Thesis (MTech (Chemical Engineering))--Cape Peninsula University of Technology, 2016. / The Bushveld igneous complex in northern South Africa has the largest deposit of platinum group elements (PGE) in the world. In trace amounts, these are closely associated with base metal sulphides (BMS). Froth flotation is used to beneficiate these PGE ores. The process constitutes a bulk sulphide recovery. Improvement of recovery of the BMS is required to maximise the recovery of PGEs. The performance of the froth flotation process is largely dependent on the chemical additives used and these chemicals have been extensively studied. Mixtures of collectors are widely used in the flotation of sulphide and platinum group mineral (PGM) ores. A range of performance benefits for the use of mixtures over pure collectors have been observed on many systems. These include improved valuable metal grades and recoveries, lower reagent dosage requirements, improved rates of flotation and enhanced recovery of coarse particles. Improvements observed with mixtures of chemical reagent have been attributed to synergism; defined as the interaction of two or more agents to produce a combined effect greater than the sum of their individual effects. Synergism is highly desired in froth flotation. For this study, mixtures of thiol collectors were used in batch froth flotation tests in an attempt to identify synergism between the different collectors on flotation performance of a typical platinum ore from the Merensky reef. Flotation performance was evaluated in terms of grades and recoveries of copper and nickel, and the rate of metal flotation. Single thiol collectors of xanthate (SIBX), a dithiocarbamate (DTC) and a dithiophosphate (DTP) were evaluated to determine the effect of functional group on flotation performance. SIBX was then used in mixtures with both DTC and DTP at various molar ratios to establish whether synergism occurs between these collectors on this particular platinum ore. Molar ratios of 90:10, 80:20, 70:30 60:40 and 50:50 were considered with SIBX being the major component. Further tests were conducted with the addition of a carboxymethyl cellulose depressant to the collector mixtures.

A química de carboidratos têm sido um importante link entre a síntese orgânica, a biologia e a química medicinal devido ao papel fundamental que açúcares apresentam na glicobiologia. Neste contexto, a ligação amida glicosídica é uma importante conexão encontrada na natureza, sendo uma das formas de ligar um núcleo de carboidrato a outras biomoléculas e produtos naturais, como glicopeptídeos e N-glicosil amidas. Dessa forma, o desenvolvimento de métodos sintéticos para a introdução de núcleos de carboidratos em diferentes estruturas é fundamental. Tendo em vista o interesse do nosso grupo de pesquisa em desenvolver novas estratégias utilizando a química de selênio na funcionalização de derivados de carboidratos, o presente projeto descreve uma metodologia de síntese de N-glicosil amidas e de glicoconjugação via formação de ligação amida, envolvendo a reação entre selenocarboxilatos, gerados in situ, com azidas glicosídicas. Foi possível sintetizar com sucesso uma série de derivados de carboidratos, para uma variedade de substratos que incluíram: N-glicosil amidas furanosídicas (20 exemplos), piranosídicas (13 exemplos) e também N-glicoconjugados graxos (10 exemplos). A metodologia foi baseada na geração in situ de selenocarboxilatos de lítio, a partir de Se0/ LiEt3BH e derivados de ácidos carboxílicos, e suas reações com azidas derivadas de açúcares. Um aspecto importante deste protocolo é que a reação se inicia com selênio elementar e apresenta como subprodutos N2 e Se0. O isolamento e manipulação de espécies intermediárias reativas de selênio são evitadas durante o curso reacional, conferindo ao selenocarboxilato o status de reagente traceless. / Carbohydrate chemistry has been an important link between organic synthesis, biology and medicinal chemistry due to the fundamental roles that sugars play in glycobiology. In this context, the glycosyl amide linkage is an important connection found in nature, since it is one of the ways in which a sugar unit can be found attached to other biomolecules and natural products, such as N-glycosyl amides and glycopeptides that are known for possessing a wide range of bioactivities. Therefore, the development of synthetic methods for the introduction of sugar moieties into various different scaffolds is of paramount importance. In connection with our interest on the development of new strategies using selenium chemistry for the functionalization of carbohydrate derivatives, we describe herein an efficient synthesis of glycosyl amides and glycoconjugation methodology via amide bond-formation, enabled by the reaction of in situ generated selenocarboxylates with glycosyl azides. Carbohydrate-derived amides were successfully prepared in good yields for a broad range of substrates, including: furanosyl (20 examples), pyranosyl (13 examples) N-glycosil amides derivatives and also fatty acids glycoconjugates (10 examples). The methodology relied in the in situ generation of lithium selenocarboxylates, from Se/LiEt3BH and acyl chlorides or carboxylic acids and their reaction with sugar azides. A key aspect of the present protocol is that we start from elemental selenium and as by-products we have harmless gaseous nitrogen and elemental selenium. Isolation and handling of all reactive and sensitive seleniumcontaining intermediates is avoided, therefore assigning to the selenocarboxylate the status of a traceless reagent.

The concept of combining two well established areas of organic chemistry, viz., organosilicon chemistry and the use of chiral auxiliaries, into a viable, alternative method of asymmetric synthesis has only very recently begun to receive attention. At the outset of this investigation, no asymmetric reactions of silyl enol ethers, chiral by virtue of optically active substituents on the silicon, had been reported. A range of novel chiral silyl enol ethers have thus been prepared from a variety of ketones, including pinacolone, cyclohexanone, and α-tetralone, and employing menthol, borneol, and cholesterol as chiral auxiliaries. These preparations have been achieved via several distinct routes, including a novel convergent approach involving the isolation of either the chloro(menthyloxy)dimethylsilane or the (bornyloxy)chlorodimethylsilane. The MS and NMR spectra of these silyl enol ethers were examined in detail and, in the case of the crystalline cholesteryloxy silyl enol ether, the X-ray structure has been determined. The potential of chloroalkoxysilanes to act as general, chiral derivatizing agents has been established by the preparation of diastereomeric silyl acetal mixtures of racemic secondary alcohols (e.g. I-phenylethanol and 2-octanol). The experimental diastereomeric ratios, obtained by GLC and ¹H NMR spectroscopy, approached the expected value of unity, confirming the potential of the alkoxychlorosilanes as chiral probes. The chiral silyl enol ethers have been successfully oxidized to the corresponding α-siloxy ketones employing MCPBA, MMPP, and 2-(phenylsulphonyl)-3-phenyloxaziridine as oxidizing agents and the diastereomeric excesses obtained, which varied from 0 to 16%, indicated some potential for stereochemical control. Alkylation and hydroxyalkylation reactions of the silyl enol ethers have yielded the expected α-iert-butyl and β-hydroxy ketones in good to excellent material yields, with the enantiomeric excesses, as determined by chiral shift reagent studies, reaching 14%. To improve the stereo control in these reactions, attempts have been made to prepare chiral silyl enol ethers with auxiliaries possessing the potential for transition state complex co-ordination in the reactions under consideration. The preparation of such silyl enol ethers, incorporating the proline-derived auxiliaries, N-methyl-2-hydroxymethylpyrrolidine and 2-methoxymethylpyrrolidine met with only limited success. In an alternative approach, three derivatives of 2,3-dihydroxybornane have been prepared. However, two of these auxiliaries, viz., 3-exo-benzyloxy-2-exo-hydroxybornane and 3-exo-(1-methoxyethoxy)-2-exo-hydroxybornane failed to form silyl enol ethers, even under considerably more vigorous conditions than normally employed. The third derivative, 3,3-ethylenedioxy-2-hydroxybornane has been successfully utilized in the preparation of a pinacolone-derived chiral silyl enol ether. Hydroxyalkylation of this compound with benzaldehyde has yielded the β-hydroxyketone with significantly improved enantiomeric excess (26%) and a transition state complex has been proposed to rationalize this improvement.

Trithiocarbonates (TTCs) with less than six carbon atoms per molecule historically have proved to be better bulk sulphide mineral collectors than conventional dithiocarbonates (DTCs). However, high vapor pressures of the short-chain mercaptan decomposition products prevented them from general industrial use. Impala’s commitment in TTC development changed in 2002 when the nC12-trithiocarbonate indicated strong synergism when added to their existing flotation suite. A concerted research effort at the University of Utah followed, and in particular on their surface chemistry. To compliment current research and development at Impala, fundamental work regarding the surface hydrophobicity of pyrrhotite under electrochemically controlled conditions was undertaken at Utah University. Controlled contact angle measurements showed that the surface hydrophobicity of pyrrhotite can be increased by small additions of nC12-trithiocarbonate to SIBX. It was also found that this improvement in the surface hydrophobicity with the SIBX-TTC mixture was more significant at lower oxidation potentials. Work at Utah University further showed that a C12 decomposition product may or may not be present with an adsorbed TTC molecule. External reflectance infrared spectroscopy in the mid infrared region suggested a “crowding” of the collectors at the surface when SIBX and TTC are combined. This was based on an increase in the absorbance of the -CH2- peaks in the mixed collector system. In bench scale flotation tests on PGM bearing samples from the Merensky reef, it was found that a 5 molar percent replacement of SIBX with nC12-trithiocarbonate improved the flotation activity relative to the standard SIBX-DTP mixture. Improvements were in the recoveries of PGMs, copper and nickel. The addition of TTC also increased the flotation rates of both slow and fast floating valuables as is predicted by the Kelsall equation. The optimum mixture for the pilot plant trials was thus a 5 molar percent replacement of the current collector suite with nC12-TTC. Based on the bench flotation results, research was extended to a pilot plant trial. At a depressant dosage of 100g/ton, the PGM concentrate grades from the first rougher cell improved from 120g/ton to 175g/ton when the TTC was introduced. This was achieved without any effect on the recovery from the first cell. This increase in concentrate grade is believed to arise from the nature of both: <ul> <li>The mineral-collector surface state, and</li> <li>The bubble surface interaction.</li> </ul> Overall, the standard SIBX-DTP collector combination and the new SIBX-DTP-TTC collector combination (both at 100g/ton depressant) was also compared to pilot plant tests with SIBX-DTP at high (350g/ton) depressant dosages. The latter suite forms the currents reagent suite at Impala Platinum. When comparing the first two trials, at 100g/ton depressant, the addition of TTC as a ternary collector resulted in a recovery improvement of approximately 2.2% with a simultaneous increase in final concentrate grade from 57g/ton to 73g/ton. The result was a reduction in solids recovery from 5.3% to 4.1%. When comparing the TTC trial to the standard collector suite at high depressant dosages, only a small reduction (3.6% vs. 4.1%) in solids recovery was achieved with a final concentrate grade of 85g/ton. The PGM recoveries were very similar. Based on current Merensky milling rates, depressant and TTC costs, and calculated replacements based on the pilot plant tests, a projected cost saving on chemicals is R9.6 million per annum. Financial impacts on processing, grade and kinetics have not been made. It was also concluded that the detrimental effect of mild steel milling on the flotation activity of SIBX-DTP was diminished with the addition of the long-chain TTC with SIBX and DTP. As part to this research, a preliminary plant trial on UG-2 underground material showed a reduced primary rougher chromite grade as well as a significant increase in PGM concentrate grade for the first two primary rougher cells. This is an important finding, especially for the melting process. In this final study a partial (5 molar percent) replacement of the standard collector used was also made. What was further realised was a significant increase in the final concentrate grade when compared to the standard conditions. / Dissertation (MEng (Metallurgical Engineering))--University of Pretoria, 2007. / Materials Science and Metallurgical Engineering / MEng / unrestricted

Sasol endeavors to expand its current business through the beneficiation of commodity feedstreams having marginal value into high-value chemicals via cost-effective processes. In this regard Merisol, a division of Sasol has access to phenolic and cresylic feedstreams, which have the potential to be converted to fine chemicals. Targeted products include para-anisaldehyde, ortho- and para-hydroxybenzaldehyde which are important intermediates for the manufacture of chemicals used in the flavor and fragrance market and various other chemicals. The use of CO technology (HF/BF3) to produce these aldehydes in a two-step process from phenol as reagent is economically attractive due to the relative low cost and other benefits associated with syngas as reagent. The aim of the study was to evaluate and understand this relatively unexplored approach to the formylation of aromatic compounds. The reactivity of both phenol and anisole proved to be much lower than that of toluene. The main aldehyde isomer (para) produced in these HF/BF3/CO formylations as well as of other ortho-para directing mono-substituted benzenes tested in our laboratories were in accordance with published results. Efforts to increase substrate conversion resulted in substantial secondary product formation and mechanistic investigations showed this to be a consequence of the inherent high acidity of the reaction environment. The effect of different substituents on the relative formylation rates of benzene derivatives was investigated. These results showed that methyl groups are activating while halogens are deactivating relative to benzene as substrate. The decrease in reactivity from fluorobenzene> chlorobenzene> bromobenzene is in accordance with formylation trends observed in other acidic systems. Deuterium labeling experiments were applied to gain additional information on the formylation reaction mechanism. This study provided interesting but inconclusive results in support of the so-called intra-complex mechanism. All reported studies as well as our own work suggested that HF and BF3 in (at least) stoichiometric amounts are required for effective formylation with CO. Under these conditions this methodology for effecting aromatic formylation is not economically viable. Industrial application of formylation using CO will require the development of new catalysts or methodology to allow the use of HF/BF3 in a catalytic way. In this regard ionic liquids as a new and ecological-friendly field was explored. Chloro-aluminate ionic liquids promote the carbonylation of alkylated aromatic compounds, but fails in the case of oxygenated aromatics. Aldehyde yields of formylation in the acidified neutral ionic liquids were generally similar compared to reactions conducted in HF as solvent/catalyst. Formylation of anisole and toluene, but not of phenol in the neutral ionic liquids resulted in increased secondary product formation in comparison with hydrogen fluoride used as solvent/catalyst. This difference in behavior is not understood at present, but suggests that phenol is a good substrate for formylation in this medium, particularly with the development of a system catalytic with respect to HF/BF3 in mind. / Prof. C.W. Holzapfel

A vast majority of coal and mineral cleaning and upgrading processes involve the addition of water. The water allows the movement of particles throughout the processing plant and the upgrading of the material. When the process is complete the finished product must be dewatered. This is due to storage concerns, in which the water takes up a majority of the space, and high transportation costs, in which no compensation is obtained from the buyer for the shipment of the liquid. Dewatering is accomplished by many devices, with the two most common pieces of equipment being the screen-bowl centrifuge and disk filter. This thesis tests and compares the effect of reagents on dewatering using the screen-bowl centrifuge and disk filter. Coal was obtained from the Upper Banner, Pittsburgh No. 8, Taggart, and Dorchester seams, crushed and ground to the desired size, and run through the dewatering circuits. The results showed that the moisture content of the product can be greatly reduced in the disk filter while being only slightly reduced in the screen-bowl centrifuge. It was also shown that the recovery can be slightly increased in the screen-bowl centrifuge. Overall, with the addition of reagents, the disk filter outperformed the centrifuge in both recovery and moisture content. A model was also developed for the screen-bowl centrifuge. The results from the screen-bowl tests helped in the development of this model. This model can be used to predict the moisture content of the product, the recovery, particle size distribution of the effluent and particle size distribution of the product. The model also predicted how the product moisture and recovery were affected by changing the feed flow rate, feed percent solids, centrifuge speed, and particle size distribution. / Master of Science

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The versatility of organoboron compounds has been demonstrated by their use as synthetic intermediates and more recently in therapeutic applications since the FDA approval of Velcade©. As a result, transition metal-catalyzed protocols to incorporate boron reagents into unsaturated compounds have been extensively researched. While an abundance of literature protocols have been reported, the majority utilize harsh reaction conditions in combination with expensive reagents. This dissertation discloses the author’s contributions to the development of efficient, cost-effective, and operationally simple transition metal-catalyzed borylation protocols with alkynes and diboron reagents. An open-to-air copper(II)-catalyzed aqueous borylation protocol of alkynoates and a symmetrical diboron reagent is reported. Conjugate addition of the boryl-copper species to the electrophilic β-carbon provided β-boryl-α,β-unsaturated esters in moderate to excellent yields. Exclusive (Z)-stereochemistry was confirmed by nOe experiments. The resulting vinyl boronate esters are useful cross-coupling partners. The scope of the aqueous β-borylation protocol was extended to the unsymmetrical diboron reagent, pinB-Bdan. This alternative protecting group has emerged as an orthogonal protecting group and alters the reactivity of the boron moiety. Activation of the pinacol moiety to form the Lewis acid-base adduct allowed for the chemoselective transfer of the 1,8- diaminonapthalene moiety to the β-carbon. An alternative novel synthesis of vinyl, allyl diboronate esters from propargylic alcohols has also been described. Formation of a leaving group in-situ with a palladium- and coppercatalyzed protocol can lead to several competing reaction pathways and the formation of multiple products. Fortunately, the resulting vinyl, allyl diboronate esters were stereoselectively synthesized in moderate GC yields despite significate decomposition during purification, as confirmed by stability studies. The terminal diboration of allenes was previously the only reported method for the synthesis of vinyl, allyl diboronate esters. / Ph. D. / The unique properties of organoboron compounds allow them to be used as synthetic intermediates and as drugs targets. This dissertation discloses three environmentally friendly and simple methods to incorporate boron into alkynes using transition metal catalysts. In particular, alkynoates were successfully borylated under copper(II)-catalyzed aqueous conditions using symmetrical and unsymmetrical diboron reagents. Propargylic alcohols were also borylated using bimetallic conditions to afford vinyl, allyl diboronate esters, which were previously hard to obtain.

Silicon micromachining is the collective name for several processes by which three dimensional structures may be constructed from or on silicon wafers. One of these processes is anisotropic etching, which utilizes etchants such as KOH and ethylene diamine pyrocatechol (EDP) to fabricate structures from the wafer bulk. This project is a study of the use of KOH to anisotropically etch (lOO)-oriented silicon wafers. The thesis provides a thorough review of the theory and principles of anisotropic etching as applied to (100) wafers, followed by a few examples which serve to illustrate the theory. Next, the thesis describes the development and experimental verification of a standardized procedure by which anisotropic etching may be reliably performed in a typical research laboratory environment. After the development of this procedure, several more etching experiments were performed to compare the effects of various modifications of the etching process. Multi-step etching processes were demonstrated, as well as simultaneous doublesided etching using two different masks. The advantages and limitations of both methods are addressed in this thesis. A comparison of experiments performed at different etchant temperatures indicates that high temperatures (800 C) produces reasonably good results at a very high etch rate, while lower temperatures (500 C) are more suited to high-precision structures since they produce smoother, higher-quality surfaces. / Master of Science