Design, synthesis and testing of reagents for high-value mineral collection
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Waterson, Calum Neil
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Small organic ‘collector’ ligands play an important role in the recovery of platinum group minerals (PGMs) from the industrial platinum mining process via the froth flotation process, which separates finely ground minerals on the basis of relative hydrophobicity. Design of novel ligands to improve PGM recovery is an ongoing industrial interest. This thesis involves the application of computational chemistry techniques to gain a first-principles understanding of simple mineral-collector ligand interactions, with a view to applying this understanding to the design of novel collector ligands. Experimental techniques are also used, where appropriate, to validate computational modelling in order to gauge the applicability of computational chemistry to this field. Sperrylite (PtAs2), the world’s most common PGM, was used as a model for a typical platinum group sulfide mineral. Pentlandite ((Fe,Ni)9S8) and pyrite (FeS2), two base metal sulfide minerals commonly associated with PGMs, were used as competitor surfaces to gauge collector selectivity. α-quartz (SiO2) was used as to model silicaceous waste material, and pure platinum (Pt) as an internal standard to gauge Pt-collector interactions. Chapter 1 provides an overview of PGM mining with particular focus on the froth flotation process. A brief overview of the computational methods applied in this work is provided in Chapter 2. Chapter 3 presents modelling work based on assessing the various mineral and metal surfaces upon which ligands adsorption is modelled. Stable ‘working surfaces’ are defined by calculating surface energies for various low Miller index cleavages of the bulk unit cells of these solids. Surface stability with respect to slab depth is also assessed. A number of methods, including application of the virtual crystal approximation, a pairwise cluster expansion and explicit site modelling, are used to resolve the issue of positional disorder of the metal sites in pentlandite. This leads to the observation that pentlandite slabs with a higher concentration of Ni atoms at the mineral/vacuum interface are more stable. A global minimum energy bulk unit cell of pentlandite is described. Chapters 4 and 5 deal with the adsorption of collector and aqua ligands onto these surfaces, with Chapter 5 also reporting attempts at rational in-silico ligand design. A novel method for calculating the binding energy of anionic species in periodic systems via a work-function based correction is described and tested for both mono- and dianionic species. Modelling of ethyl xanthate (H5C2OCS2-) and xanthate-based analogues (H5C2XCS2-, where X=N, NH, NC2H5, S, CH, CH2) shows a trend of increased binding strength upon formation of dianionic species. Whilst this observation was supported (to a lesser degree) by geometrical parameters, the extension of the work-function based correction to deal with dianionic species tended to significantly overbind these ligands and so the work function correction was found to be inappropriate for use in models with a charge state greater than -1. Modelling of heterocyclic ligands on selected surfaces shows weaker adsorption than non-heterocyclic species due to unfavourable electronic effects of the delocalised heterocycle on the R-CS2- head group. Efforts in ligand design focussed on optimising the electronic properties of the tail group in the xanthate structure to provide maximum electron density to the CS2- system. The output from this process was p-methoxyphenyl dithiocarbamate (H2CO-C6H4-N=CS2²-), which performed well in computational models. Synthesis of this ligand, as well as protonated Nethyl dithiocarbamate (H5C2NHCS2-) failed, however, due to the intrinsic instability of monosubstituted dithiocarbamates. Attempts to validate modelling results using two experimental techniques are reported in Chapter 6. Firstly, cyclic voltammetry experiments using sperrylite, pentlandite and platinum working electrodes suspended in collector solutions of concentration 1x10-3 M are reported, which show some correlation between the order of calculated binding energies and the relative position of the oxidation potential for the formation of disulfide oxidation products, a process which is affected by surface adsorption. Correlation is best for ethyl xanthate and diisobutyl dithiophospinate, but poor for N,N-diethyl dithiocarbamate ((H5C2)2NCS2-). Secondly, microflotation experiments for the recovery of sperrylite, pentlandite and pyrite using various collector ligands were conducted. Results broadly agree with prior microflotation literature, but show no simple correlation between ligand binding energies and flotation recovery, suggesting that more complex factors than simple ligand/mineral adsorption are involved.