Uranium-Molybdenum Dissolution Flowsheet Studies (2007)

The Super Kukla (SK) Prompt Burst Reactor operated at the Nevada Test Site from 1964 to 1978. The SK material is a uranium-molybdenum (U-Mo) alloy material of 90% U/10% Mo by weight at approximately 20% 235U enrichment. H-Canyon Engineering (HCE) requested that the Savannah River National Lab (SRNL) define a flowsheet for safely and efficiently dissolving the SK material. The objective is to dissolve the material in nitric acid (HNO3) in the H-Canyon dissolvers to a U concentration of 15-20 g/L (3-4 g/L 235U) without the formation of precipitates or the generation of a flammable gas mixture. Testing with SK material validated the applicability of dissolution and solubility data reported in the literature for various U and U-Mo metals. Based on the data, the SK material can be dissolved in boiling 3.0-6.0 M HNO3 to a U concentration of 15-20 g/L and a corresponding Mo concentration of 1.7-2.2 g/L. The optimum flowsheet will use 4.0-5.0 M HNO3 for the starting acid. Any nickel (Ni) cladding associated with the material will dissolve readily. After dissolution is complete, traditional solvent extraction flowsheets can be used to recover and purify the U. Dissolution rates for the SK material are consistent with those reported in the literature and are adequate for H-Canyon processing. When the SK material dissolved at 70-100 o C in 1-6 M HNO3, the reaction bubbled vigorously and released nitrogen oxide (NO) and nitrogen dioxide (NO2) gas. Gas generation tests in 1 M and 2 M HNO3 at 100 o C generated less than 0.1 volume percent hydrogen (H2) gas. It is known that higher HNO3 concentrations are less favorable for H2 production. All tests at 70-100 o C produced sufficient gas to mix the solutions without external agitation. At room temperature in 5 M HNO3, the U-Mo dissolved slowly and the U-laden solution sank to the bottom of the dissolution vessel because of its greater density. The effect of the density difference insures that the SK material cannot dissolve and concentrate within the charge bundles. Solubility behavior of the SK material during dissolution at 70 o C reflected data reported in the literature for 100 o C. When solutions containing solids at 70 o C were heated to 105 o C, the solids dissolved. After 21 days, the samples that had been heated closely resembled the non-heated ones with respect to solids content. Super-saturated solutions of U-Mo have been produced which can be stable for more than 10 days, but these conditions are outside of the bounds of the recommended flowsheet. It is not known how the different dissolution pathways affect solution stability, but the results agree with the fact that solubility should not be affected by the dissolution pathway. Therefore, the literature data should be used as the bounding condition for solubility. Dissolution of the SK material consumed 2.8-8.0 moles of acid per mole of metal dissolved, which agrees with behavior reported elsewhere for U and U-Mo metals. The acid consumption values confirmed that a starting acid concentration in the dissolver of 4.0-5.0 M HNO3 will allow H-Canyon Operations to avoid adjusting the feed from the dissolver prior to solvent extraction while providing maximum operating margin for avoiding precipitate formation.