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Title: Annual Report, Fall 2016: Alternative Chemical Cleaning of Radioactive High Level Waste Tanks - Corrosion Test Results

Abstract

The testing presented in this report is in support of the investigation of the Alternative Chemical Cleaning program to aid in developing strategies and technologies to chemically clean radioactive High Level Waste tanks prior to tank closure. The data and conclusions presented here were the examination of the corrosion rates of A285 carbon steel and 304L stainless steel exposed to two proposed chemical cleaning solutions: acidic permanganate (0.18 M nitric acid and 0.05M sodium permanganate) and caustic permanganate. (10 M sodium hydroxide and 0.05M sodium permanganate). These solutions have been proposed as a chemical cleaning solution for the retrieval of actinides in the sludge in the waste tanks, and were tested with both HM and PUREX sludge simulants at a 20:1 ratio.

Authors:
 [1]
  1. Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)
Publication Date:
Research Org.:
Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)
Sponsoring Org.:
USDOE Office of Environmental Management (EM)
OSTI Identifier:
1323878
Report Number(s):
SRNL-STI-2016-00465
TRN: US1601909
DOE Contract Number:
AC09-08SR22470
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; HIGH-LEVEL RADIOACTIVE WASTES; STAINLESS STEEL-304L; PERMANGANATES; SODIUM COMPOUNDS; SOLUTIONS; TANKS; CARBON STEELS; CORROSION; CLEANING; NITRIC ACID; SODIUM HYDROXIDES; ACTINIDES; CARBON; SLUDGES; REMOVAL; SIMULATION; PUREX PROCESS; enhanced chemical cleaning; corrosion; permanganate; oxalic acid; nitric acid; tank waste heel

Citation Formats

Wyrwas, R. B. Annual Report, Fall 2016: Alternative Chemical Cleaning of Radioactive High Level Waste Tanks - Corrosion Test Results. United States: N. p., 2016. Web. doi:10.2172/1323878.
Wyrwas, R. B. Annual Report, Fall 2016: Alternative Chemical Cleaning of Radioactive High Level Waste Tanks - Corrosion Test Results. United States. doi:10.2172/1323878.
Wyrwas, R. B. 2016. "Annual Report, Fall 2016: Alternative Chemical Cleaning of Radioactive High Level Waste Tanks - Corrosion Test Results". United States. doi:10.2172/1323878. https://www.osti.gov/servlets/purl/1323878.
@article{osti_1323878,
title = {Annual Report, Fall 2016: Alternative Chemical Cleaning of Radioactive High Level Waste Tanks - Corrosion Test Results},
author = {Wyrwas, R. B.},
abstractNote = {The testing presented in this report is in support of the investigation of the Alternative Chemical Cleaning program to aid in developing strategies and technologies to chemically clean radioactive High Level Waste tanks prior to tank closure. The data and conclusions presented here were the examination of the corrosion rates of A285 carbon steel and 304L stainless steel exposed to two proposed chemical cleaning solutions: acidic permanganate (0.18 M nitric acid and 0.05M sodium permanganate) and caustic permanganate. (10 M sodium hydroxide and 0.05M sodium permanganate). These solutions have been proposed as a chemical cleaning solution for the retrieval of actinides in the sludge in the waste tanks, and were tested with both HM and PUREX sludge simulants at a 20:1 ratio.},
doi = {10.2172/1323878},
journal = {},
number = ,
volume = ,
place = {United States},
year = 2016,
month = 9
}

Technical Report:

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  • The testing presented in this report is in support of the investigation of the Alternative Chemical Cleaning program to aid in developing strategies and technologies to chemically clean radioactive High Level Waste tanks prior to tank closure. The data and conclusions presented here were the examination of the corrosion rates of A285 carbon steel and 304L stainless steel when interacted with the chemical cleaning solution composed of 0.18 M nitric acid and 0.5 wt. % oxalic acid. This solution has been proposed as a dissolution solution that would be used to remove the remaining hard heel portion of the sludgemore » in the waste tanks. This solution was combined with the HM and PUREX simulated sludge with dilution ratios that represent the bulk oxalic cleaning process (20:1 ratio, acid solution to simulant) and the cumulative volume associated with multiple acid strikes (50:1 ratio). The testing was conducted over 28 days at 50°C and deployed two methods to invest the corrosion conditions; passive weight loss coupon and an active electrochemical probe were used to collect data on the corrosion rate and material performance. In addition to investigating the chemical cleaning solutions, electrochemical corrosion testing was performed on acidic and basic solutions containing sodium permanganate at room temperature to explore the corrosion impacts if these solutions were to be implemented to retrieve remaining actinides that are currently in the sludge of the tank.« less
  • 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 beenmore » 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.« less
  • Solubility testing with simulated High Level Waste tank heel solids has been conducted in order to evaluate two alternative chemical cleaning technologies for the dissolution of sludge residuals remaining in the tanks after the exhaustion of mechanical cleaning and sludge washing efforts. Tests were conducted with non-radioactive pure phase metal reagents, binary mixtures of reagents, and a Savannah River Site PUREX heel simulant to determine the effectiveness of an optimized, dilute oxalic/nitric acid cleaning reagent and pure, dilute nitric acid toward dissolving the bulk non-radioactive waste components. A focus of this testing was on minimization of oxalic acid additions duringmore » tank cleaning. For comparison purposes, separate samples were also contacted with pure, concentrated oxalic acid which is the current baseline chemical cleaning reagent. In a separate study, solubility tests were conducted with radioactive tank heel simulants using acidic and caustic permanganate-based methods focused on the “targeted” dissolution of actinide species known to be drivers for Savannah River Site tank closure Performance Assessments. Permanganate-based cleaning methods were evaluated prior to and after oxalic acid contact.« less
  • Several 300 series stainless steels were corrosion tested in raffinate storage tanks made of the same materials. After exposure to the rafflnate solutions for periods of up to seven years, maximum penetration rates of 0.1 mil/ yr were noted. (auth)
  • 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 previousmore » 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/O{sub 3}/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.« less