| Autor: |
Casella AJ; Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States., Ahlers LR; Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States., Campbell EL; Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States., Levitskaia TG; Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States., Peterson JM; Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States., Smith FN; Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States., Bryan SA; Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States. |
| Abstrakt: |
In nuclear fuel reprocessing, separating trivalent minor actinides and lanthanide fission products is extremely challenging and often necessitates tight pH control in TALSPEAK (Trivalent Actinide-Lanthanide Separation by Phosphorus reagent Extraction from Aqueous Komplexes) separations. In TALSPEAK and similar advanced processes, aqueous pH is one of the most important factors governing the partitioning of lanthanides and actinides between an aqueous phase containing a polyaminopolycarboxylate complexing agent and a weak carboxylic acid buffer and an organic phase containing an acidic organophosphorus extractant. Real-time pH monitoring would significantly increase confidence in the separation performance. Our research is focused on developing a general method for online determination of the pH of aqueous solutions through chemometric analysis of Raman spectra. Spectroscopic process-monitoring capabilities, incorporated in a counter-current centrifugal contactor bank, provide a pathway for online, real-time measurement of solution pH. The spectroscopic techniques are process-friendly and can be easily configured for online applications, whereas classic potentiometric pH measurements require frequent calibration/maintenance and have poor long-term stability in aggressive chemical and radiation environments. Raman spectroscopy discriminates between the protonated and deprotonated forms of the carboxylic acid buffer, and the chemometric processing of the Raman spectral data with PLS (partial least-squares) regression provides a means to quantify their respective abundances and therefore determine the solution pH. Interpretive quantitative models have been developed and validated under a range of chemical composition and pH conditions using a lactic acid/lactate buffer system. The developed model was applied to new spectra obtained from online spectral measurements during a solvent extraction experiment using a counter-current centrifugal contactor bank. The model predicted the pH of this validation data set within 11% for pH > 2, thus demonstrating that this technique could provide the capability of monitoring pH online in applications such as nuclear fuel reprocessing. |
