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Title: PROCESSING ALTERNATIVES FOR DESTRUCTION OF TETRAPHENYLBORATE

Abstract

Two processes were chosen in the 1980's at the Savannah River Site (SRS) to decontaminate the soluble High Level Waste (HLW). The In Tank Precipitation (ITP) process (1,2) was developed at SRS for the removal of radioactive cesium and actinides from the soluble HLW. Sodium tetraphenylborate was added to the waste to precipitate cesium and monosodium titanate (MST) was added to adsorb actinides, primarily uranium and plutonium. Two products of this process were a low activity waste stream and a concentrated organic stream containing cesium tetraphenylborate and actinides adsorbed on monosodium titanate (MST). A copper catalyzed acid hydrolysis process was built to process (3, 4) the Tank 48H cesium tetraphenylborate waste in the SRS's Defense Waste Processing Facility (DWPF). Operation of the DWPF would have resulted in the production of benzene for incineration in SRS's Consolidated Incineration Facility. This process was abandoned together with the ITP process in 1998 due to high benzene in ITP caused by decomposition of excess sodium tetraphenylborate. Processing in ITP resulted in the production of approximately 1.0 million liters of HLW. SRS has chosen a solvent extraction process combined with adsorption of the actinides to decontaminate the soluble HLW stream (5). However, the waste inmore » Tank 48H is incompatible with existing waste processing facilities. As a result, a processing facility is needed to disposition the HLW in Tank 48H. This paper will describe the process for searching for processing options by SRS task teams for the disposition of the waste in Tank 48H. In addition, attempts to develop a caustic hydrolysis process for in tank destruction of tetraphenylborate will be presented. Lastly, the development of both a caustic and acidic copper catalyzed peroxide oxidation process will be discussed.« less

Authors:
; ;
Publication Date:
Research Org.:
SRS
Sponsoring Org.:
USDOE
OSTI Identifier:
901917
Report Number(s):
WSRC-STI-2007-00107
TRN: US0702711
DOE Contract Number:
DE-AC09-96SR18500
Resource Type:
Conference
Resource Relation:
Conference: International Conference on Incineration and Thermal Treatment Technologies Conference, May 14-18, 2007, Phoenix, AZ
Country of Publication:
United States
Language:
English
Subject:
12 MANAGEMENT OF RADIOACTIVE WASTES, AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; BORATES; CESIUM COMPOUNDS; ACID HYDROLYSIS; ACTINIDES; ADSORPTION; SOLVENT EXTRACTION; RADIOACTIVE WASTE PROCESSING; HIGH-LEVEL RADIOACTIVE WASTES; SAVANNAH RIVER PLANT; ALKALINE HYDROLYSIS

Citation Formats

Lambert, D, Thomas Peters, T, and Samuel Fink, S. PROCESSING ALTERNATIVES FOR DESTRUCTION OF TETRAPHENYLBORATE. United States: N. p., 2007. Web.
Lambert, D, Thomas Peters, T, & Samuel Fink, S. PROCESSING ALTERNATIVES FOR DESTRUCTION OF TETRAPHENYLBORATE. United States.
Lambert, D, Thomas Peters, T, and Samuel Fink, S. Tue . "PROCESSING ALTERNATIVES FOR DESTRUCTION OF TETRAPHENYLBORATE". United States. doi:. https://www.osti.gov/servlets/purl/901917.
@article{osti_901917,
title = {PROCESSING ALTERNATIVES FOR DESTRUCTION OF TETRAPHENYLBORATE},
author = {Lambert, D and Thomas Peters, T and Samuel Fink, S},
abstractNote = {Two processes were chosen in the 1980's at the Savannah River Site (SRS) to decontaminate the soluble High Level Waste (HLW). The In Tank Precipitation (ITP) process (1,2) was developed at SRS for the removal of radioactive cesium and actinides from the soluble HLW. Sodium tetraphenylborate was added to the waste to precipitate cesium and monosodium titanate (MST) was added to adsorb actinides, primarily uranium and plutonium. Two products of this process were a low activity waste stream and a concentrated organic stream containing cesium tetraphenylborate and actinides adsorbed on monosodium titanate (MST). A copper catalyzed acid hydrolysis process was built to process (3, 4) the Tank 48H cesium tetraphenylborate waste in the SRS's Defense Waste Processing Facility (DWPF). Operation of the DWPF would have resulted in the production of benzene for incineration in SRS's Consolidated Incineration Facility. This process was abandoned together with the ITP process in 1998 due to high benzene in ITP caused by decomposition of excess sodium tetraphenylborate. Processing in ITP resulted in the production of approximately 1.0 million liters of HLW. SRS has chosen a solvent extraction process combined with adsorption of the actinides to decontaminate the soluble HLW stream (5). However, the waste in Tank 48H is incompatible with existing waste processing facilities. As a result, a processing facility is needed to disposition the HLW in Tank 48H. This paper will describe the process for searching for processing options by SRS task teams for the disposition of the waste in Tank 48H. In addition, attempts to develop a caustic hydrolysis process for in tank destruction of tetraphenylborate will be presented. Lastly, the development of both a caustic and acidic copper catalyzed peroxide oxidation process will be discussed.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Tue Feb 27 00:00:00 EST 2007},
month = {Tue Feb 27 00:00:00 EST 2007}
}

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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 nonradioactive 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 themore » 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.« less
  • 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 formore » 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.« less
  • The Savannah River Site has generated 77 million gallons of high level radioactive waste since the early 1950's. By 1987, evaporation had reduced the concentration of the waste inventory to 35 million gallons. Currently, the wastes reside in large underground tanks as a soluble fraction stored, crystallized salts, and an insoluble fraction, sludge, which consists of hydrated transition metal oxides. The bulk of the radionuclides, 67 percent, are in the sludge while the crystallized salts and supernate are composed of the nitrates, nitrites, sulfates and hydroxides of sodium, potassium, and cesium. The principal radionuclide in the soluble waste is {supmore » 137}Cs with traces of {sup 90}Sr. The transformation of the high level wastes into a borosilicate glass suitable for permanent disposal is the goal of the Defense Waste Processing Facility (DWPF). To minimize the volume of glass produced, the soluble fraction of the waste is treated with sodium tetraphenylborate and sodium titanate in the waste tanks to precipitate the radioactive cesium ion and absorb the radioactive strontium ion. The precipitate is washed in the waste tanks and is then pumped to the DWPF. The precipitate, as received, is incompatible with the vitrification process because of the high aromatic carbon content and requires further chemical treatment. Within the DWPF, the precipitate is processed in the Salt Processing Cell to remove the aromatic carbon as benzene. The precipitate hydrolysis process hydrolyzes the tetraphenylborate anion to produce borate anion and benzene. The benzene is removed by distillation, decontaminated and transferred out of the DWPF for disposal.« less
  • The Savannah River Site has generated 77 million gallons of high level radioactive waste since the early 1950`s. By 1987, evaporation had reduced the concentration of the waste inventory to 35 million gallons. Currently, the wastes reside in large underground tanks as a soluble fraction stored, crystallized salts, and an insoluble fraction, sludge, which consists of hydrated transition metal oxides. The bulk of the radionuclides, 67 percent, are in the sludge while the crystallized salts and supernate are composed of the nitrates, nitrites, sulfates and hydroxides of sodium, potassium, and cesium. The principal radionuclide in the soluble waste is {supmore » 137}Cs with traces of {sup 90}Sr. The transformation of the high level wastes into a borosilicate glass suitable for permanent disposal is the goal of the Defense Waste Processing Facility (DWPF). To minimize the volume of glass produced, the soluble fraction of the waste is treated with sodium tetraphenylborate and sodium titanate in the waste tanks to precipitate the radioactive cesium ion and absorb the radioactive strontium ion. The precipitate is washed in the waste tanks and is then pumped to the DWPF. The precipitate, as received, is incompatible with the vitrification process because of the high aromatic carbon content and requires further chemical treatment. Within the DWPF, the precipitate is processed in the Salt Processing Cell to remove the aromatic carbon as benzene. The precipitate hydrolysis process hydrolyzes the tetraphenylborate anion to produce borate anion and benzene. The benzene is removed by distillation, decontaminated and transferred out of the DWPF for disposal.« less
  • In February of 1977, the U.S. EPA initiated a feasibility study to evaluate the effectiveness, costs, and impacts associated with alternatives for removing and/or degrading Kepone in the James River, Virginia. The results of that work and their implications to other in-place toxic problems are discussed. Kepone from production discharges and bulk disposal of bad batches of product was released into the environment over the years between 1967 and mid-1975. During that time it is estimated that up to 200,000 lbs may have been discharged. It is further estimated that up to one quarter of that amount currently resides inmore » the sediments of the James River. Ecological studies have indicated that nearly all of the tidal area of the James, over 70 miles, will require amelioration. Hence, if the impact of Kepone in the James River is to be eliminated, over 200 square miles of river bottom may require restoration. It is against this backdrop that the EPA feasibility study was conducted. The investigation covered biological, physical, and chemical alternatives for both restoration of the river and disposal of dredge spoils. The results of that work are summarized.« less