PNNL

Abstract

The co-decontamination (CoDCon) project was established in FY 2016 with the objectives of (a) evaluating the uncertainty in the uranium (U)/plutonium (Pu) ratio in a mixed U/Pu product from a tributyl phosphate (TBP)–based solvent extraction flowsheet and (b) developing and demonstrating on-line optical spectroscopy for real-time monitoring of key components (e.g., Pu, U, and HNO3 concentrations) in the process solutions. We are interested in establishing the accuracy and precision to which a specific uranium-to-plutonium (U/Pu) ratio can be achieved, which for the purposes of this project is set at a U/Pu mass ratio of 7/3. The uncertainty associated with achieving this specific target U/Pu ratio is being established through multiple flowsheet tests using laboratory-scale solvent extraction equipment. In addition, optical spectroscopic techniques have been incorporated into the CoDCon solvent extraction testing system, allowing real time monitoring of all input and output process streams. Two CoDCon flowsheet tests were successfully performed in FY 2018. In FY 2019, two additional flowsheet tests were performed. For the first of these (CoDCon Run 3), the dissolved fuel simulant was similar to that used in the first two tests, with the inclusion of 1 mM neptunium (Np). The second test conducted in FY 2019 (CoDCon Run 4) used a more representative dissolved fuel simulant, including addition of non-radioactive fission product elements. All tests used a bank of sixteen 2 cm centrifugal contactors. The tests involved first loading the solvent (30 vol% TBP dissolved in n-dodecane) with U and Pu, then the Pu was stripped from the loaded solvent with a U(IV) solution (~50 mM) and the flowsheet conditions were adjusted such that some U partitioned into the Pu-containing product stream. The amount of U accompanying the Pu was monitored in real time using optical spectroscopic techniques coupled with chemometric modeling. Based on the real-time spectroscopic measurement of the U/Pu ratio, adjustments were made to the flowrate of the fresh TBP solvent phase used to scrub U from the aqueous Pu-containing product. This proved to be a very effective way to control the U/Pu mass ratio in the product.