A Novel Methodology for Processing of Plutonium-Bearing Waste as Ammonium Plutonium(III)-Oxalate

A novel methodology has been developed for the recovery of Pu from different types of waste solutions generated during various operations involved in the chemical quality control/assurance of nuclear fuels. The method is based on the precipitation of Pu as ammonium plutonium(III)-oxalate and involves the adjustment of acidity of the Pu solution to 1 N, the addition of ascorbic acid (0.05 M) to reduce Pu to Pu(III), followed by the addition of (NH₄)₂SO₄ (0.5 M) and a stoichiometric amount of saturated oxalic acid maintaining a 0.2 M excess of oxalic acid concentration in the supernatant. The precipitate was characterized by X-ray powder diffraction and thermal and chemical analysis and was found to have the composition NH₄Pu(C₂O₄)₂3H₂O. This compound can be easily decomposed to PuO₂ on heating in air at 823 K. Decontamination factors of U, Fe, and Cr determined showed quantitative removal of these ions during the precipitation of Pu as ammonium plutonium(III)-oxalate.

A semiautomatic assembly based on the transfer of solutions by suction arrangement was designed and fabricated for processing large volumes of Pu solution. This assembly reduced the corrosion of the glove-box material and offered the advantage of lower radiation exposure to the working personnel.