The U.S. Department of Energy has embarked on an effort to retrieve, immobilize, and dispose of the 2.1 × 105 m3 of radioactive tank wastes that were generated during weapons production and other operations at the Hanford Site in Washington State. One of the major challenges associated with this effort is the processing of the 4.2 × 104 m3 of high-level waste sludges. These sludges consist of a complex mixture of amorphous and crystalline mineral phases. The current plan for processing the sludge solids consists of leaching with aqueous NaOH, washing out the NaOH and dissolved components, then vitrifying the solids in borosilicate glass. The purpose of the NaOH leaching step is to remove components such as Al, Cr, and P that can lead to the production of an unacceptable quantity of high-level waste glass. In this paper, we will discuss the chemistry underlying the leaching and washing processes, focusing on the specific mineral phases present in the sludge solids and how these phases respond to the leaching process. The chemical phases present in the Hanford tank sludge solids have been identified through microscopy coupled with electron diffraction and through powder X-ray diffraction. We have also recently been applying nuclear magnetic resonance spectroscopy to characterize chemical species in tank sludge solids. Numerous chemical species have been identified including the aluminum oxy/hydroxides gibbsite and boehmite, aluminosilicates, iron oxy/hydroxides, and mixed Cr/Fe oxyhydroxides. Identification of these phases has led to a more fundamental understanding of the behavior of the various sludge components during leaching; in turn, this understanding will allow for improved process flow sheets. For example, we have shown that certain tank sludges are high in boehmite, Υ-AIOOH. This mineral phase is much more refractory than other AI phases such as gibbsite. Thus, more severe leaching conditions (e.g., increased temperature, NaOH concentration, and leaching duration) are required to remove AI from wastes high in boehmite.

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