvent to increase the cesium decontamination factor. To support this integration of NGS into the MCU facility the Savannah River National Laboratory (SRNL) performed testing of a blend of the NGS (MaxCalix based solvent) with the current solvent (BOBCalixC6 based solvent) for the removal of cesium (Cs) from the liquid salt waste stream. This testing utilized a blend of BOBCalixC6 based solvent and the NGS with the new extractant, MaxCalix, as well as a new suppressor, tris(3,7dimethyloctyl) guanidine. Single stage tests were conducted using the full size V-05 and V-10 liquid-to-liquid centrifugal contactors installed at SRNL. These tests were designed to determine the mass transfer and hydraulic characteristics with the NGS solvent blended with the projected heel of the BOBCalixC6 based solvent that will exist in MCU at time of transition. The test program evaluated the amount of organic carryover and the droplet size of the organic carryover phases using several analytical methods. The results indicate that hydraulically, the NGS solvent performed hydraulically similar to the current solvent which was expected. For the organic carryover 93% of the solvent is predicted to be recovered from the stripping operation and 96% from the extraction operation. As for the mass transfer, the NGS solvent significantly improved the cesium DF by at least an order of magnitude when extrapolating the One-stage results to actual Seven-stage extraction operation with a stage efficiency of 95%.
Date: January 6, 2014
Creator: Herman, D. T.; Peters, T. B.; Duignan, M. R.; Williams, M. R.; Poirier, M. R.; Brass, E. A. et al.
Partner: UNT Libraries Government Documents Department