DOE OSTI2011
Antifoam 747 is added to minimize foam produced by process gases and water vapor during chemical processing of sludge in the Defense Waste Processing Facility (DWPF). This allows DWPF to maximize acid addition and evaporation rates to minimize the cycle time in the Chemical Processing Cell (CPC). Improvements in DWPF melt rate due to the addition of bubblers in the melter have resulted in the need for further reductions in cycle time in the CPC. This can only be accomplished with an effective antifoam agent. DWPF production was suspended on March 22, 2011 as the result of a Flammable Gas New Information/(NI) Potential Inadequacy in the Safety Analysis (PISA). The issue was that the DWPF melter offgas flammability strategy did not take into account the H and C in the antifoam, potentially flammable components, in the melter feed. It was also determined the DWPF was using much more antifoam than anticipated due to a combination of longer processing in the CPC due to high Hg, longer processing due to Actinide Removal Process (ARP)/Modular Caustic Side Solvent Extraction Unit (MCU) additions, and adding more antifoam than recommended. The resolution to the PISA involved and assessment of the impact of the antifoam on melter flammability and the implementation of a strategy to control additions within acceptable levels. This led to the need to minimize the use of Antifoam 747 in processing beginning in May 2011. DWPF has had limited success in using Antifoam 747 in caustic processing. Since starting up the ARP facility, the ARP product (similar chemically to caustic sludge) is added to the Sludge Receipt and Adjustment Tank (SRAT) at boiling and evaporated to maintain a constant SRAT volume. Although there is very little offgas generated during caustic boiling, there is a large volume of water vapor produced which can lead to foaming. High additions and more frequent use of antifoam are used to mitigate the foaming during caustic boiling. The result of these three issues above is that DWPF had three antifoam needs in FY2011: (1) Determine the cause of the poor Antifoam 747 performance during caustic boiling; (2) Determine the decomposition products of Antifoam 747 during CPC processing; and (3) Improve the effectiveness of Antifoam 747, in order to minimize the amount used. Testing was completed by Illinois Institute of Technology (IIT) and Savannah River National Laboratory (SRNL) researchers to address these questions. The testing results reported were funded by both DWPF and DOE/EM 31. Both sets of results are reported in this document for completeness. The results of this research are summarized: (1) The cause for the poor Antifoam 747 performance during caustic boiling was the high hydrolysis rate, cleaving the antifoam molecule in two, leading to poor antifoam performance. In testing with pH solutions from 1 to 13, the antifoam degraded quickly at a pH < 4 and pH > 10. As the antifoam decomposed it lost its spreading ability (wetting agent performance), which is crucial to its antifoaming performance. During testing of a caustic sludge simulants, there was more foam in tests with added Antifoam 747 than in tests without added antifoam. (2) Analyses were completed to determine the composition of the two antifoam components and Antifoam 747. In addition, the decomposition products of Antifoam 747 were determined during CPC processing of sludge simulants. The main decomposition products were identified primarily as Long Chain Siloxanes, boiling point > 400 C. Total antifoam recovery was 33% by mass. In a subsequent study, various compounds potentially related to antifoam were found using semi-volatile organic analysis and volatile organic analysis on the hexane extractions and hexane rinses. These included siloxanes, trimethyl silanol, methoxy trimethyl silane, hexamethyl disiloxane, aliphatic hydrocarbons, dioctyl phthalate, and emulsifiers. Cumulatively, these species amounted to less than 3% of the antifoam mass. The majority of the antifoam was identified using carbon analysis of the SRAT product (40-80% by mass) and silicon analysis (23-83% by mass) of the condensate. Both studies recommended a better solvent for antifoam and more specific tests for antifoam degradation products than the Si and C analyses used. (3) The DWPF Antifoam 747 Purchase Specification was revised in Month, 2011 with a goal of increasing the quality of Antifoam 747. The purchase specification was changed to specify the manufacturer and product for both components that are blended by Siovation to produce Antifoam 747 for DWPF. Testing of Antifoam produced using both the old and new antifoam specifications perform very similarly in testing. Since the change in purchase specification has not improved antifoam performance, an improved antifoam agent is required.