Measuring and Predicting Fission Product Noble Metals in SRS HLW Sludges

Bibler, N

Savannah River Site (S.C.)

关键词: Fission Yield;    Fission;    Lanthanum;    Wastes;    08 Hydrogen;   

DOI  :  10.2172/890173
RP-ID  :  WSRC-TR-2005-00098
RP-ID  :  DE-AC09-96SR18500
RP-ID  :  890173

美国|英语

来源: UNT Digital Library

【 摘 要 】

The noble metals Ru, Rh, Pd, and Ag were produced in the Savannah River Site (SRS) reactors as products of the fission of U-235. Consequently they are in the High Level Waste (HLW) sludges that are currently being immobilized into a borosilicate glass in the Defense Waste Processing Facility (DWPF). The noble metals are a concern in the DWPF because they catalyze the decomposition of formic acid used in the process to produce the flammable gas hydrogen. As the concentration of these noble metals in the sludge increases, more hydrogen will be produced when this sludge is processed. In the SRS Tank Farm it takes approximately two years to prepare a sludge batch for processing in the DWPF. This length of time is necessary to mix the appropriate sludges, blend them to form a sludge batch and then wash it to enable processing in the DWPF. This means that the exact composition of a sludge batch is not known for {approx}two years. During this time, studies with simulated nonradioactive sludges must be performed to determine the desired DWPF processing parameters for the new sludge batch. Consequently, prediction of the noble metal concentrations is desirable to prepare appropriate simulated sludges for studies of the DWPF process for that sludge batch. These studies give a measure of the amount of hydrogen that will be produced when that sludge batch is processed. This report describes in detail the measurement of these noble metal concentrations in sludges and a way to predict their concentrations from an estimate of the lanthanum concentration in the sludge. Results for two sludges are presented in this report. These are Sludge Batch 3 (SB3) currently being processed by the DWPF and a sample of unwashed sludge from Tank 11 that will be part of Sludge Batch 4. The concentrations of the noble metals in HLW sludges are measured by using mass spectroscopy to determine concentrations of the isotopes that comprise each noble metal. For example, the noble metal Ru is comprised of isotopes with masses 101, 102, and 104. The element Rh has a single isotope with mass 103. The element Pd is comprised of five isotopes. These are at masses 105-108 and mass 110. As does Rh, Ag has only one isotope. This is at mass 109. However, results in this report show that the Ag concentration in the two samples was due to natural Ag being in the samples. Natural Ag has masses at 107 and 109. The Ag-107 interferes with the measurement of Pd-107. This Ag was used in one of the processes at SRS. The results also show that natural Cd is in the two samples. Cadmium has isotopes at masses 106, 108 and 110, thus it interferes with the analysis of the Pd isotopes at these masses. Cadmium was also used in one of the processes at SRS. However, the concentrations of the Pd isotopes at masses 106, 107, 108 and 110 could be calculated using the fission yields for the Pd isotopes, and the measured concentration of Pd at mass 105 where there is no Ag or Cd interference. Based on the measurements of the concentrations of the isotopes of each noble metal, the total concentration of that noble metal can be determined by summing the concentrations of the individual isotopes. The results in this report show that the relative concentrations of the isotopes of Ru and Rh are in proportion to their yields from the fission of U-235 in the reactors. These results were expected since these elements are very insoluble in caustic and thus are primarily in the sludge tanks rather then the salt tanks of the SRS Tank Farm. The relative concentration of Pd is somewhat lower than that based on the relative fission yields of its five isotopes. This indicates that some of the Pd is in the salt tanks rather than the sludge tanks of the Tank Farm. The concentrations of the noble metals were predicted using the High Level Waste Characterization System (WCS) at SRS. This system keeps record of the inventory of the major compounds and select radionuclides that are in each of the SRS HLW tanks. Using this system, the Closure Business Unit (CBU) can predict the major composition of a sludge batch by knowing the tanks involved in that batch and the estimates of the volume of sludge from each tank that will be blended to make the final sludge batch. The system does not track the inventories of Rh, Pd, and Ag. It does track Ru, but Ru is not included in the projections by CBU. However, another U-235 fission product is tracked by WCS. This fission product is La. The element La was not used in any of the chemical processes at SRS. Results in this study show that it is in the HLW primarily as a U-235 fission product. This fission product is comprised solely of the isotope La-139 which can be measured along with the isotopes of the noble metals that do not have interferences from Ag or Cd. The concentrations of La in SB3 and in the Tank 11 sample have been estimated by the CBU using WCS projections.