IMPACT OF INCREASED ALUMINATE CONCENTRATIONS ON PROPERTIES OF SALTSTONE MIXES

Abstract

One of the goals of the Saltstone variability study is to identify the operational and compositional variables that control or influence the important processing and performance properties of Saltstone mixes. The protocols developed in this variability study are ideally suited as a tool to assess the impact of proposed changes to the processing flow sheet for Liquid Waste Operations (LWO). One such proposal that is currently under consideration is to introduce a leaching step in the treatment of the High Level Waste (HLW) sludge to remove aluminum prior to vitrification at the Defense Waste Processing Facility (DWPF). This leachate would significantly increase the soluble aluminate concentrations as well as the free hydroxide ion concentration in the salt feed that will be processed at the Saltstone Processing Facility (SPF). Consequently, an initial study of the impact of increased aluminate concentration on the Saltstone grout properties was performed. The projected compositions and ranges of the aluminate rich salt stream (which includes the blending strategy) are not yet available and consequently, in this initial report, two separate salt stream compositions were investigated. The first stream starts with the previously projected baseline composition of the salt solution that will be fed to SPF frommore » the Salt Waste Processing Facility (SWPF). The second stream is the solution that results from washing of the current Tank 51 sludge and subsequent transfer of the salt solution to Tank 11. The SWPF simulant has higher nitrate and lower free hydroxide than the Tank 11 simulant. In both of these cases, the aluminate was varied up to a maximum of 0.40 to 0.45M aluminate in order to evaluate the impact of increasing aluminate ion concentration on the grout properties. In general, the fresh grout properties of mixes made with SWPF and Tank 11 simulants were relatively insensitive to an increase in aluminate concentration in the salt solutions. However, the overall trends observed as the aluminate concentration increased in the salt solution were decreased Bingham Plastic yield stress and plastic viscosity, greater flowability of the grout, and reduced gel times and bleed volume for SWPF based mixes. On the other hand, the set times increased significantly with increasing aluminate concentration in the salt solutions. For the SWPF mixes, the set time increased from 1 to 4 days and for the Tank 11 mixes, the set time increased from 1 to 2 days. Heat of hydration measurements were consistent with the increased set times with extended induction periods (2 to 4 days) as aluminate concentration increased in the salt solution. This extended induction period of heat evolution observed with increasing aluminate concentrations must be addressed for Saltstone operations to avoid exceeding temperature limits. It is anticipated that the induction period will be temperature dependent and should be measured for future projections and included in the thermal modeling. The overall heat generation was greater in the mixes containing higher concentrations of aluminate. In fact, for the total heat release values calculated using curve fitting for longer times, the amount of heat was increased by 33% for SWPF based solutions and by 46% for Tank 11 based solutions. The larger amount of heat from mixes containing higher aluminate concentration must be accounted for in the modeling effort which determines the pour schedule for Saltstone. The increased induction periods were shown to be associated with hydration reactions of the blast furnace slag. The rate of heat generation with high aluminate solutions and Portland cement were only accelerated whereas high aluminate mixes containing blast furnace slag only showed the characteristic increase in induction time that was observed with mixes prepared using the premix blend of cementitious materials. It was shown that fly ash does not react significantly during the first seven days of curing but then undergoes an accelerated burst for 15 days before beginning to level off. The total amount of heat generated from a fly ash only mix with SWPF solution containing aluminate at 0.33 M is approximately 100 J/g vs. 87 J/g for SWPF with 0.11 M aluminate. Finally, the heat of hydration measurements revealed that the ternary system of cementitious materials (premix) leads to interactions between the hydration reactions of these three components that actually reduce the overall heat generation compared to the summation of the heats of hydration for mixes made only from portland cement, blast furnace slag or fly ash.« less