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Title: Oxidative-Alkaline Leaching of Washed 241-SY-102 and 241-SX-101 Tank Sludges and Its Impact on Immobilized High-Level Waste

Abstract

This report describes work designed to evaluate the effectiveness of alkaline permanganate contacts at selectively removing chromium from the Hanford tank sludges 241-SY-102 and 241-SX-101. The key variables examined in this study, as compared to contact with the standard conditions of stoichiometric permanganate in 3 M hydroxide at elevated temperature, were: a) excess permanganate and hydroxide at elevated temperature, b) the separation of an elevated temperature 3 M hydroxide leach with either a room temperature permanganate contact or an elevated temperature permanganate contact at 0.25 M hydroxide. It was determined that sequential permanganate and caustic leaching can provide as effective removal of Cr as the combined high hydroxide permanganate contact at elevated temperature while minimizing concomitant Pu dissolution.

Authors:
 [1];  [1];  [1];  [1]
  1. Battelle, Richland, WA (United States). Pacific Northwest Division
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
889529
Report Number(s):
PNWD-SA-7160
Journal ID: ISSN 0149-6395; SSTEDS; TRN: US0604408
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Separation Science and Technology; Journal Volume: 41; Journal Issue: 10
Country of Publication:
United States
Language:
English
Subject:
12 MANAGEMENT OF RADIOACTIVE WASTES, AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; CHROMIUM; REMOVAL; DISSOLUTION; LEACHING; PERMANGANATES; SLUDGES; STORAGE FACILITIES; HANFORD RESERVATION; HIGH-LEVEL RADIOACTIVE WASTES; Oxidative Leaching; chromium; Hanford Tank Sludge

Citation Formats

Rapko, Brian M., Geeting, John G.H., Sinkov, Sergei I., and Vienna, John D. Oxidative-Alkaline Leaching of Washed 241-SY-102 and 241-SX-101 Tank Sludges and Its Impact on Immobilized High-Level Waste. United States: N. p., 2007. Web. doi:10.1080/01496390600750917.
Rapko, Brian M., Geeting, John G.H., Sinkov, Sergei I., & Vienna, John D. Oxidative-Alkaline Leaching of Washed 241-SY-102 and 241-SX-101 Tank Sludges and Its Impact on Immobilized High-Level Waste. United States. doi:10.1080/01496390600750917.
Rapko, Brian M., Geeting, John G.H., Sinkov, Sergei I., and Vienna, John D. Thu . "Oxidative-Alkaline Leaching of Washed 241-SY-102 and 241-SX-101 Tank Sludges and Its Impact on Immobilized High-Level Waste". United States. doi:10.1080/01496390600750917.
@article{osti_889529,
title = {Oxidative-Alkaline Leaching of Washed 241-SY-102 and 241-SX-101 Tank Sludges and Its Impact on Immobilized High-Level Waste},
author = {Rapko, Brian M. and Geeting, John G.H. and Sinkov, Sergei I. and Vienna, John D.},
abstractNote = {This report describes work designed to evaluate the effectiveness of alkaline permanganate contacts at selectively removing chromium from the Hanford tank sludges 241-SY-102 and 241-SX-101. The key variables examined in this study, as compared to contact with the standard conditions of stoichiometric permanganate in 3 M hydroxide at elevated temperature, were: a) excess permanganate and hydroxide at elevated temperature, b) the separation of an elevated temperature 3 M hydroxide leach with either a room temperature permanganate contact or an elevated temperature permanganate contact at 0.25 M hydroxide. It was determined that sequential permanganate and caustic leaching can provide as effective removal of Cr as the combined high hydroxide permanganate contact at elevated temperature while minimizing concomitant Pu dissolution.},
doi = {10.1080/01496390600750917},
journal = {Separation Science and Technology},
number = 10,
volume = 41,
place = {United States},
year = {Thu Feb 15 00:00:00 EST 2007},
month = {Thu Feb 15 00:00:00 EST 2007}
}
  • Oxidative alkaline leaching has been proposed to pre-treat the high-level nuclear waste sludges to remove some of the problematic (e.g., Cr) and/or non-radioactive (e.g., Na, Al) constituents before vitrification. It is critical to understand the behavior of actinides, americium and plutonium in particular, in oxidative alkaline leaching. We have studied the leaching behavior of americium from four different sludge simulants (BiPO{sub 4}, BiPO{sub 4 modified}, Redox, PUREX) using potassium permanganate and potassium persulfate in alkaline solutions. Up to 60% of americium sorbed onto the simulants is leached from the sludges by alkaline persulfate and permanganate. The percentage of americium leachedmore » increases with [NaOH] (between 1.0 and 5.0 M). The initial rate of americium leaching by potassium persulfate increases in the order BiPO{sub 4} sludge < Redox sludge < PUREX sludge. The data are most consistent with oxidation of Am{sup 3+} in the sludge to either AmO{sub 2}{sup +} or AmO{sub 2}{sup 2+} in solution. Though neither of these species is expected to exhibit long-term stability in solution, the potential for mobilization of americium from sludge samples would have to be accommodated in the design of any oxidative leaching process for real sludge samples.« less
  • Tank 241-SY-101 (SY-101) is a double-shell, radioactive waste storage tank with waste that, before the recent transfer and water back-dilution operations, was capable of retaining gas and producing buoyant displacement (BD) gas release events (GREs). Some BD GREs caused gas concentrations in the tank headspace to exceed the lower flammability limit (LFL). A BD GRE occurs when a portion of the nonconvective layer retains enough gas to become buoyant, rises to the waste surface, breaks up, and releases some of its stored gas. The installation of a mixer pump in 1993 successfully mitigated gas retention in the settled solids layermore » in SY-101 and has since prevented BD GREs. However, operation of the mixer pump over the years caused gas retention in the floating crust layer and a corresponding accelerated waste level growth. The accelerating crust growth trend observed in 1997--98 led to initiation of sequences of waste removal and water back-dilutions in December 1999. Waste is removed from the mixed slurry layer in Tank SY-101 and transferred into Tank 241-Sy-102 (SY-102). Water is then added back to dissolve soluble solids that retain gas. The initial transfer of 89,500 gallons of SY-101 waste, diluted in-line at 0.94:1 by volume with water, to SY-102 was conducted in December 1999. The second transfer of 230,000 gallons of original SY-101 waste, diluted approximately 0.9:1, was completed in January 2000, and the third transfer of 205,500 gallons of original SY-101 waste diluted at 0.9:1 was completed in March 2000.« less
  • Tank 241-SY-101 (SY-101) waste level growth is an emergent, high priority issue. The purpose of this document is to record the hazards evaluation process and document potential hazardous conditions that could lead to the release of radiological and toxicological material from the proposed transfer of a limited quantity (approximately 100,000 gallons) of waste from SY-101 to 241-SY-102 (SY-102). The results of the hazards evaluation will be compared to the current Tank Waste Remediation System (TWRS) Basis for Interim Operation (HNF-SD-WM-BIO-001, 1998, Revision 1) to identify any hazardous conditions where Authorization Basis (AB) controls may not be sufficient or may notmore » exist. Comparison to LA-UR-92-3196, A Safety Assessment for Proposed Pump Mixing Operations to Mitigate Episodic Gas Releases in Tank 241-SY-101, was also made in the case of transfer pump removal activities. This document is not intended to authorize the activity or determine the adequacy of controls; it is only intended to provide information about the hazardous conditions associated with this activity. The Unreviewed Safety Question (USQ) process will be used to determine the adequacy of controls and whether the proposed activity is within the AB. This hazard evaluation does not constitute an accident analysis.« less
  • Tank 241-SY-101 waste level growth is an emergent, high priority issue. The purpose of this document is to record the hazards evaluation process and document potential hazardous conditions that could lead to the release of radiological and toxicological material from the proposed transfer of a limited quantity (approximately 100,000 gallons) of waste from Tank 241-SY-101 to Tank 241-SY-102. The results of the hazards evaluation were compared to the current Tank Waste Remediation System (TWRS) Basis for Interim Operation (HNF-SD-WM-BIO-001, 1998, Revision 1) to identify any hazardous conditions where Authorization Basis (AB) controls may not be sufficient or may not exist.more » Comparison to LA-UR-92-3196, A Safety Assessment for Proposed Pump Mixing Operations to Mitigate Episodic Gas Releases in Tank 241-SY-101, was also made in the case of transfer pump removal activities. Revision 1 of this document deletes hazardous conditions no longer applicable to the current waste transfer design and incorporates hazardous conditions related to the use of an above ground pump pit and overground transfer line. This document is not part of the AB and is not a vehicle for requesting authorization of the activity; it is only intended to provide information about the hazardous conditions associated with this activity. The AB Control Decision process will be used to determine the adequacy of controls and whether the proposed activity is within the AB. This hazard evaluation does not constitute an accident analysis.« less
  • Tank 241-SY-101 is a double-shell radioactive waste storage tank containing waste that, before recent transfer and water back-dilution operations, was capable of retaining gas and producing flammable buoyant displacement gas release events (BD GREs). A BD GRE occurs when a portion of the nonconvective layer waste retains enough gas to become buoyant, rises to the waste surface, breaks up, and releases some of the stored gas. Installing the mixer pump in 1993 successfully mitigated gas retention in the settled solids layer in SY-101 and has prevented BD GREs. Gas retention in the floating drust layer and the corresponding accelerated wastemore » level growth made it necessary to begin waste removal and back-dilution with water in December 1999. During these operations, some of the SY-101 mixed slurry layer is removed and transferred into Tank 241-SY-102. There was some concern that adding the SY-101 waste into SY-102 could create a waste configuration in SY-102 capable of BD GREs. This report updates and extends earlier assessments of the potential for BD GRE conditions in SY-102 after waste is transferred from SY-101. We determined that, under the given assumptions, no possibility of BD GREs exists in SY-102 from the SY-101 waste being added during from December 1999 through March 2000.« less