BEHAVIOR OF MERCURY DURING DWPF CHEMICAL PROCESS CELL PROCESSING
The Defense Waste Processing Facility has experienced significant issues with the stripping and recovery of mercury in the Chemical Processing Cell (CPC). The stripping rate has been inconsistent, often resulting in extended processing times to remove mercury to the required endpoint concentration. The recovery of mercury in the Mercury Water Wash Tank has never been high, and has decreased significantly since the Mercury Water Wash Tank was replaced after the seventh batch of Sludge Batch 5. Since this time, essentially no recovery of mercury has been seen. Pertinent literature was reviewed, previous lab-scale data on mercury stripping and recovery was examined, and new lab-scale CPC Sludge Receipt and Adjustment Tank (SRAT) runs were conducted. For previous lab-scale data, many of the runs with sufficient mercury recovery data were examined to determine what factors affect the stripping and recovery of mercury and to improve closure of the mercury material balance. Ten new lab-scale SRAT runs (HG runs) were performed to examine the effects of acid stoichiometry, sludge solids concentration, antifoam concentration, form of mercury added to simulant, presence of a SRAT heel, operation of the SRAT condenser at higher than prototypic temperature, varying noble metals from none to very high concentrations, and higher agitation rate. Data from simulant runs from SB6, SB7a, glycolic/formic, and the HG tests showed that a significant amount of Hg metal was found on the vessel bottom at the end of tests. Material balance closure improved from 12-71% to 48-93% when this segregated Hg was considered. The amount of Hg segregated as elemental Hg on the vessel bottom was 4-77% of the amount added. The highest recovery of mercury in the offgas system generally correlated with the highest retention of Hg in the slurry. Low retention in the slurry (high segregation on the vessel bottom) resulted in low recovery in the offgas system. High agitation rates appear to result in lower retention of mercury in the slurry. Both recovery of mercury in the offgas system and removal (segregation + recovery) from the slurry correlate with slurry consistency. Higher slurry consistency results in better retention of Hg in the slurry (less segregation) and better recovery in the offgas system, but the relationships of recovery and retention with consistency are sludge dependent. Some correlation with slurry yield stress and acid stoichiometry was also found. Better retention of mercury in the slurry results in better recovery in the offgas system because the mercury in the slurry is stripped more easily than the segregated mercury at the bottom of the vessel. Although better retention gives better recovery, the time to reach a particular slurry mercury content (wt%) is longer than if the retention is poorer because the segregation is faster. The segregation of mercury is generally a faster process than stripping. The stripping factor (mass of water evaporated per mass of mercury stripped) of mercury at the start of boiling were found to be less than 1000 compared to the assumed design basis value of 750 (the theoretical factor is 250). However, within two hours, this value increased to at least 2000 lb water per lb Hg. For runs with higher mercury recovery in the offgas system, the stripping factor remained around 2000, but runs with low recovery had stripping factors of 4000 to 40,000. DWPF data shows similar trends with the stripping factor value increasing during boiling. These high values correspond to high segregation and low retention of mercury in the sludge. The stripping factor for a pure Hg metal bead in water was found to be about 10,000 lb/lb. About 10-36% of the total Hg evaporated in a SRAT cycle was refluxed back to the SRAT during formic acid addition and boiling. Mercury is dissolved as a result of nitric acid formation from absorption of NO{sub x}. The actual solubility of dissolved mercury in the acidic condensate is about 100 times higher than the actual concentrations measured. Mercury metal present in the MWWT from previous batches could be dissolved by this acidic condensate. The test of the effect of higher SRAT condenser temperature on recovery of mercury in the MWWT and offgas system was inconclusive. The recovery at higher temperature was lower than several low temperature runs, but about the same as other runs. Factors other than temperature appear to affect the mercury recovery. The presence of chloride and iodide in simulants resulted in the formation of mercurous chloride and mercurous iodide, respectively, in the offgas system. Actual waste data shows that the chloride content is much less than the simulant concentrations. Future simulant tests should minimize the addition of chloride. Similarly, iodine addition should be eliminated unless actual waste analyses show it to be present; currently, total iodine is not measured on actual waste samples.
- Research Organization:
- Savannah River Site (SRS), Aiken, SC (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- DE-AC09-08SR22470
- OSTI ID:
- 1038732
- Report Number(s):
- SRNL-STI-2012-00051; TRN: US201209%%265
- Country of Publication:
- United States
- Language:
- English
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