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Title: REVIEW OF ALTERNATIVE ENHANCED CHEMICAL CLEANING OPTIONS FOR SRS WASTE TANKS

Technical Report ·
DOI:https://doi.org/10.2172/967269· OSTI ID:967269

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 previous 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.

Research Organization:
Savannah River Site (SRS), Aiken, SC (United States)
Sponsoring Organization:
USDOE
DOE Contract Number:
DE-AC09-08SR22470
OSTI ID:
967269
Report Number(s):
SRNL-STI-2009-00500; TRN: US200923%%528
Country of Publication:
United States
Language:
English