Investigation into the mode of action of chloride and chloridoplatinate extraction: a computational and experimental study
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Date
07/07/2017Item status
Restricted AccessEmbargo end date
31/12/2100Author
MacRuary, Kirstian Jennifer
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Abstract
This thesis investigates the mode of action of cationic reagents in the recovery of platinum
group metals (PGMs) by anion exchange solvent extraction. Industry uses a range of
extractants to achieve efficient concentration and separation of PGMs in hydrometallurgical
processes, but an understanding of the processes at a molecular level is limited and restricts
the options to improve efficiency. The research, sponsored in part by Johnson Matthey and
Anglo American, explores two different aspects of the mode of action of reagents used to
recover chloride and platinum.
Chapter 1 reviews the extraction of chloridometalates in hydrometallurgy and other
methods used to recover PGMs. The chapter also covers current ideas on whether formation
of outer-sphere anion-cation molecular assemblies or whether larger supramolecular
aggregates are responsible for the extraction of PGMs. These two separate routes of study
can be investigated by various computational and experimental methods, which are
discussed in Chapter 2.
In Chapter 3, the model systems chosen to develop the methodologies utilised throughout
the thesis are presented. The development involves the extraction of chloride ions by tributyl-phosphate (TBP) and then is extended to extraction of PGM chloridometalates in
Chapter 4. Computational methods are used to probe the atomistic and supramolecular
theories in predicting the most likely assemblies which will be formed in the transfer of
anions between the aqueous and organic phase. Slope analysis and the determination of the
contents of the organic phase is used to validate computational models, along with
spectroscopic techniques to determine shape and size of assemblies formed during
extraction.
The application of these methodologies to an amide extractant is discussed in Chapter 5.
Computational methods predict the probability of formation of specific complex assemblies
during the extraction of PtCl62- by protonated forms of the amide. Determination of the
stoichiometry involved in formation of the complex assemblies by slope analysis is reported
along with analysis of water, metal and chloride content to confirm the computational
model.
Final conclusions on all systems explored within the thesis and suggestions for future work
are presented in the final chapter. The combination of experimental and computational
methods are shown to be very efficient in defining mechanisms of extraction, involving
determination of structures formed during the process and how and why they form.