DISSOLUTION OF FISSILE MATERIALS CONTAINING TANTALUM METAL

The dissolution of composite materials containing plutonium (Pu) and tantalum (Ta) metals is currently performed in Phase I of the HB-Line facility. The conditions for the present flowsheet are the dissolution of 500 g of Pu metal in the 15 L dissolver using a 4 M nitric acid (HNO{sub 3}) solution containing 0.2 M potassium fluoride (KF) at 95 C for 4-6 h.[1] The Ta metal, which is essentially insoluble in HNO{sub 3}/fluoride solutions, is rinsed with process water to remove residual acid, and then burned to destroy classified information. During the initial dissolution campaign, the total mass of Pu and Ta in the dissolver charge was limited to nominally 300 g. The reduced amount of Pu in the dissolver charge coupled with significant evaporation of solution during processing of several dissolver charges resulted in the precipitation of a fluoride salt contain Pu. Dissolution of the salt required the addition of aluminum nitrate (Al(NO{sub 3}){sub 3}) and a subsequent undesired 4 h heating cycle. As a result of this issue, HB-Line Engineering requested the Savannah River National Laboratory (SRNL) to optimize the dissolution flowsheet to reduce the cycle time, reduce the risk of precipitating solids, and obtain hydrogen (H{sub 2}) generation data at lower fluoride concentrations.[2] Using samples of the Pu/Ta composite material, we performed three experiments to demonstrate the dissolution of the Pu metal using HNO{sub 3} solutions containing 0.15 and 0.175 M KF. When 0.15 M KF was used in the dissolving solution, 95.5% of the Pu in the sample dissolved in approximately 6 h. The undissolved material included a small amount of Pu metal and plutonium oxide (PuO{sub 2}) solids. Complete dissolution of the metal would have likely occurred if the dissolution time had been extended. This assumption is based on the steady increase in the Pu concentration observed during the last several hours of the experiment. We attribute the formation of PuO{sub 2} to the complexation of fluoride by the Pu. The fluoride became unavailable to catalyze the dissolution of PuO{sub 2} as it formed on the surface of the metal. The mass of Pu dissolved is equivalent to the dissolution of 343 g of Pu in the HB-Line dissolvers. In the initial experiment with 0.175 M KF in the solution, we achieved complete dissolution of the Pu in 6 h. The mass of Pu dissolved scales to the dissolution of 358 g of Pu in the HB-Line dissolvers. The second experiment using 0.175 M KF was terminated after approximately 6 h following the dissolution of 92.7% of the Pu in the sample; however, dissolution of additional Pu was severely limited due to the slow dissolution rate observed beyond approximately 4 h. A small amount of PuO{sub 2} was also produced in the solution. The slow rate of dissolution was attributed to the diminishing surface area of the Pu and a reduction in the fluoride activity due to complexation with Pu. Given time (>4 h), the Pu metal may have dissolved using the original solution or a significant portion may have oxidized to PuO{sub 2}. If the metal oxidized to PuO{sub 2}, we expect little of the material would have dissolved due to the fluoride complexation and the low HNO{sub 3} concentration. The mass of Pu dissolved in the second experiment scales to the dissolution of 309 g of Pu in the HB-Line dissolvers. Based on the data from the Pu/Ta dissolution experiments we recommend the use of 4 M HNO{sub 3} containing 0.175 M KF for the dissolution of 300 g of Pu metal in the 15 L HB-Line dissolver. A dissolution temperature of nominally 95 C should allow for essentially complete dissolution of the metal in 6 h. Although the H{sub 2} concentration in the offgas from the experiments was at or below the detection limit of the gas chromatograph (GC) used in these experiments, small concentrations (<3 vol %) of H{sub 2} are typically produced in the offgas during Pu metal dissolutions. Therefore, appropriate controls must be established to address the small H{sub 3} generation rates in accordance with this work and the earlier flowsheet demonstrated for Pu metal.[3