Ditopic reagents for the solvent extraction of platinum group metals

This work aims to develop solvent extractants to recover platinum and palladium from highly acidic chloride solutions bearing other platinum group metals (PGMs). In general, metal values can be recovered by solvent extraction through three different mechanisms: metal cation extraction (1); metalate anion extraction (2); or metal salt extraction (3). Mn- + n(LH)(org) ⇌ [M(L)n](org) + nH+ (1) MClx n- + nL(org) + nH+ ⇌ [MClx(LH)n](org) (2) MClx + nL(org) ⇌ [MClxLn](org) (3) The main objective of this thesis is to establish whether ditopic extractants can be developed which have chemical functionalities that allow both mechanisms (2) and (3) to operate, co-extracting Pt(IV) and Pd(II) as their chloridometalates in an outer sphere binding site (2) and allowing their separation by raising pH to transfer the more kinetically labile Pd(II) to an inner sphere binding site (3) and releasing H2PtCl6 to the aqueous strip solution. A review of the literature is presented in Chapter 1, noting current commercially available extractants and the processes in which they are, or have been, applied. Particular attention is paid to the mode of action of the reported extractants and whether they extract metal cations, anions or metal salts. This chapter also outlines the proposed solvent extraction circuit in which new reagents developed in this thesis would be incorporated and the methods applied during the screening of candidate extractants. Chapter 2 deals exclusively with the use of reagents with inner-sphere binding sites for the selective extraction of palladium over platinum. Work on a series of oxime reagents synthesised for palladium extraction as part of preliminary MSci research (Andrew M. Wilson, MSci Thesis, University of Edinburgh, 2011) is reviewed. Studies of the hydrolytic stability of oximes indicate that they are unsuitable for incorporation into ditopic reagents for use in a circuit with a highly acidic feed solution. Thioethers were studied as alternatives as they show high kinetic selectivity for palladium over platinum and are more stable under acidic conditions. The synthesis and extraction properties of model reagents (largely arylalkyl thioethers) are reported and compared with those of the commercially available di-n-hexylsulfide. Incorporation of a polar group such as an amide provides phase transfer catalysis, accelerating the rate of transport of Pd(II) into the organic phase, but reducing selectivity over Pt(IV). The identification of functionalities that operate as receptors for chloridometalates by forming outer-sphere assemblies is explored in Chapter 3. The synthesis of amine, amide and amino-amide extractants from acid chloride streams and the effects of variations of functional groups on the extraction of PtCl6 2− are described. Secondary amides were found to be stronger extractants than tertiary amides, and aliphatic amides also show better metalate extraction than aromatic amides. The interactions between protonated aminoamide reagents and PtCl6 2− werre analysed by X-ray crystallography, noting that C-H∙∙∙Cl interactions with the “soft” chloridometalate anion are more common than with the “hard” chloride ion which shows a preference for more conventional N-H∙∙∙Cl interactions. Chapter 4 combines the reagent types explored in Chapters 2 and 3, in ditopic extractants that have both inner- and outer sphere binding sites. The synthesis and characterisation of a series of thioether amide reagents are reported and the selective extraction of platinum and palladium over other PGMs are discussed. In-house screenings of aryl- and alkylthioetheramide extractants showed selective co-extraction of Pd(II) and Pt(IV), rejecting Ir(III). Pt(IV) can be selectively water-stripped followed by ammonia-stripping of Pd(II). Industrial screenings at Johnson Matthey Technology Centre further exemplified the selectivity of these extractants over Ru(III) and Rh(III), although third phases were formed when the reagents were used for recovery from highly concentrated metal-feed solutions. The mode of action of the ditopic extractants is discussed, based on DFT calculations, crystal structure determinations and NMR studies, which support the formation of outersphere metalate assemblies and inner-sphere palladium complexes. Chapter 5 describes new difunctional (inner + outer sphere complexation) extraction by a single chemical entity, in this case an unsaturated N-heterocycle (an azole). The synthesis and characterisation of a series of hydrophobic azoles are described. These have basicities which allow protonation when contacted with strongly acidic solutions (2), but can be deprotonated in contact with water to allow their neutral forms to form inner-sphere complexes with Pd(II). Triazole-based reagents show the selective co-extraction of Pt(IV) and Pd(II) and, as with the ditopic thioetheramide reagents reported in Chapter 4, allow the selective water stripping of Pt(IV) and subsequent ammonia stripping of Pd(II)