Bulk Vitrification Castable Refractory Block Protection Study
Bulk vitrification (BV) was selected for a pilot-scale test and demonstration facility for supplemental treatment to accelerate the cleanup of low-activity waste (LAW) at the Hanford U.S. DOE Site. During engineering-scale (ES) tests, a small fraction of radioactive Tc (and Re, its nonradioactive surrogate) were transferred out of the LAW glass feed and molten LAW glass, and deposited on the surface and within the pores of the castable refractory block (CRB). Laboratory experiments were undertaken to understand the mechanisms of the transport Tc/Re into the CRB during vitrification and to evaluate various means of CRB protection against the deposition of leachable Tc/Re. The tests used Re as a chemical surrogate for Tc. The tests with the baseline CRB showed that the molten LAW penetrates into CRB pores before it converts to glass, leaving deposits of sulfates and chlorides when the nitrate components decompose. Na2O from the LAW reacts with the CRB to create a durable glass phase that may contain Tc/Re. Limited data from a single CRB sample taken from an ES experiment indicate that, while a fraction of Tc/Re is present in the CRB in a readily leachable form, most of the Tc/Re deposited in the refractory is retained in the form of a durable glass phase. In addition, the molten salts from the LAW, mainly sulfates, chlorides, and nitrates, begin to evaporate from BV feeds at temperatures below 800 C and condense on solid surfaces at temperatures below 530 C. Three approaches aimed at reducing or preventing the deposition of soluble Tc/Re within the CRB were proposed: metal lining, sealing the CRB surface with a glaze, and lining the CRB with ceramic tiles. Metal liners were deemed unsuitable because evaluations showed that they can cause unacceptable distortions of the electric field in the BV system. Sodium silicate and a low-alkali borosilicate glaze were selected for testing. The glazes slowed down molten salt condensate penetration, but did little to reduce the penetration of molten salt. Out of several refractory tile candidates, only greystone and fused-cast alumina-zirconia-silica (AZS) refractory remained intact and well bonded to the CRB after firing to 1000 C. The deformation of the refractory-tile composite was avoided by prefiring the greystone tile to 800 C. Condensed vapors did not penetrate the tiles, but Re salts condensed on their surface. Refractory corrosion tests indicated that a 0.25-inch-thick greystone tile would not corrode during a BV melt. Tiles can reduce both vapor penetration and molten salt penetration, but vapor deposition above the melt line will occur even on tiles. The Tc/Re transport scenario was outlined as follows. At temperatures below 700 C, molten ionic salt (MIS) that includes all the Tc/Re penetrates, by capillarity, from the feed into the CRB open porosity. At approximately 750 C, the MIS decomposes through the loss of NOx, leaving mainly sulfate and chloride salts. The Na2O formed in the decomposition of the nitrates reacts with insoluble grains in the feed and with the aluminosilicates in the CRB to form more viscous liquids that reduce further liquid penetration into the CRB. At 800 to 1000 C, a continuous glass phase traps the remains of the MIS in the form of inclusions in the bulk glass melt. At 1000 to 1200 C, the salt inclusions in the glass slowly dissolve but also rise to the surface. The Tc/Re salts also evaporate from the free surface of the glass melt that is rapidly renewed by convective currents. The vapors condense on cooler surfaces in the upper portion of the CRB, the box lid, and the off-gas system.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 877052
- Report Number(s):
- PNNL-15193; 830403000; TRN: US0601602
- Country of Publication:
- United States
- Language:
- English
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