DESTRUCTION OF TETRAPHENYLBORATE IN TANK 48H USING WET AIR OXIDATION BATCH BENCH SCALE AUTOCLAVE TESTING WITH ACTUAL RADIOACTIVE TANK 48H WASTE.

DESTRUCTION OF TETRAPHENYLBORATE IN TANK 48H USING WET AIR OXIDATION BATCH BENCH SCALE AUTOCLAVE TESTING WITH ACTUAL RADIOACTIVE TANK 48H WASTE.
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Release: 2009
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Wet Air Oxidation (WAO) is one of the two technologies being considered for the destruction of Tetraphenylborate (TPB) in Tank 48H. Batch bench-scale autoclave testing with radioactive (actual) Tank 48H waste is among the tests required in the WAO Technology Maturation Plan. The goal of the autoclave testing is to validate that the simulant being used for extensive WAO vendor testing adequately represents the Tank 48H waste. The test objective was to demonstrate comparable test results when running simulated waste and real waste under similar test conditions. Specifically: (1) Confirm the TPB destruction efficiency and rate (same reaction times) obtained from comparable simulant tests, (2) Determine the destruction efficiency of other organics including biphenyl, (3) Identify and quantify the reaction byproducts, and (4) Determine off-gas composition. Batch bench-scale stirred autoclave tests were conducted with simulated and actual Tank 48H wastes at SRNL. Experimental conditions were chosen based on continuous-flow pilot-scale simulant testing performed at Siemens Water Technologies Corporation (SWT) in Rothschild, Wisconsin. The following items were demonstrated as a result of this testing. (1) Tetraphenylborate was destroyed to below detection limits during the 1-hour reaction time at 280 C. Destruction efficiency of TPB was> 99.997%. (2) Other organics (TPB associated compounds), except biphenyl, were destroyed to below their respective detection limits. Biphenyl was partially destroyed in the process, mainly due to its propensity to reside in the vapor phase during the WAO reaction. Biphenyl is expected to be removed in the gas phase during the actual process, which is a continuous-flow system. (3) Reaction byproducts, remnants of MST, and the PUREX sludge, were characterized in this work. Radioactive species, such as Pu, Sr-90 and Cs-137 were quantified in the filtrate and slurry samples. Notably, Cs-137, boron and potassium were shown as soluble as a result of the WAO reaction. (4) Off-gas composition was measured in the resulting gas phase from the reaction. Benzene and hydrogen were formed during the reaction, but they were reasonably low in the off-gas at 0.096 and 0.0063 vol% respectively. Considering the consistency in replicating similar test results with simulated waste and Tank 48H waste under similar test conditions, the results confirm the validity of the simulant for other WAO test conditions.

TASK TECHNICAL AND QUALITY ASSURANCE PLAN FOR OUT-OF-TANK DESTRUCTION OF TETRAPHENYLBORATE VIA WET AIR OXIDATION TECHNOLOGY

TASK TECHNICAL AND QUALITY ASSURANCE PLAN FOR OUT-OF-TANK DESTRUCTION OF TETRAPHENYLBORATE VIA WET AIR OXIDATION TECHNOLOGY
Author: K. Adu-Wusu
Publisher:
Total Pages:
Release: 2006
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ISBN:

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Tank 48H return to service is critical to the processing of high level waste (HLW) at Savannah River Site (SRS). Liquid Waste Disposition (LWD) management has the goal of returning Tank 48H to routine service by January 2010 or as soon as practical. Tank 48H currently holds legacy material containing organic tetraphenylborate (TPB) compounds from the operation of the In-Tank Precipitation process. This material is not compatible with the waste treatment facilities at SRS and must be removed or undergo treatment to destroy the organic compounds before the tank can be returned to Tank Farm service. Tank 48H currently contains {approx}240,000 gallons of alkaline slurry with about 2 wt % potassium and cesium tetraphenylborate (KTPB and CsTPB). The main radioactive component in Tank 48H is {sup 137}Cs. The waste also contains {approx}0.15 wt % Monosodium Titanate (MST) which has adsorbed {sup 90}Sr, U, and Pu isotopes. A System Engineering Evaluation of technologies/ideas for the treatment of TPB identified Wet Air Oxidation (WAO) as a leading alternative technology to the baseline aggregation approach. Over 75 technologies/ideas were evaluated overall. Forty-one technologies/ideas passed the initial screening evaluation. The 41 technologies/ideas were then combined to 16 complete solutions for the disposition of TPB and evaluated in detail. Wet Air Oxidation (WAO) is an aqueous phase process in which soluble or suspended waste components are oxidized using molecular oxygen contained in air. The process operates at elevated temperatures and pressures ranging from 150 to 320 C and 7 to 210 atmospheres, respectively. The products of the reaction are CO{sub 2}, H{sub 2}O, and low molecular weight oxygenated organics (e.g. acetate, oxalate). The basic flow scheme for a typical WAO system is as follows. The waste solution or slurry is pumped through a high-pressure feed pump. An air stream containing sufficient oxygen to meet the oxygen requirements of the waste stream is injected into the pressurized waste stream, and the air/liquid mixture is preheated to the required reactor inlet temperature. The reactor provides sufficient retention time to allow the oxidation to approach the desired level of organic decomposition. Typical reaction time is about 30-120 minutes. Heat exchangers are routinely employed to recover energy contained in the reactor effluent to preheat the waste feed/air entering the reactor. Auxiliary energy, usually steam, is necessary for startup and can provide trim heat if required. Since the oxidation reactions are exothermic, sufficient energy may be released in the reactor to allow the WAO system to operate without any additional heat input. After cooling, the oxidized reactor effluent passes through a pressure control valve where the pressure is reduced. A separator downstream of the pressure control valve allows the depressurized and cooled vapor to separate from the liquid. Typical industrial WAO applications have a feed flow rate of 1 to 220 gallons per minute (gpm) per train, with a chemical oxygen demand (COD) from 10,000 to 150,000 mg/L (higher CODs with dilution). Note that catalysts, such as homogeneous copper and iron, their heterogeneous counterparts, or precious metals can be used to enhance the effectiveness (i.e., to lower temperature, pressure, and residence time as well as increase oxidation efficiencies) of the WAO reaction if deemed necessary.

A bientôt

A bientôt
Author: Heinz Haberzettl
Publisher:
Total Pages:
Release: 1981
Genre:
ISBN:

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CRUCIBLE TESTING OF TANK 48H RADIOACTIVEWASTE SAMPLE USING FLUIDIZED BED STEAMREFORMING TECHNOLOGY FOR ORGANICDESTRUCTION.

CRUCIBLE TESTING OF TANK 48H RADIOACTIVEWASTE SAMPLE USING FLUIDIZED BED STEAMREFORMING TECHNOLOGY FOR ORGANICDESTRUCTION.
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Release: 2008
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The purpose of crucible scale testing with actual radioactive Tank 48H material was to duplicate the test results that had been previously performed on simulant Tank 48H material. The earlier crucible scale testing using simulants was successful in demonstrating that bench scale crucible tests produce results that are indicative of actual Fluidized Bed Steam Reforming (FBSR) pilot scale tests. Thus, comparison of the results using radioactive Tank 48H feed to those reported earlier with simulants would then provide proof that the radioactive tank waste behaves in a similar manner to the simulant. Demonstration of similar behavior for the actual radioactive Tank 48H slurry to the simulant is important as a preliminary or preparation step for the more complex bench-scale steam reformer unit that is planned for radioactive application in the Savannah River National Laboratory (SRNL) Shielded Cells Facility (SCF) later in 2008. The goals of this crucible-scale testing were to show 99% destruction of tetraphenylborate and to demonstrate that the final solid product produced is sodium carbonate. Testing protocol was repeated using the specifications of earlier simulant crucible scale testing, that is sealed high purity alumina crucibles containing a pre-carbonated and evaporated Tank 48H material. Sealing of the crucibles was accomplished by using an inorganic 'nepheline' sealant. The sealed crucibles were heat-treated at 650 C under constant argon flow to inert the system. Final product REDOX measurements were performed to establish the REDuction/OXidation (REDOX) state of known amounts of added iron species in the final product. These REDOX measurements confirm the processing conditions (pyrolysis occurring at low oxygen fugacity) of the sealed crucible environment which is the environment actually achieved in the fluidized bed steam reformer process. Solid product dissolution in water was used to measure soluble cations and anions, and to investigate insoluble fractions of the product solids. Radioanalytical measurements were performed on the Tank 48H feed material and on the dissolved products in order to estimate retention of Cs-137 in the process. All aspects of prior crucible scale testing with simulant Tank 48H slurry were demonstrated to be repeatable with the actual radioactive feed. Tetraphenylborate destruction was shown to be>99% and the final solid product is sodium carbonate crystalline material. Less than 10 wt% of the final solid products are insoluble components comprised of Fe/Ni/Cr/Mn containing sludge components and Ti from monosodium titanate present in Tank 48H. REDOX measurements on the radioactive solid products indicate a reducing atmosphere with extremely low oxygen fugacity--evidence that the sealed crucible tests performed in the presence of a reductant (sugar) under constant argon purge were successful in duplicating the pyrolysis reactions occurring with the Tank 48H feed. Soluble anion measurements confirm that using sugar as reductant at 1X stoichiometry was successful in destroying nitrate/nitrite in the Tank 48H feed. Radioanalytical measurements indicate that (almost equal to)75% of the starting Cs-137 is retained in the solid product. No attempts were made to analyze/measure other potential Cs-137 in the process, i.e., as possible volatile components on the inner surface of the alumina crucible/lid or as offgas escaping the sealed crucible. The collective results from these crucible scale tests on radioactive material are in good agreement with simulant testing. Crucible scale processing has been shown to duplicate the complex reactions of an actual fluidized bed steam reformer. Thus this current testing should provide a high degree of confidence that upcoming bench-scale steam reforming with radioactive Tank 48H slurry will be successful in tetraphenylborate destruction and production of sodium carbonate product.

CRUCIBLE TESTING OF TANK 48 RADIOACTIVE WASTE SAMPLE USING FBSR TECHNOLOGY FOR ORGANIC DESTRUCTION.

CRUCIBLE TESTING OF TANK 48 RADIOACTIVE WASTE SAMPLE USING FBSR TECHNOLOGY FOR ORGANIC DESTRUCTION.
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Release: 2008
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The purpose of crucible scale testing with actual radioactive Tank 48H material was to duplicate the test results that had been previously performed on simulant Tank 48H material. The earlier crucible scale testing using simulants was successful in demonstrating that bench scale crucible tests produce results that are indicative of actual Fluidized Bed Steam Reforming (FBSR) pilot scale tests. Thus, comparison of the results using radioactive Tank 48H feed to those reported earlier with simulants would then provide proof that the radioactive tank waste behaves in a similar manner to the simulant. Demonstration of similar behavior for the actual radioactive Tank 48H slurry to the simulant is important as a preliminary or preparation step for the more complex bench-scale steam reformer unit that is planned for radioactive application in the Savannah River National Laboratory (SRNL) Shielded Cells Facility (SCF) later in 2008. The goals of this crucible-scale testing were to show 99% destruction of tetraphenylborate and to demonstrate that the final solid product produced is sodium carbonate. Testing protocol was repeated using the specifications of earlier simulant crucible scale testing, that is sealed high purity alumina crucibles containing a pre-carbonated and evaporated Tank 48H material. Sealing of the crucibles was accomplished by using an inorganic 'nepheline' sealant. The sealed crucibles were heat-treated at 650 C under constant argon flow to inert the system. Final product REDOX measurements were performed to establish the REDuction/OXidation (REDOX) state of known amounts of added iron species in the final product. These REDOX measurements confirm the processing conditions (pyrolysis occurring at low oxygen fugacity) of the sealed crucible environment which is the environment actually achieved in the fluidized bed steam reformer process. Solid product dissolution in water was used to measure soluble cations and anions, and to investigate insoluble fractions of the product solids. Radioanalytical measurements were performed on the Tank 48H feed material and on the dissolved products in order to estimate retention of Cs-137 in the process. All aspects of prior crucible scale testing with simulant Tank 48H slurry were demonstrated to be repeatable with the actual radioactive feed. Tetraphenylborate destruction was shown to be>99% and the final solid product is sodium carbonate crystalline material. Less than 10 wt% of the final solid products are insoluble components comprised of Fe/Ni/Cr/Mn containing sludge components and Ti from monosodium titanate present in Tank 48H. REDOX measurements on the radioactive solid products indicate a reducing atmosphere with extremely low oxygen fugacity--evidence that the sealed crucible tests performed in the presence of a reductant (sugar) under constant argon purge were successful in duplicating the pyrolysis reactions occurring with the Tank 48H feed. Soluble anion measurements confirm that using sugar as reductant at 1X stoichiometry was successful in destroying nitrate/nitrite in the Tank 48H feed. Radioanalytical measurements indicate that (almost equal to)75% of the starting Cs-137 is retained in the solid product. No attempts were made to analyze/measure other potential Cs-137 in the process, i.e., as possible volatile components on the inner surface of the alumina crucible/lid or as offgas escaping the sealed crucible. The collective results from these crucible scale tests on radioactive material are in good agreement with simulant testing. Crucible scale processing has been shown to duplicate the complex reactions of an actual fluidized bed steam reformer. Thus this current testing should provide a high degree of confidence that upcoming bench-scale steam reforming with radioactive Tank 48H slurry will be successful in tetraphenylborate destruction and production of sodium carbonate product.

Development of Chemical Treatment Alternatives for Tetraphenylborate Destruction in Tank 48H.

Development of Chemical Treatment Alternatives for Tetraphenylborate Destruction in Tank 48H.
Author: D. P. Lambert
Publisher:
Total Pages: 5
Release: 2003
Genre:
ISBN:

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This study assessed chemical treatment options for decomposing the tetraphenylborate in High Level Waste (HLW) Tank 48H. Tank 48H, located at the Savannah River Site in Aiken, SC, contains approximately one million liters of HLW. The tetraphenylborate slurry represents legacy material from commissioning of an In Tank Precipitation process to separate radioactive cesium and actinides from the non radioactive chemicals. During early operations, the process encountered an unplanned chemical reaction that catalytically decomposed the excess tetraphenylborate producing benzene. Subsequent research indicated that personnel could not control the operations within the existing equipment to both meet the desired treatment rate for the waste and maintain the benzene concentration within allowable concentrations. Since then, the Department of Energy selected an alternate treatment process for handling high-level waste at the site. However, the site must destroy the tetraphenylborate before returning the tank to HLW service. The research focuses on identifying treatments to decompose tetraphenylborate to the maximum extent feasible, with a preference for decomposition methods that produce carbon dioxide rather than benzene. A number of experiments examined whether the use of oxidants, catalysts or acids proved effective in decomposing the tetraphenylborate. Additional experiments developed an understanding of the solid, liquid and gas decomposition products. The testing identified several successful treatment options including: an iron catalyst combined with hydrogen peroxide (Fenton's reagent) with added acid; sodium permanganate with added acid; and copper catalyst with added acid. A mistake occurred in the selection and make-up of the Tank 48H simulant recipe which led to an under representation of the amount of monosodium titanate and insoluble sludge solids compared to the simulant target. The amount of added MST and sludge proved about a factor of 40 low relative to the measured Tank 48H values. The MST and sludge are insoluble solids that were likely inert in the testing completed. As a result, the mistake had no impact on the testing. Any future Tank 48H research should be completed using the latest Tank 48H simulant recipe.

Evaluation of the Small-Tank Tetraphenylborate Process Using a Bench-Scale, 20-L Continuous Stirred Tank Reactor System at Oak Ridge National Laboratory

Evaluation of the Small-Tank Tetraphenylborate Process Using a Bench-Scale, 20-L Continuous Stirred Tank Reactor System at Oak Ridge National Laboratory
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Total Pages: 87
Release: 2001
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The goal of the Savannah River Salt Waste Processing Program (SPP) is to evaluate the presently available technologies and select the most effective approach for treatment of high-level waste salt solutions currently stored in underground tanks at the U.S. Department of Energy's Savannah River Site in Aiken, South Carolina. One of the three technologies currently being developed for this application is the Small-Tank Tetraphenylborate Process (STTP). This process uses sodium tetraphenylborate (TPB) to precipitate and remove radioactive cesium from the waste and monosodium titanate (MST) to sorb and remove radioactive strontium and actinides. Oak Ridge National Laboratory is demonstrating this process at the 1:4000 scale using a 20-L-capacity continuous-flow stirred-tank reactor (CSTR) system. Since March 1999, five operating campaigns of the 20-L CSTR have been conducted. The ultimate goal is to verify that this process, under certain extremes of operating conditions, can meet the minimum treatment criteria necessary for processing and disposing of the salt waste at the Savannah River Saltstone Facility. The waste acceptance criteria (WAC) for 137Cs, 9°Sr, and total alpha nuclides are

Tank 50H Tetraphenylborate Destruction Results

Tank 50H Tetraphenylborate Destruction Results
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Publisher:
Total Pages: 5
Release: 2003
Genre:
ISBN:

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We conducted several scoping tests with both Tank 50H surrogate materials (KTPB and phenol) as well as with actual Tank 50H solids. These tests examined whether we could destroy the tetraphenylborate in the surrogates or actual Tank 50H material either by use of Fenton's Reagent or by hydrolysis (in Tank 50H conditions at a maximum temperature of 50 degrees C) under a range of conditions. The results of these tests showed that destruction of the solids occurred only under a minority of conditions. (1)Using Fenton's Reagent and KTPB as the Tank 50H surrogate, no reaction occurred at pH ranges greater than 9. (2)Using Fenton's Reagent and phenol as the Tank 50H surrogate, no reaction occurred at a pH of 14. (3)Using Fenton's Reagent and actual Tank 50H slurry, a reaction occurred at a pH of 9.5 in the presence of ECC additives. (4)Using Fenton's Reagent and actual Tank 50H slurry, after a thirty three day period, all attempts at hydrolysis (at pH 14) were too slow to be viable. This happened even in the case of higher temperature (50 degrees C) and added (100 ppm) copper. Tank 50H is scheduled to return to HLW Tank Farm service with capabilities of transferring and receiving salt supernate solutions to and from the Tank Farms and staging feed for the Saltstone Facility. Before returning Tank 50H to Tank Farm service as a non-organic tank, less than 5 kg of TPB must remain in Tank 50H. Recently, camera inspections in Tank 50H revealed two large mounds of solid material, one in the vicinity of the B5 Riser Transfer Pump and the other on the opposite side of the tank. Personnel sampled and analyzed this material to determine its composition. The sample analysis indicated presence of a significant quantity of organics in the solid material. This quantity of organic material exceeds the 5 kg limit for declaring only trace amounts of organic material remain in Tank 50H. Additionally, these large volumes of solids, calculated as approximately 61K gallons, present other obstacles upon returning Tank 50H to HLW service. The concerns include the potential for retention of flammable gases, nuclear criticality safety implications, and possible combustible solids formation. A recent document describes the initial results of that work.

Methods of Seawater Analysis

Methods of Seawater Analysis
Author: Klaus Grasshoff
Publisher: John Wiley & Sons
Total Pages: 632
Release: 2009-07-30
Genre: Science
ISBN: 3527613994

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Since the book first appeared in 1976, Methods of Seawater Analysis has found widespread acceptance as a reliable and detailed source of information. Its second extended and revised edition published in 1983 reflected the rapid pace of instrumental and methodological evolution in the preceding years. The development has lost nothing of its momentum, and many methods and procedures still suffering their teething troubles then have now matured into dependable tools for the analyst. This is especially evident for trace and ultra-trace analyses of organic and inorganic seawater constituents which have diversified considerably and now require more space for their description than before. Methods to determine volatile halocarbons, dimethyl sulphide, photosynthetic pigments and natural radioactive tracers have been added as well as applications of X-ray fluorescence spectroscopy and various electrochemical methods for trace metal analysis. Another method not previously described deals with the determination of the partial pressure of carbon dioxide as part of standardised procedures to describe the marine CO2 system.

Microwave Assisted Organic Synthesis

Microwave Assisted Organic Synthesis
Author: Jason Tierney
Publisher: John Wiley & Sons
Total Pages: 296
Release: 2009-02-12
Genre: Science
ISBN: 1405168447

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The first reports on the application of microwaves in organicsynthesis date back to 1986, but it was not until the recentintroduction of specifically designed and constructed equipment,which countered the safety and reproducibility concerns, thatsynthetic application of microwaves has become established as alaboratory technique. Microwave assisted synthesis is now beingadopted in many industrial and academic laboratories to takeadvantage of the novel chemistry that can be carried out using avariety of organic reaction types. This book demonstrates the underlying principles of microwavedielectric heating and, by reference to a range of organic reactiontypes, it's effective use in synthetic organic chemistry. Toillustrate the impact microwave assisted organic synthesis can haveon chemical research, case studies drawn mainly from thepharmaceutical industry are presented.