Download or read book Actual Waste Tests of Enhanced Chemical Cleaning for Retrieval of SRS HLW Sludge Tank Heels and Decomposition of Oxalic Acid written by and published by . This book was released on 2012 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.

Download or read book Testing of Enhanced Chemical Cleaning of SRS Actual Waste Tank 5F and Tank 12H Sludges written by and published by . This book was released on 2011 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Forty three of the High Level Waste (HLW) tanks at the Savannah River Site (SRS) have internal structures that hinder removal of the last approximately five thousand gallons of waste sludge solely by mechanical means. Chemical cleaning can be utilized to dissolve the sludge heel with oxalic acid (OA) and pump the material to a separate waste tank in preparation for final disposition. This dissolved sludge material is pH adjusted downstream of the dissolution process, precipitating the sludge components along with sodium oxalate solids. The large quantities of sodium oxalate and other metal oxalates formed impact downstream processes by requiring additional washing during sludge batch preparation and increase the amount of material that must be processed in the tank farm evaporator systems and the Saltstone Processing Facility. Enhanced Chemical Cleaning (ECC) was identified as a potential method for greatly reducing the impact of oxalate additions to the SRS Tank Farms without adding additional components to the waste that would extend processing or increase waste form volumes. In support of Savannah River Site (SRS) tank closure efforts, the Savannah River National Laboratory (SRNL) conducted Real Waste Testing (RWT) to evaluate an alternative to the baseline 8 wt. % OA chemical cleaning technology for tank sludge heel removal. The baseline OA technology results in the addition of significant volumes of oxalate salts to the SRS tank farm and there is insufficient space to accommodate the neutralized streams resulting from the treatment of the multiple remaining waste tanks requiring closure. ECC is a promising alternative to bulk OA cleaning, which utilizes a more dilute OA (nominally 2 wt. % at a pH of around 2) and an oxalate destruction technology. The technology is being adapted by AREVA from their decontamination technology for Nuclear Power Plant secondary side scale removal. This report contains results from the SRNL small scale testing of the ECC process using SRS sludge tank sample material. A Task Technical and Quality Assurance Plan (TTQAP) details the experimental plan as outlined by the Technical Task Request (TTR). The TTR identifies that the data produced by this testing and results included in this report will support the technical baseline with portions having a safety class functional classification. The primary goals for SRNL RWT are as follows: (1) to confirm ECC performance with real tank sludge samples, (2) to determine the impact of ECC on fate of actinides and the other sludge metals, and (3) to determine changes, if any, in solids flow and settling behavior.

Download or read book ACTUAL WASTE TESTING OF ULTRAVIOLET LIGHT TO AUGMENT THE ENHANCED CHEMICAL CLEANING OF SRS SLUDGE written by and published by . This book was released on 2012 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: 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

Download or read book Enhanced Chemical Cleaning written by and published by . This book was released on 2008 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.

Download or read book Alternative Chemical Cleaning Methods for High Level Waste Tanks written by and published by . This book was released on 2016 with total page 38 pages. Available in PDF, EPUB and Kindle. Book excerpt: Solubility testing with actual High Level Waste tank sludge has been conducted in order to evaluate several alternative chemical cleaning technologies for the dissolution of sludge residuals remaining in the tanks after the exhaustion of mechanical cleaning and sludge sluicing efforts. Tests were conducted with archived Savannah River Site (SRS) radioactive sludge solids that had been retrieved from Tank 5F in order to determine the effectiveness of an optimized, dilute oxalic/nitric acid cleaning reagent toward dissolving the bulk non-radioactive waste components. Solubility tests were performed by direct sludge contact with the oxalic/nitric acid reagent and with sludge that had been pretreated and acidified with dilute nitric acid. For comparison purposes, separate samples were also contacted with pure, concentrated oxalic acid following current baseline tank chemical cleaning methods. One goal of testing with the optimized reagent was to compare the total amounts of oxalic acid and water required for sludge dissolution using the baseline and optimized cleaning methods. A second objective was to compare the two methods with regard to the dissolution of actinide species known to be drivers for SRS tank closure Performance Assessments (PA). Additionally, solubility tests were conducted with Tank 5 sludge using acidic and caustic permanganate-based methods focused on the "targeted" dissolution of actinide species.

Download or read book REVIEW OF ALTERNATIVE ENHANCED CHEMICAL CLEANING OPTIONS FOR SRS WASTE TANKS written by and published by . This book was released on 2009 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: A literature review was conducted to support the Task Technical and Quality Assurance Plan for Alternative Enhanced Chemical Cleaning (AECC) for sludge heel removal funded as part of the EM-21 Engineering and Technology program. The goal was to identify potential technologies or enhancements to the baseline oxalic acid cleaning process for chemically dissolving or mobilizing Savannah River Site (SRS) sludge heels. The issues with the potentially large volume of oxalate solids generated from the baseline process have driven an effort to find an improved or enhanced chemical cleaning technology for the tank heels. This literature review builds on a previous review conducted in 2003. A team was charged with evaluating the information in these reviews and developing recommendations of alternative technologies to pursue. The new information in this report supports the conclusion of the previous review that oxalic acid remains the chemical cleaning agent of choice for dissolving the metal oxides and hydroxides found in sludge heels in carbon steel tanks. The potential negative impact of large volumes of sodium oxalate on downstream processes indicates that the amount of oxalic acid used for chemical cleaning needs to be minimized as much as possible or the oxalic acid must be destroyed prior to pH adjustment in the receipt tank. The most straightforward way of minimizing the volume of oxalic acid needed for chemical cleaning is through more effective mechanical cleaning. Using a mineral acid to adjust the pH of the sludge prior to adding oxalic acid may also help to minimize the volume of oxalic acid used in chemical cleaning. If minimization of oxalic acid proves insufficient in reducing the volume of oxalate salts, several methods were found that could be used for oxalic acid destruction. For some waste tank heels, another acid or even caustic treatment (or pretreatment) might be more appropriate than the baseline oxalic acid cleaning process. Caustic treatment of high aluminum sludge heels may be appropriate as a means of reducing oxalic acid usage. Reagents other than oxalic acid may also be needed for removing actinide elements from the tank heels. A systems engineering evaluation (SEE) was performed on the various alternative chemical cleaning reagents and organic oxidation technologies discussed in the literature review. The objective of the evaluation was to develop a short list of chemical cleaning reagents and oxalic acid destruction methods that should be the focus of further research and development. The results of the SEE found that eight of the thirteen organic oxidation technologies scored relatively close together. Six of the chemical cleaning reagents were also recommended for further investigation. Based on the results of the SEE and plan set out in the TTQAP the following broad areas are recommended for future study as part of the AECC task: (1) Basic Chemistry of Sludge Dissolution in Oxalic Acid: A better understanding of the variables effecting dissolution of sludge species is needed to efficiently remove sludge heels while minimizing the use of oxalic acid or other chemical reagents. Tests should investigate the effects of pH, acid concentration, phase ratios, temperature, and kinetics of the dissolution reactions of sludge components with oxalic acid, mineral acids, and combinations of oxalic/mineral acids. Real waste sludge samples should be characterized to obtain additional data on the mineral phases present in sludge heels. (2) Simulant Development Program: Current sludge simulants developed by other programs for use in waste processing tests, while compositionally similar to real sludge waste, generally have more hydrated forms of the major metal phases and dissolve more easily in acids. Better simulants containing the mineral phases identified by real waste characterization should be developed to test chemical cleaning methods. (3) Oxalic Acid Oxidation Technologies: The two Mn based oxidation methods that scored highly in the SEE should be studied to evaluate long term potential. One of the AOP's (UV/O3/Solids Separator) is currently being implemented by the SRS liquid waste organization for use in tank heel chemical cleaning. (4) Corrosion Issues: A program will be needed to address potential corrosion issues from the use of low molarity mineral acids and mixtures of oxalic/mineral acids in the waste tanks for short durations. The addition of corrosion inhibitors to the acids to reduce corrosion rates should be investigated.

Download or read book Alternative Enhanced Chemical Cleaning Basic Studies Results FY09 written by and published by . This book was released on 2010 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Due to the need to close waste storage tanks, chemical cleaning methods are needed for the effective removal of the heels. Oxalic acid is the preferred cleaning reagent for sludge heel dissolution, particularly for iron-based sludge, due to the strong complexing strength of the oxalate. However, the large quantity of oxalate added to the tank farm from oxalic acid based chemical cleaning has significant downstream impacts. Optimization of the oxalic acid cleaning process can potentially reduce the downstream impacts from chemical cleaning. To optimize oxalic acid usage, a detailed understanding of the chemistry of oxalic acid based sludge dissolution is required. Additionally, other acid systems may be required for specific waste components with low solubility in oxalic acid and as a means to reduce oxalic acid usage in general. Solubility tests were conducted using non-radioactive, pure metal phases known to be the primary phases present in High Level Waste sludge. The metal phases studied included the aluminum phases gibbsite and boehmite and the iron phases magnetite and hematite. Hematite and boehmite are expected to be the most difficult iron and aluminum phases to dissolve. These mineral phases have been identified in both SRS and Hanford High Level Waste sludge. Acids evaluated for dissolution included oxalic, nitric, and sulfuric acids. The results of the solubility tests indicate that oxalic and sulfuric acids are more effective for the dissolution of the primary sludge phases. For boehmite, elevated temperature will be required to promote effective phase dissolution in the acids studied. Literature reviews, thermodynamic modeling, and experimental results have all confirmed that pH control using a supplemental proton source (additional acid) is critical for minimization of oxalic acid usage during the dissolution of hematite. These results emphasize the importance of pH control in optimizing hematite dissolution in oxalic acid and may explain the somewhat limited success observed during recent attempts to remove sludge heels from SRS Tanks 5F and 6F using oxalic acid. Additionally, based on the results of the solubility tests conducted, the following conclusions can be drawn: (1) Hematite dissolution in oxalic acid is a stoichiometric process dependant upon the provision of sufficient oxalate molar equivalents to complex the iron and sufficient H to promote the dissolution reaction. (2) The optimal utilization of oxalic acid for hematite dissolution requires an additional proton source, such as nitric acid, and a pH of (less-than or equal to) 1. In the absence of a supplemental proton source, greater than stoichiometric amounts of oxalate are required. (3) Magnetite is generally more soluble than hematite in all acids tested. (4) Gibbsite is generally more soluble than the boehmite form of aluminum in all acids tested. (5) The OLI Thermodynamic Model is a useful tool for the prediction of equilibrium iron concentrations, but predictions must be experimentally verified. The OLI model appears to over-predict the solubility of the iron and aluminum phases studied in mineral acids.

Download or read book Alternative and Enhanced Chemical Cleaning written by and published by . This book was released on 2011 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: In an effort to develop and optimize chemical cleaning methods for the removal of sludge heels from High Level Waste tanks, solubility tests have been conducted using nonradioactive, pure metal phases. The metal phases studied included the aluminum phase gibbsite and the iron phases hematite, maghemite, goethite, lepidocrocite, magnetite, and wustite. Many of these mineral phases have been identified in radioactive, High Level Waste sludge at the Savannah River and Hanford Sites. Acids evaluated for dissolution included oxalic, nitric, and sulfuric acids and a variety of other complexing organic acids. The results of the solubility tests indicate that mixtures of oxalic acid with either nitric or sulfuric acid are the most effective cleaning solutions for the dissolution of the primary metal phases in sludge waste. Based on the results, optimized conditions for hematite dissolution in oxalic acid were selected using nitric or sulfuric acid as a supplemental proton source. Electrochemical corrosion studies were also conducted (reported separately; Wiersma, 2010) with oxalic/mineral acid mixtures to evaluate the effects of these solutions on waste tank integrity. The following specific conclusions can be drawn from the test results: (1) Oxalic acid was shown to be superior to all of the other organic acids evaluated in promoting the dissolution of the primary sludge phases. (2) All iron phases showed similar solubility trends in oxalic acid versus pH, with hematite exhibiting the lowest solubility and the slowest dissolution. (3) Greater than 90% hematite dissolution occurred in oxalic/nitric acid mixtures within one week for two hematite sources and within three weeks for a third hematite sample with a larger average particle size. This dissolution rate appears acceptable for waste tank cleaning applications. (4) Stoichiometric dissolution of iron phases in oxalic acid (based on the oxalate concentration) and the formation of the preferred 1:1 Fe to oxalate complex is possible with the addition of a supplemental hydrogen ion source (HNO3 or H2SO4) and pH control. (5) Sulfuric acid is nearly twice as effective as nitric acid (on a molar basis) at promoting hematite dissolution in oxalic acid solutions, most likely due to the fact that it is diprotic. (6) The greater the oxalic acid concentration, the greater the demand for supplemental H to promote optimal dissolution. Minimum mineral acid concentrations required for optimal oxalic acid utilization based on hematite solubility tests are provided. (7) Corrosion studies conducted (reported elsewhere) with 1 wt.% oxalic acid revealed that carbon steel corrosion rates are manageable at lower mineral acid concentrations (0.1 M HNO3 and 0.05 M H2SO4) and lower temperatures (45 C). (8) Proposed conditions for waste tank heel dissolution based on the solubility and corrosion test results are 0.5 wt.% oxalic acid and 0.18 M HNO3 or 0.09 M H2SO4 at 50 C. (9) The OLI Thermodynamic Model appears to over-predict the solubility of the iron phases studied in oxalic acid and oxalic/nitric acid mixtures. The predictions show better agreement with experimental results at higher pH and in sulfuric/oxalic acid mixtures. (10) Oxalic, nitric, and sulfuric acids are effective at quickly dissolving gibbsite (e"6% dissolution in 2 weeks), with oxalic/sulfuric acid mixtures being particularly effective. (11) Limited dissolution tests conducted with carbon steel coupons revealed that the presence of metallic iron can, in some cases, result in dramatically different results. Additional studies in this area are recommended. Based on the current results, the optimal approach for the removal of sludge heels for HLW tanks would include the following steps: (1) removal of the maximum possible amount of heel materials by mechanical means; (2) neutralization and acidification of the heel using dilute mineral acid (This step should promote significant dissolution of certain metal hydroxides and salts, including gibbsite.); and (3) dissolution of the residual heel material at 50 C using an acid mixture containing 0.5 wt.% oxalic acid and 0.18 M nitric acid (This step should dissolve the iron phases.).

Download or read book Deposition Tank Corrosion Testing for Enhanced Chemical Cleaning Post Oxalic Acid Destruction written by and published by . This book was released on 2011 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: An Enhanced Chemical Cleaning (ECC) process is being developed to aid in the high level waste tank closure at the Savannah River Site. The ECC process uses an advanced oxidation process (AOP) to destroy the oxalic acid that is used to remove residual sludge from a waste tank prior to closure. The AOP process treats the dissolved sludge with ozone to decompose the oxalic acid through reactions with hydroxyl radicals. The effluent from this oxalic acid decomposition is to be sent to a Type III waste tank and may be corrosive to these tanks. As part of the hazardous simulant testing that was conducted at the ECC vendor location, corrosion testing was conducted to determine the general corrosion rate for the deposition tank and to assess the susceptibility to localized corrosion, especially pitting. Both of these factors impact the calculation of hydrogen gas generation and the structural integrity of the tanks, which are considered safety class functions. The testing consisted of immersion and electrochemical testing of A537 carbon steel, the material of construction of Type III tanks, and 304L stainless steel, the material of construction for transfer piping. Tests were conducted in solutions removed from the destruction loop of the prototype ECC set up. Hazardous simulants, which were manufactured at SRNL, were used as representative sludges for F-area and H-area waste tanks. Oxalic acid concentrations of 1 and 2.5% were used to dissolve the sludge as a feed to the ECC process. Test solutions included the uninhibited effluent, as well as the effluent treated for corrosion control. The corrosion control options included mixing with an inhibited supernate and the addition of hydroxide. Evaporation of the uninhibited effluent was also tested since it may have a positive impact on reducing corrosion. All corrosion testing was conducted at 50 C. The uninhibited effluent was found to increase the corrosion rate by an order of magnitude from less than 1 mil per year (mpy) for an inhibited waste to a range of 5 to 23.4 mpy, depending on sludge chemistry. F-area-based effluents were, in general, more corrosive. Effective corrosion control measures included evaporation, hydroxide additions and mixing with supernates containing a representative supernate chemistry (5 M hydroxide and 1.5 M nitrite). Corrosion rates with these measures were generally 0.2 mpy. The A537 carbon steel was found to be susceptible to pitting when the corrosion control measure involved mixing the ECC effluent with a supernate chemistry having minimal inhibitor concentrations (0.5 M hydroxide and 0.3 M nitrite). Corrosion rates in this case were near 1 mpy.

Download or read book Waste Tank Heel Chemical Cleaning Summary written by M. J. Barnes and published by . This book was released on 2003 with total page 5 pages. Available in PDF, EPUB and Kindle. Book excerpt: At the Savannah River Site in Aiken, South Carolina, there are approximately 40 million gallons of legacy High Level Waste stored in large capacity sub-surface tanks. Twelve of these tanks are single-containment, non-conforming tanks with leaks. These tanks were built in the 1950s. Some of these tanks contain sludge heels and are being considered for near-term removal efforts and vitrification. Currently, only mechanical methods (i.e., pumps) are used to remove the sludge waste with varying degrees of success. To provide for additional levels of removal, chemically-aided techniques are being considered. The objective of the was to collect and evaluate information available on chemical-based methods for removing residual solids from the Site's waste tanks. As part of this study, the team was requested to develop recommendations for chemical treatments to remove residual heels (primarily sludge). Ideally, one agent alone would be efficient at dissolving all residual tank heels and yet satisfy all safety and process concerns. No such chemical cleaning agent was found. The cleaning agents identified from the literature, included oxalic acid, a mixture of oxalic acid and citric acid, a combination of oxalic acid with hydrogen peroxide, nitric acid, formic acid, and organics. A criteria matrix for evaluating the various cleaning agents was developed. The results of the evaluation conclusively support oxalic acid as the cleaning agent of choice for the immediate future. Oxalic acid scored nearly double the next closest cleaning agent. Nitric acid, formic acid, and oxalic acid with hydrogen peroxide were all closely grouped for the next best choice. The mixture of oxalic acid and citric acid rated poorly. Organics rated even more poorly due to large uncertainties in performance and downstream impacts.

Download or read book ANALYSIS OF SAMPLES FROM TANK 5F CHEMICAL CLEANING written by and published by . This book was released on 2011 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: The Savannah River Site (SRS) is preparing Tank 5F for closure. The first step in preparing the tank for closure is mechanical sludge removal. Following mechanical sludge removal, SRS performed chemical cleaning with oxalic acid to remove the sludge heel. Personnel are currently assessing the effectiveness of the chemical cleaning. SRS personnel collected liquid samples during chemical cleaning and submitted them to Savannah River National Laboratory (SRNL) for analysis. Following chemical cleaning, they collected a solid sample (also known as 'process sample') and submitted it to SRNL for analysis. The authors analyzed these samples to assess the effectiveness of the chemical cleaning process. The conclusions from this work are: (1) With the exception of iron, the dissolution of sludge components from Tank 5F agreed with results from the actual waste demonstration performed in 2007. The fraction of iron removed from Tank 5F by chemical cleaning was significantly less than the fraction removed in the SRNL demonstrations. The likely cause of this difference is the high pH following the first oxalic acid strike. (2) Most of the sludge mass remaining in the tank is iron and nickel. (3) The remaining sludge contains approximately 26 kg of barium, 37 kg of chromium, and 37 kg of mercury. (4) Most of the radioactivity remaining in the residual material is beta emitters and 9°Sr. (5) The chemical cleaning removed more than ≈ 90% of the uranium isotopes and 137Cs. (6) The chemical cleaning removed ≈ 70% of the neptunium, ≈ 83% of the 9°Sr, and ≈ 21% of the 6°Co. (7) The chemical cleaning removed less than 10% of the plutonium, americium, and curium isotopes. (8) The chemical cleaning removed more than 90% of the aluminium, calcium, and sodium from the tank. (9) The cleaning operations removed 61% of lithium, 88% of non-radioactive strontium, and 65% of zirconium. The 9°Sr and non-radioactive strontium were measured by different methods, and the differences in the fraction removed are not statistically significant. (10) Chemical cleaning removed 10-50% of the barium, chromium, iron, magnesium, manganese, and silicon. (11) Chemical cleaning removed only ≈1% of the nickel.

Download or read book DEVELOPING AN OPTIMIZED PROCESS STRATEGY FOR ACID CLEANING OF THE SAVANNAH RIVERSITE HLW TANKS written by and published by . This book was released on 2006 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: 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).

Download or read book EM 31 ALTERNATIVE AND ENHANCED CHEMICAL CLEANING PROGRAM FOR SLUDGE HEEL REMOVAL 11220 written by and published by . This book was released on 2010 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Mixtures of oxalic acid with nitric acid have been shown to be superior to oxalic acid alone for the dissolution of iron-rich High Level Waste sludge heels. Optimized conditions resulting in minimal oxalate usage and stoichiometric iron dissolution (based on added oxalate ion) have been determined for hematite (a primary sludge iron phase) in oxalic/nitric acid mixtures. The acid mixtures performed better than expected based on the solubility of hematite in the individual acids through a synergistic effect in which the preferred 1:1 Fe:oxalate complex is formed. This allows for the minimization of oxalate additions to the waste stream. Carbon steel corrosion rates were measured in oxalic/nitric acid mixtures to evaluate the impacts of chemical cleaning with these solutions on waste tank integrity. Manageable corrosion rates were observed in the concentration ranges of interest for an acid contact timescale of 1 month. Kinetics tests involving hematite and gibbsite (a primary sludge aluminum phase) have confirmed that ≥90% solids dissolution occurs within 3 weeks. Based on these results, the chemical cleaning conditions recommended to promote minimal oxalate usage and manageable corrosion include: 0.5 wt. % oxalic acid/0.175 M nitric acid mixture, 50 C, 2-3 week contact time with agitation.

Download or read book CHARACTERIZATION AND ACTUAL WASTE TEST WITH TANK 5F SAMPLES written by and published by . This book was released on 2007 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: The initial phase of bulk waste removal operations was recently completed in Tank 5F. Video inspection of the tank indicates several mounds of sludge still remain in the tank. Additionally, a mound of white solids was observed under Riser 5. In support of chemical cleaning and heel removal programs, samples of the sludge and the mound of white solids were obtained from the tank for characterization and testing. A core sample of the sludge and Super Snapper sample of the white solids were characterized. A supernate dip sample from Tank 7F was also characterized. A portion of the sludge was used in two tank cleaning tests using oxalic acid at 50 C and 75 C. The filtered oxalic acid from the tank cleaning tests was subsequently neutralized by addition to a simulated Tank 7F supernate. Solids and liquid samples from the tank cleaning test and neutralization test were characterized. A separate report documents the results of the gas generation from the tank cleaning test using oxalic acid and Tank 5F sludge. The characterization results for the Tank 5F sludge sample (FTF-05-06-55) appear quite good with respect to the tight precision of the sample replicates, good results for the glass standards, and minimal contamination found in the blanks and glass standards. The aqua regia and sodium peroxide fusion data also show good agreement between the two dissolution methods. Iron dominates the sludge composition with other major contributors being uranium, manganese, nickel, sodium, aluminum, and silicon. The low sodium value for the sludge reflects the absence of supernate present in the sample due to the core sampler employed for obtaining the sample. The XRD and CSEM results for the Super Snapper salt sample (i.e., white solids) from Tank 5F (FTF-05-07-1) indicate the material contains hydrated sodium carbonate and bicarbonate salts along with some aluminum hydroxide. These compounds likely precipitated from the supernate in the tank. A solubility test showed the material to be water-soluble consistent with the determined composition. The analytical data for the solid residues filtered from the oxalic acid solution and filtered oxalic acid indicate a large portion of the Tank 5F sludge used in the tank cleaning test dissolved into the oxalic acid. The results of a material balance calculation indicate a high percentage of the iron, uranium, sodium, and aluminum dissolved during both tests. Approximately half of the manganese, a small portion of the plutonium, and essentially none of the nickel dissolved during the tank cleaning tests. Additionally, the results show slightly higher dissolution of the sludge in the 75 C test compared to the 50 C test however, the amount of sludge dissolution gained by using the higher temperature remains small. Some uncertainty remains with respect to the amount of plutonium dissolved in the tank cleaning test. The neutralization of the filtered oxalic acid solutions from the cleaning test produced a large volume of solids ((almost equal to)2X the original sludge mass after filtration and air drying). A large portion of the increase in solids could be attributed to the formation of sodium oxalate. The data from analysis of the solid residues filtered from the neutralization tests and the filtrate obtained indicate most of the iron, uranium, manganese, and a large portion of the aluminum precipitated during the neutralization tests. The data for the 50 C test and the 75 C test show good agreement with the exception of the amount of aluminum precipitated from the neutralization. The slower addition rate of the oxalic acid filtrate to the simulated Tank 7F supernate in the 75 C test might account for the smaller amount of aluminum precipitated and differences in the particle size/morphology and composition of the particulates. Some evidence of uranium separation from other sludge elements appears in the 75 C data. Data collected from the tank cleaning and neutralization tests indicates most of the uranium dissolved during the cleaning test with oxalic acid along with the iron, aluminum, and sodium in the sludge. During the neutralization of the oxalic acid, the majority of the uranium precipitates from solution along with the iron and other typical sludge elements. The CSEM results of the 75 C neutralization test provide some evidence of uranium separation from other sludge elements. However, the CSEM analysis looked at a very small amount of sample, which might not be representative of the bulk material and the sludge sample also showed areas of high uranium concentration. Additionally, how the test results will scale to the full-scale neutralization in a waste tank remains uncertain. The analysis of the oxalic acid filtrates indicates that only a small portion of the plutonium dissolved during the tank cleaning test. However, the analytical data from the solid residues filtered from the cleaning test contradict the solution data and indicate approximately half of the plutonium dissolved.

Download or read book Analysis of Samples from Tank 6F Chemical Cleaning written by and published by . This book was released on 2010 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Savannah River Remediation (SRR) is preparing Tank 6F for closure. The first step in preparing the tank for closure is mechanical sludge removal. In mechanical sludge removal, personnel add liquid (e.g., inhibited water or supernate salt solution) to the tank to form a slurry. They mix the liquid and sludge with pumps, and transfer the slurry to another tank for further processing. Mechanical sludge removal effectively removes the bulk of the sludge from a tank, but is not able to remove all of the sludge. In Tank 6F, SRR estimated a sludge heel of 5,984 gallons remained after mechanical sludge removal. To remove this sludge heel, SRR performed chemical cleaning. The chemical cleaning included two oxalic acid strikes, a spray wash, and a water wash. SRR conducted the first oxalic acid strike as follows. Personnel added 110,830 gallons of 8 wt % oxalic acid to Tank 6F and mixed the contents of Tank 6F with two submersible mixer pumps (SMPs) for approximately four days. Following the mixing, they transferred 115,903 gallons of Tank 6F material to Tank 7F. The SMPs were operating when the transfer started and were shut down approximately five hours after the transfer started. SRR collected a sample of the liquid from Tank 6F and submitted it to SRNL for analysis. Mapping of the tank following the transfer indicated that 2,400 gallons of solids remained in the tank. SRR conducted the second oxalic acid strike as follows. Personnel added 28,881 gallons of 8 wt % oxalic acid to Tank 6F. Following the acid addition, they visually inspected the tank and transferred 32,247 gallons of Tank 6F material to Tank 7F. SRR collected a sample of the liquid from Tank 6F and submitted it to SRNL for analysis. Mapping of the tank following the transfer indicated that 3,248 gallons of solids remained in the tank. Following the oxalic acid strikes, SRR performed Spray Washing with oxalic acid to remove waste collected on internal structures, cooling coils, tank top internals, and tank walls. The Acid Spray Wash was followed by a Water Spray Wash to remove oxalic acid from the tank internals. SRR conducted the Spray Wash as follows. Personnel added 4,802 gallons of 8 wt % oxalic acid to Tank 6F through the spray mast installed in Riser 2, added 4,875 gallons of oxalic acid through Riser 7, added 5,000 gallons of deionized water into the tank via Riser 2, and 5,000 gallons of deionized water into the tank via Riser 7. Following the Spray Wash, they visually inspected the tank and transferred 22,430 gallons of Tank 6F material to Tank 7F. SRR collected a sample of the liquid from Tank 6F and submitted it to SRNL for analysis. Following the Spray Wash and transfer, Savannah River Site (SRS) added 113,935 gallons of well water to Tank 6F. They mixed the tank contents with a single SMP and transferred 112,699 gallons from Tank 6F to Tank 7F. SRR collected a sample of the liquid from Tank 6F and submitted to SRNL for analysis. Mapping of the tank following the transfer indicated that 3,488 gallons of solids remained in the tank. Following the Water Wash, SRR personnel collected a solid sample and submitted it to SRNL for analysis to assess the effectiveness of the chemical cleaning and to provide a preliminary indication of the composition of the material remaining in the tank.

Download or read book SAVANNAH RIVER SITE TANK CLEANING written by and published by . This book was released on 2011 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: 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. Both the 1-wt% and the 8-wt% testing demonstrated that if the sludge was removed from the testing, there would be a significant increase in the CR. Specifically, the CR for an agitated 1-wt% pure oxalic acid solution at 45 or 75 C was about 4 to 10 times greater than those for a 1-wt% solution with sludge. For 8-wt% at 50 C, the effect was even larger. The lower CRs suggest that the cathodic reactions were altered by the sludge. For both the 1-wt% and 8-wt% solution, increasing the temperature did not result in an increased CR. Although the CR for a 1-wt% acid with sludge was considered to be non-temperature dependent, a stagnant solution with sludge resulted in a CR that was greater at 45 C than at 75 C, suggesting that the oxalate film formed at a higher temperature was better in mitigating corrosion. For both a 1 and an 8-wt% solution, agitation typically resulted in a higher CR. Overall, the testing showed that the general CR to the SRS carbon steel tanks from 1-wt% oxalic acid solution will remain bounded by those from an 8-wt% oxalic acid solution.

Download or read book Treatment Tank Off Gas Testing for the Enhanced Chemical Cleaning Process written by and published by . This book was released on 2011 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: The purpose of this activity was to provide a bounding estimate of the volume of hydrogen gas generated during Enhanced Chemical Cleaning (ECC) of residual sludge remaining in a Type I or Type II treatment tank as well as to provide results independent of the sludge volume in the waste tank to be cleaned. Previous testing to support Chemical Cleaning was based on a 20:1 oxalic acid to sludge ratio. Hydrogen gas evolution is the primary safety concern. Sealed vessel coupon tests were performed to estimate the hydrogen generation rate due to corrosion of carbon steel by 2.5 wt.% oxalic acid. These tests determined the maximum instantaneous hydrogen generation rate, the rate at which the generation rate decays, and the total hydrogen generated. These values were quantified based on a small scale methodology similar to the one described in WSRC-STI-2007-00209, Rev. 0. The measured rates support identified Safety Class functions. The tests were performed with ASTM A285 Grade C carbon steel coupons. Bounding conditions were determined for the solution environment. The oxalic acid concentration was 2.5 wt.% and the test temperature was 75 C. The test solution was agitated and contained no sludge simulant. Duplicate tests were performed and showed excellent reproducibility for the hydrogen generation rate and total hydrogen generated. The results showed that the hydrogen generation rate was initially high, but decayed rapidly within a couple of days. A statistical model was developed to predict the instantaneous hydrogen generation rate as a function of exposure time by combining both sets of data. An upper bound on the maximum hydrogen generation rate was determined from the upper 95% confidence limit. The upper bound confidence limit for the hydrogen generation rate is represented by the following equation. ln (G{sub v}) = -8.22-0.0584 t + 0.0002 t2. This equation should be utilized to estimate the instantaneous hydrogen generation rate per unit surface area, G{sub v}, at a given time, t. The units for G{sub v} and t are ft3/ft2/min and hours, respectively. The total volume of hydrogen gas generated during the test was calculated from the model equation. An upper bound on the total gas generated was determined from the upper 95% confidence limit. The upper bound limit on the total hydrogen generated during the 163 hour test was 0.332 ft3/ft2. The maximum instantaneous hydrogen generation rate for this scenario is greater than that previously measured in the 8 wt.% oxalic acid tests due to both the absence of sludge in the test (i.e., greater than 20:1 ratio of acid to sludge) and the use of polished coupons (vs. mill scale coupons). However, due to passivation of the carbon steel surface, the corrosion rate decays by an order of magnitude within the first three days of exposure such that the instantaneous hydrogen generation rates are less than that previously measure in the 8 wt.% oxalic acid tests. While the results of these tests are bounding, the conditions used in this study may not be representative of the ECC flowsheet, and the applicability of these results to the flowsheet should be evaluated for the following reasons: (1) The absence of sludge results in higher instantaneous hydrogen generation rates than when the sludge is present; and (2) Polished coupons do not represent the condition of the carbon steel interior of the tank, which are covered with mill scale. Based on lower instantaneous corrosion rates measured on mill scale coupons exposed to oxalic acid, lower instantaneous hydrogen generation rates are expected for the tank interior than measured on the polished coupons. Corrosion rates were determined from the coupon tests and also calculated from the measured hydrogen generation rates. Excellent agreement was achieved between the time averaged corrosion rate calculated from the hydrogen generation rates and the corrosion rates determined from the coupon tests. The corrosion rates were on the order of 18 to 28 mpy. Good agreement was also observed between the maximum instantaneous corrosion rate as calculated from the hydrogen generation rate and the corrosion rate determined by previous electrochemical tests.