Physical, Chemical and Structural Evolution of Zeolite-Containing Waste Forms Produced from Metakaolinite and Calcined HLW

Natural and synthetic zeolites are extremely versatile materials. They can adsorb a variety of liquids and gases, and also take part in cation exchange reactions. Zeolites are easy to synthesize from a wide variety of natural and man made materials. One combination of starting materials that exhibits a great deal of promise is a mixture of metakaolinite and/or Class F fly ash and concentrated sodium hydroxide solution. Once these ingredients are mixed and cured at elevated temperatures, they react to form a hard, dense, ceramic-like material that contains significant amounts of crystalline tectosilicates (zeolites and feldspathoids). Zeolites have the ability to sequester ions in lattice positions or within their networks of channels and voids. As such they are nearly perfect waste forms, the zeolites can host alkali, alkaline earth and a variety of higher valance cations. In addition to zeolites, it has been found that the zeolites are accompanied by an alkali aluminosilicate hydrate matrix that is a host, not only to the zeolites, but to residual amounts of insoluble hydroxide phases as well. A previous publication has established the fact that a mixture of a calcined equivalent ICPP waste (sodium aluminate/hydroxide solution containing {approx}3:1 Na:Al) and fly ash and/or metakaolinite could be cured at various temperatures to produce a monolith containing Zeolite A (80 C) or Na-P1 plus hydroxy sodalite (130 C) crystals dispersed in an alkali aluminosilicate hydrate matrix. Dissolution tests have shown these materials (so-called hydroceramics) to have superior retention for alkali, alkaline earth and heavy metal ions. The zeolitization process is a simple one. Metakaolinite and/or Class F fly ash is mixed with a caustic sodium-bearing calcine and enough water to make a thick paste. The paste is transferred to a metal canister and ''soaked'' for a few hours at 70-80 C prior to steam autoclaving the sample at {approx}200 C for 6-8 hours. The waste form produced in this fashion could be a viable alternative for fixation of low activity waste (LAW) calcines. Our objective is to adapt this technology for use in site remediation and clean up of caustic waste solutions now in storage in tanks at Hanford and the Savannah River sites. The proposed work is meant to develop a clearer understanding of the advantages and limitations of producing a zeolite-containing waste form (hydroceramic) from calcined radioactive waste, i.e. the effect of processing variables, reaction kinetics, crystal and phase chemistry, and microstructure on their performance