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Title: An experimental and computational investigation into the radiolysis of PUREX solvent systems
Author: Horne, Gregory
ISNI:       0000 0004 6497 6651
Awarding Body: University of Manchester
Current Institution: University of Manchester
Date of Award: 2016
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Plutonium Uranium Reduction EXtraction (PUREX) technology is a solvent extraction process used to recover plutonium and uranium from spent nuclear fuel. The solvent system is composed of an aqueous nitric acid phase in contact with an organic phase made up of tributyl phosphate in an organic diluent. During the separation process, the PUREX solvent system is subject to an intense multi-component radiation field (gamma rays, alpha particles, beta particles, neutrons, and fission fragments) rendering it susceptible to radiolytic degradation, which reduces its performance. Despite the PUREX process being used for over sixty years, a complete quantitative mechanistic understanding of the radiolytic degradation processes is not available. Nitrous acid is the most significant radiolytic degradation product of nitric acid, especially as its chemical and physical properties alter the formulation of the PUREX solvent system. Furthermore, nitrous acid exhibits complex redox relationships with a number of actinides, with plutonium being of greatest concern to the performance of the PUREX process. A combination of experimental and computational (stochastic and deterministic) techniques have been used to investigate the radiolysis of the PUREX solvent system's aqueous phase, specifically the radiolytic formation of nitrous acid, and its conjugate base nitrite, as a function of solvent system formulation, absorbed dose (up to 1.7 kGy), and radiation quality (cobalt-60 gamma rays and alpha particles from plutonium and americium alpha decay). The research presented in this thesis focuses on: (i) the experimental radiation chemistry of solutions of nitric acid and sodium nitrate over the range of concentrations 1 × 10-3 to 6 mol dm-3, and (ii) the development of a multi-scale modelling approach for evaluating the radiolysis of aqueous systems in terms of reaction mechanisms. The experimental and modelling studies provide insight into the radiation chemistry of the PUREX solvent system's aqueous phase, mechanistically demonstrating how the radiation chemical yield of nitrous acid and nitrite is dependent upon the interplay between non-homogeneous radiation track chemistry and secondary bulk homogeneous chemistry. This interplay is influenced by low pH, the presence of chemical scavengers and redox active metal ions, and radiation quality. These findings will act as a benchmark for the development of advanced reprocessing schemes, which must seriously consider how modifications in solvent system formulation and fuel composition may affect this dynamic interplay, and ultimately the generation of secondary highly active liquid waste.
Supervisor: Pimblott, Simon Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Multi-scale modelling ; Americium ; Gamma ; Plutonium ; Nitric acid ; Radiolysis ; PUREX ; Nitrate