skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: FLUIDIZED BED STEAM REFORMING TECHNOLOGY FOR ORGANIC AND NITRATE SALT SUPERNATE

Abstract

About two decades ago a process was developed at the Savannah River Site (SRS) to remove Cs137 from radioactive high level waste (HLW) supernates so the supernates could be land disposed as low activity waste (LAW). Sodium tetraphenylborate (NaTPB) was used to precipitate Cs{sup 137} as CsTPB. The flowsheet called for destruction of the organic TPB by acid hydrolysis so that the Cs{sup 137} enriched residue could be mixed with other HLW sludge, vitrified, and disposed of in a federal geologic repository. The precipitation process was demonstrated full scale with actual HLW waste and a 2.5 wt% Cs137 rich precipitate containing organic TPB was produced admixed with 240,000 gallons of salt supernate. Organic destruction by acid hydrolysis proved to be problematic and other disposal technologies were investigated. Fluidized Bed Steam Reforming (FBSR), which destroys organics by pyrolysis, is the current baseline technology for destroying the TPB and the waste nitrates prior to vitrification. Bench scale tests were designed and conducted at the Savannah River National Laboratory (SRNL) to reproduce the pyrolysis reactions. The formation of alkali carbonate phases that are compatible with DWPF waste pre-processing and vitrification were demonstrated in the bench scale tests. Test parameters were optimized for amore » pilot scale FBSR demonstration that was performed at the SAIC Science & Technology Application Research (STAR) Center in Idaho Falls, ID by Idaho National Laboratory (INL) and SRNL in 2003. An engineering scale demonstration was completed by THOR{reg_sign} Treatment Technologies (TTT) and SRNL in 2006 at the Hazen Research, Inc. test facility in Golden, CO. The same mineral carbonate phases, the same organic destruction (>99.99%) and the same nitrate/nitrite destruction (>99.99%) were produced at the bench scale, pilot scale, and engineering scale although different sources of carbon were used during testing.« less

Authors:
;
Publication Date:
Research Org.:
SRS
Sponsoring Org.:
USDOE
OSTI Identifier:
902850
Report Number(s):
WSRC-STI-2007-00170
TRN: US0703001
DOE Contract Number:
DE-AC09-96SR18500
Resource Type:
Conference
Resource Relation:
Conference: 26th Annual International Conference on Incineration and Thermal Treatment Technologies
Country of Publication:
United States
Language:
English
Subject:
12 MANAGEMENT OF RADIOACTIVE WASTES, AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; ACID HYDROLYSIS; CARBON; CARBONATES; COMBUSTION; FLOWSHEETS; FLUIDIZED BEDS; NITRATES; PRECIPITATION; PYROLYSIS; RESIDUES; SODIUM; STEAM; TESTING; VITRIFICATION; WASTES

Citation Formats

Jantzen, C, and Michael02 Smith, M. FLUIDIZED BED STEAM REFORMING TECHNOLOGY FOR ORGANIC AND NITRATE SALT SUPERNATE. United States: N. p., 2007. Web.
Jantzen, C, & Michael02 Smith, M. FLUIDIZED BED STEAM REFORMING TECHNOLOGY FOR ORGANIC AND NITRATE SALT SUPERNATE. United States.
Jantzen, C, and Michael02 Smith, M. Fri . "FLUIDIZED BED STEAM REFORMING TECHNOLOGY FOR ORGANIC AND NITRATE SALT SUPERNATE". United States. doi:. https://www.osti.gov/servlets/purl/902850.
@article{osti_902850,
title = {FLUIDIZED BED STEAM REFORMING TECHNOLOGY FOR ORGANIC AND NITRATE SALT SUPERNATE},
author = {Jantzen, C and Michael02 Smith, M},
abstractNote = {About two decades ago a process was developed at the Savannah River Site (SRS) to remove Cs137 from radioactive high level waste (HLW) supernates so the supernates could be land disposed as low activity waste (LAW). Sodium tetraphenylborate (NaTPB) was used to precipitate Cs{sup 137} as CsTPB. The flowsheet called for destruction of the organic TPB by acid hydrolysis so that the Cs{sup 137} enriched residue could be mixed with other HLW sludge, vitrified, and disposed of in a federal geologic repository. The precipitation process was demonstrated full scale with actual HLW waste and a 2.5 wt% Cs137 rich precipitate containing organic TPB was produced admixed with 240,000 gallons of salt supernate. Organic destruction by acid hydrolysis proved to be problematic and other disposal technologies were investigated. Fluidized Bed Steam Reforming (FBSR), which destroys organics by pyrolysis, is the current baseline technology for destroying the TPB and the waste nitrates prior to vitrification. Bench scale tests were designed and conducted at the Savannah River National Laboratory (SRNL) to reproduce the pyrolysis reactions. The formation of alkali carbonate phases that are compatible with DWPF waste pre-processing and vitrification were demonstrated in the bench scale tests. Test parameters were optimized for a pilot scale FBSR demonstration that was performed at the SAIC Science & Technology Application Research (STAR) Center in Idaho Falls, ID by Idaho National Laboratory (INL) and SRNL in 2003. An engineering scale demonstration was completed by THOR{reg_sign} Treatment Technologies (TTT) and SRNL in 2006 at the Hazen Research, Inc. test facility in Golden, CO. The same mineral carbonate phases, the same organic destruction (>99.99%) and the same nitrate/nitrite destruction (>99.99%) were produced at the bench scale, pilot scale, and engineering scale although different sources of carbon were used during testing.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Fri Mar 30 00:00:00 EDT 2007},
month = {Fri Mar 30 00:00:00 EDT 2007}
}

Conference:
Other availability
Please see Document Availability for additional information on obtaining the full-text document. Library patrons may search WorldCat to identify libraries that hold this conference proceeding.

Save / Share:
  • A salt supernate waste (Tank 48H) generated at the Savannah River Site (SRS) during demonstration of In Tank Precipitation (ITP) process for Cs removal contains nitrates, nitrites, and sodium tetraphenyl borate (NaTPB). This slurry must be pre-processed in order to reduce the impacts of the nitrate and organic species on subsequent vitrification in the Defense Waste Processing Facility (DWPF). Fluidized Bed Steam Reforming (FBSR) is a candidate technology for destroying the nitrates, nitrites, and organics (NaTPB) prior to melting. Bench scale tests were designed and conducted at the Savannah River National Laboratory (SRNL) to demonstrate that bench scale testing canmore » adequately reproduce the CO/CO2 and H2/H2O fugacities representative of the FBSR process and form the appropriate product phases. Carbonate and silicate product phases that were compatible with DWPF vitrification were achieved in the bench scale testing and test parameters were optimized for a pilot scale FBSR demonstration.« less
  • Waste streams that may be generated by the Global Nuclear Energy Partnership (GNEP) Advanced Energy Initiative may contain significant quantities of organics (0-53 wt%) and/or nitrates (0-56 wt%). Decomposition of high nitrate streams requires reducing conditions, e.g. organic additives such as sugar or coal, to reduce the NO{sub x} in the off-gas to N{sub 2} to meet the Clean Air Act (CAA) standards during processing. Thus, organics will be present during waste form stabilization regardless of which GNEP processes are chosen, e.g. organics in the feed or organics for nitrate destruction. High organic containing wastes cannot be stabilized with themore » existing HLW Best Developed Available Technology (BDAT) which is HLW vitrification (HLVIT) unless the organics are removed by preprocessing. Alternative waste stabilization processes such as Fluidized Bed Steam Reforming (FBSR) operate at moderate temperatures (650-750 C) compared to vitrification (1150-1300 C). FBSR converts organics to CAA compliant gases, creates no secondary liquid waste streams, and creates a stable mineral waste form that is as durable as glass. For application to the high Cs-137 and Sr-90 containing GNEP waste streams a single phase mineralized Cs-mica phase was made by co-reacting illite clay and GNEP simulated waste. The Cs-mica accommodates up to 30% wt% Cs{sub 2}O and all the GNEP waste species, Ba, Sr, Rb including the Cs-137 transmutation to Ba-137. For reference, the cesium mineral pollucite (CsAlSi{sub 2}O{sub 6}), currently being studied for GNEP applications, can only be fabricated at {ge} 1000 C. Pollucite mineralization creates secondary aqueous waste streams and NO{sub x}. Pollucite is not tolerant of high concentrations of Ba, Sr or Rb and forces the divalent species into different mineral host phases. The pollucite can accommodate up to 33% wt% Cs{sub 2}O.« less
  • Over a decade ago, an in-tank precipitation process to remove Cs-137 from radioactive high level waste (HLW) supernates was demonstrated at the Savannah River Site (SRS). The full scale demonstration with actual HLW was performed in SRS Tank 48 (T48). Sodium tetraphenylborate (NaTPB) was added to enable Cs-137 extraction as CsTPB. The CsTPB, an organic, and its decomposition products proved to be problematic for subsequent processing of the Cs-137 precipitate in the SRS HLW vitrification facility for ultimate disposal in a HLW repository. Fluidized Bed Steam Reforming (FBSR) is being considered as a technology for destroying the organics and nitratesmore » in the T48 waste to render it compatible with subsequent HLW vitrification. During FBSR processing the T48 waste is converted into organic-free and nitrate-free carbonate-based minerals which are water soluble. The soluble nature of the carbonate-based minerals allows them to be dissolved and pumped to the vitrification facility or returned to the tank farm for future vitrification. The initial use of the FBSR process for T48 waste was demonstrated with simulated waste in 2003 at the Savannah River National Laboratory (SRNL) using a specially designed sealed crucible test that reproduces the FBSR pyrolysis reactions, i.e. carbonate formation, organic and nitrate destruction. This was followed by pilot scale testing of simulants at the Science Applications International Corporation (SAIC) Science & Technology Application Research (STAR) Center in Idaho Falls, ID by Idaho National Laboratory (INL) and SRNL in 2003-4 and then engineering scale demonstrations by THOR{reg_sign} Treatment Technologies (TTT) and SRS/SRNL at the Hazen Research, Inc. (HRI) test facility in Golden, CO in 2006 and 2008. Radioactive sealed crucible testing with real T48 waste was performed at SRNL in 2008, and radioactive Benchscale Steam Reformer (BSR) testing was performed in the SRNL Shielded Cell Facility (SCF) in 2008.« less
  • Waste streams that may be generated by the Global Nuclear Energy Partnership (GNEP) Advanced Energy Initiative may contain significant quantities of organics (0-53 wt%) and/or nitrates (0-56 wt%). Decomposition of high nitrate streams requires reducing conditions, e.g. organic additives such as sugar or coal, to reduce the NOx in the off-gas to N{sub 2} to meet the Clean Air Act (CAA) standards during processing. Thus, organics will be present during waste form stabilization regardless of which GNEP processes are chosen, e.g. organics in the feed or organics for nitrate destruction. High organic containing wastes cannot be stabilized with the existingmore » HLW Best Developed Available Technology (BDAT) which is HLW vitrification (HLVIT) unless the organics are removed by preprocessing. Alternative waste stabilization processes such as Fluidized Bed Steam Reforming (FBSR) operate at moderate temperatures (650-750 deg. C) compared to vitrification (1150-1300 deg. C). FBSR converts organics to CAA compliant gases, creates no secondary liquid waste streams, and creates a stable mineral waste form that is as durable as glass. For application to the high Cs-137 and Sr-90 containing GNEP waste streams a single phase mineralized Cs-mica phase was made by co-reacting illite clay and GNEP simulated waste. The Cs-mica accommodates up to 30% wt% Cs{sub 2}O and all the GNEP waste species, Ba, Sr, Rb including the Cs-137 transmutation to Ba-137. For reference, the cesium mineral pollucite (CsAlSi{sub 2}O{sub 6}), currently being studied for GNEP applications, can only be fabricated at {>=}1000 deg. C. Pollucite mineralization creates secondary aqueous waste streams and NOx. Pollucite is not tolerant of high concentrations of Ba, Sr or Rb and forces the divalent species into different mineral host phases. The pollucite can accommodate up to 33% wt% Cs{sub 2}O. (authors)« less
  • The Savannah River Site (SRS) must empty the contents of Tank 48H, a 1.3 million gallon Type IIIA HLW storage tank, to return this tank to service. The tank contains organic compounds, mainly potassium tetraphenylborate that cannot be processed downstream until the organic components are destroyed. The THOR{reg_sign} Treatment Technologies (TTT) Fluidized Bed Steam Reforming (FBSR) technology, herein after referred to as steam reforming, has been demonstrated to be a viable process to remove greater than 99.9% of the organics from Tank 48H during various bench scale and pilot scale tests. These demonstrations were supported by Savannah River Remediation (SRR)more » and the Department of Energy (DOE) has concurred with the SRR recommendation to proceed with the deployment of the FBSR technology to treat the contents of Tank 48H. The Savannah River National Laboratory (SRNL) developed and proved the concept with non-radioactive simulants for SRR beginning in 2003. By 2008, several pilot scale campaigns had been completed and extensive crucible testing and bench scale testing were performed in the SRNL Shielded Cells using Tank 48H radioactive sample. SRNL developed a Tank 48H non-radioactive simulant complete with organic compounds, salt, and metals characteristic of those measured in a sample of the radioactive contents of Tank 48H. FBSR Pilot Scaled Testing with the Tank 48H simulant has demonstrated the ability to remove greater than 98% of the nitrites and greater than 99.5% of the nitrates from the Tank 48H simulant, and to form a solid product that is primarily alkali carbonate. The alkali carbonate is soluble and, thus, amenable to pumping as a liquid to downstream facilities for processing. The FBSR technology was demonstrated in October of 2006 in the Engineering Scale Test Demonstration (ESTD) pilot scale steam reformer at the Hazen Research Inc. (HRI) facility in Golden, CO. Additional ESTD tests were completed in 2008 and in 2009 that further demonstrated the TTT steam reforming process ability to destroy organics in the Tank 48 simulant and produce a soluble carbonate waste form. The ESTD was operated at varying feed rates and Denitration and Mineralization Reformer (DMR) temperatures, and at a constant Carbon Reduction Reformer (CRR) temperature of 950 C. The process produced a dissolvable carbonate product suitable for processing downstream. ESTD testing was performed in 2009 at the Hazen facility to demonstrate the long term operability of an integrated FBSR processing system with carbonate product and carbonate slurry handling capability. The final testing demonstrated the integrated TTT FBSR capability to process the Tank 48 simulant from a slurry feed into a greater than 99.9% organic free and primarily dissolved carbonate FBSR product slurry. This paper will discuss the SRNL analytical results of samples analyzed from the 2008 and 2009 THOR{reg_sign} steam reforming ESTD performed with Tank 48H simulant at HRI in Golden, Colorado. The final analytical results will be compared to prior analytical results from samples in terms of organic, nitrite, and nitrate destruction.« less