Solubility limits of dibutyl phosphoric acid in uranium-nitric acid solutions

The Savannah River Site has enriched uranium (EU) solution that has been stored since being purified in its solvent extraction processes. The concentrations in solution are approximately 6 g/L U and 0.1 M nitric acid. Residual tributylphosphate in solution has slowly hydrolyzed to form dibutyl phosphoric acid (HDBP) at concentrations averaging 30--50 mg/L. Dibutyl phosphoric acid, in turn, is in equilibrium with (HDBP)2 and DBP-. Uranium can form compounds with the dibutylphosphate ion (DBP-) which have limited solubility, thereby creating a nuclear criticality safety issue. Literature reports and earlier SRTC tests have shown that it is feasible to precipitate U-DBP solid during the storage and processing of EU solutions. As a result, a series of solubility experiments were run at nitric acid concentrations from 0--4.0 M HNO3, uranium at 0--90 g/L, and temperatures from 0--30 C. The data shows temperature and nitric acid concentration dependence consistent with what would be expected. With respect to uranium concentration, U-DBP solubility passes through a minimum between 6 and 12 g/L U at the acid concentrations and temperatures studied. However, the minimum shows a slight shift toward lower uranium concentrations at lower nitric acid concentrations. The shifts in solubility are strongly dependent upon the overall ionic strength of the solution. The data also reveal a shift to higher DBP solubility above 0.5 M HNO3 for both 6 g/L and 12 g/L uranium solutions. Analysis of U-DBP solids from the tests identified distinct differences between precipitates from less than 0.5 M solutions and those from greater than 4 M acid. Analyses identified UO2(DBP)2 as the dominant compound present at low acid concentrations in accordance with literature reports. As the acid concentration increases, the crystalline UO2(DBP)2 shows molecular substitutions and an increase in amorphous content