Hydrogen Generation Rate Scoping Study of DOW Corning Antifoam Agent (2005)

The antifoam agent DOW Corning Q2-3183A will be added to waste streams in the Hanford River Protection Program-Waste Treatment and Immobilization Plant (RPP-WTP) to prevent foaming. It consists mostly of polydimethylsiloxane (PDMS) and polypropylene glycol (PPG). These and other minor constituents of the antifoam have organic constituents that may participate in radiolytic and chemical reactions that produce hydrogen in Hanford waste. It has been recommended by The WTP R&T Department recommended personnel to treat the organic compounds of the antifoam like the in a similar manner as other organic compounds that are native to the Hanford waste with respect to hydrogen production. This testing has investigated the radiolytic and thermal production of hydrogen from antifoam added to simulant waste solutions to determine if the organic components of the antifoam produce hydrogen in the same manner as the native organic species in Hanford waste. Antifoam additions for this testing were in the range of 4 to 10 wt% to ensure adequate hydrogen detection. Test conditions were selected to bound exposures to the antifoam agent in the WTP. These levels are higher than previously recommended values of 350 mg/L for actual applications in WTP tanks containing air spargers and pulse jet mixers. Limited degradation analyses for the organic components of the antifoam were investigated in this study. A more detailed study involving analyses of antifoam degradation and product formation is in progress at SRNL and results from that study will be reported at a later time. The total organic carbon (TOC) content of the Q2-3183A antifoam was measured to be 39.7 {+-} 4.9 wt% TOC. This measurement was performed in triplicate with on three different dilutions of the pure antifoam liquid using a TOC combustion analyzer instrument with catalytic oxidation, followed by CO{sub 2} quantification using an infrared detector. Test results from this study indicate that the WTP HGR correlation conservatively bounds hydrogen generation rates (HGRs) from antifoam-containing simulants if the antifoam organic components are treated the same as other native organics. Tests that used the combination of radiolysis and thermolysis conducted on simulants containing antifoam produced measured hydrogen that was bounded by the WTP correlation. These tests used the bounding WTP temperature of 90 C and a dose rate of 1.8 x 10{sup 5} rad/hr. This dose rate is about ten times higher than the dose rate equivalent calculated for a bounding Hanford sludge slurry composition of 10 Ci/L, or 2 x 10{sup 4} rad/hr. Hydrogen was measured using a quadrupole mass spectroscopy instrument. Based on the analyses from the 4wt% and 10wt% antifoam samples, it is expected that the HGR results are directly proportional to the antifoam concentration added. A native organic-containing simulant that did not contain any added antifoam also produced a measurable radiolytic/thermal hydrogen rates that was in bounded by the WTP correlation. A base simulant with no added organic produced a measurable radiolytic/thermal HGR that was {approx}2X higher than the predicted HGR. Analysis of antifoam-containing simulants after prolonged irradiation of 52 Mrad and heating (23 days at 90 C) indicates that essentially all of the PDMS and greater than 60% of the PPG components are degraded, likely to lower molecular weight species. The antifoam components were analyzed by extraction from the salt simulants, followed by gel permeation chromatography (GPC) by personnel at Dow Corning. A more detailed study of the antifoam degradation and product formation from radiolysis and thermolysis is currently in progress at SRNL. That study uses a dose rate of about 2 x 10{sup 4} rad/hr and bounding temperatures of 90 C. Results from that study will be reported in a future report.