In recent years, emissions of hydrogen cyanide from metallurgical operations have received renewed attention by legislative bodies, leading to the need for a reliable quantification method for HCN volatilisation. Subsequently, the purpose of this project, launched by Anglogold Ashanti Ltd. and in collaboration with MINTEK and the University of Pretoria, was to develop a prediction model for cyanide volatilisation from plant operations and tailings storage facilities in South Africa. The study was done in four stages, the first being a laboratory study of the equilibrium behaviour of hydrogen cyanide. Henry’s Law constant (kH) was determined at different solution cyanide concentrations, salinities and temperatures. A value for kH was established at 0.082 atm.L/mol, which was found to be independent on the solution cyanide concentration between 10 and 200 ppm cyanide. In addition, the effect of temperature on kH was found to be negligible at solution temperatures between 20 and 35ºC. It was also concluded that high salinities increase kH and promote volatilisation, but this effect was negligible at the typical salinity levels found in South African process water. The second stage entailed a detailed study of the mass transfer coefficient, KOL, for hydrogen cyanide from cyanide solutions and pulp mixtures, both in the laboratory and on-site. It followed from this investigation that the most important parameters affecting KOL are the HCN (aq) concentration in the liquid, the wind velocity across the solution or pulp surface, expressed in terms of a Roughness Reynolds number, Re*, and the moisture content, or solid to liquid ratio, of the pulp. Furthermore, it was concluded that KOL is highly sensitive to HCN (aq) concentrations at low concentrations, while it becomes rather insensitive to HCN (aq) at concentrations above 20 ppm HCN (aq) . The data generated by the laboratory and on-site test work was incorporated into the development of an empirical prediction model, based on the Roughness Reynolds number (Re*), moisture content (M), and aqueous cyanide concentration (HCN(aq) ) which may be described by the following equation: KOL= <font face="symbol">a</font> Re*b Mc HCN(aq)d + e The model coefficients were subsequently determined for application of the model to leach tanks, adsorption tanks, tailing storage facility surfaces and return water dams. The calculated model predictions for KOL were in excellent agreement with the measured test work data. Finally, the prediction model was validated at the leach and adsorption sections of a selected gold plant and a selected tailings storage facility. The model predicted that 9% of the cyanide lost in the leach and adsorption section could be attributed to HCN volatilisation. As for the tailings storage facility, the model assigned 63% of the cyanide lost from the tailings storage facility to HCN volatilisation, of which 95% occurred from the area on the tailings dam surface covered in a thin liquid film. It is recommended that the current methods available for the determination of HCN (aq) be further improved, due to the sensitivity of the model to the input value of the HCN (aq) concentration, in order to ensure that reliable predictions are made. It is also suggested that additional validation work be done in order to establish the generic applicability of the model to different sites. / Dissertation (MEng(Metallurgical))--University of Pretoria, 2007. / Materials Science and Metallurgical Engineering / unrestricted

During the production of ferrochrome in electric arc furnaces, a dust is captured in baghouse filters as a means of air pollution control. This dust contains various metals such as chromium, zinc, iron, aluminium and magnesium. Due to the presence of hexavalent chromium in the dust, which is both toxic and carcinogenic, it requires disposal at a hazardous waste disposal site, entailing high cost. The possibility exists that these costs could be reduced if metals such as zinc can be recovered from the dust through, inter alia, leaching. Experiments were performed to determine suitable conditions for the leaching of zinc from such a baghouse dust. A two step leaching procedure was followed which prevented the formation of silica gel. The most favourable conditions for zinc extraction was with a sulphuric acid concentration of 336 g/l and an acid to dust ratio of 0,56. Under these conditions zinc was selectively leached with regard to iron and aluminium. The percentage recovery for zinc was 71,2%, aluminium 1,8% and iron 0,1%. It was concluded that the second step (dilution) of leaching did not have a significant influence on the percentage extraction of metals from the dust. Consideration of the chemical treatment cost of waste streams produced led to the conclusion that zinc recovery from baghouse dust is not an economically feasible project viewed in isolation. However, compared to disposal at a hazardous waste disposal site such as Holfontein, approximately R467 054,00 per annum (based on a seven day week and baghouse dust production of 3 600 kg/day) can be saved. / Dissertation (MEng (Environmental Engineering))--University of Pretoria, 2006. / Chemical Engineering / unrestricted

Philosophiae Doctor - PhD / Zeolites are widely used as environmentally friendly solid catalysts or catalyst supports in the refining and petrochemical industries. ZSM-5 zeolite is composed of a three-dimensional medium pore structure (openings of 5-5.5 Å) with high silica content, high temperature stability and strong acidity making it a well-known and an established catalyst for several petroleum derived chemical processes such as cracking, aromatic alkylation, disproportionation, Methanol-to-Gasoline, isomerisation, etc. Nowadays, the synthesis of ZSM-5 zeolite from silica, alumina sources and structure directing agents (templates) is well known. Its synthesis is possible from fly ash, which is a low cost source of both silica and alumina. Fly ash is an inorganic residue resulting from the combustion of coal in electricity generating plants, consisting mostly of SiO₂ and Al₂O₃. ZSM-5 zeolite has not been synthesised from South African coal fly ash and the literature reports that fly ash-based ZSM-5 zeolite was synthesised only with tetrapropylammonium (TPA+) as structure directing agent and required an excessive amount of additional silica. The final ZSM-5 product was reported to still contain fly ash mineral phases after synthesis. This prevents the use of fly ash as a ZSM-5 zeolite precursor. Moreover, the synthesis of a high purity ZSM-5 zeolite from fly ash without additional silica has not been yet reported. This study aimed to synthesise high purity ZSM-5 zeolite from South African coal fly ash without additional silica, and with tetrapropylammonium bromide (TPABr), 1,6- hexanediamine (HDA) or 1-propylamine (PA) as structure directing agent. This aim was achieved by first optimising the synthesis of ZSM-5 zeolite from South African coal fly ash based on a formulation reported in the literature with fumed silica and TPABr as additional source of silica and structure directing agent respectively. Thereafter, the obtained optimum conditions were used to synthesise other fly ash-based ZSM-5 zeolite products by substituting TPABr with HDA or PA. Two routes of treating the as-received fly ash prior to the hydrothermal synthesis were applied in order to improve the quality of the final products or reduce the amount of the fumed silica that was used. The first route consisted of treating the as-received fly ash with concentrated H₂SO₄ in order to remove a certain amount of aluminium and increase the Si/Al in the acid treated fly ash solid residue but also remove some other elements such as Fe, Ca, Mg, and Ti which might have an undesirable effect on the product quality. The acid treated fly ash solid residue was used as ZSM-5 precursor with fumed silica as additional silica source and TPABr, HDA or PA as structure directing agent. The ZSM-5 zeolite products that were synthesised from the as-received fly ash as well as from the H₂SO₄ treated fly ash were treated with oxalic acid solution in order to reduce the aluminium content in the final products. The second route consisted of fusing the as-received fly ash with NaOH and treating the powder fused fly ash extract with oxalic acid solution. The obtained fused and oxalic acid treated fly ash extracts were used as ZSM-5 precursors without additional fumed silica and with TPABr, HDA or PA as structure directing agent. ZSM-5 zeolite was synthesised from the as-received South African coal fly ash not only with the commonly used structure directing agent TPABr but also with two other, lower cost structure directing agents, HDA and PA. The synthesis process did not generate any solid waste as fly ash was used as bulk, which could be a way of valorising South African coal fly ash. However, the final products contained some fly ash mineral phases such as mullite and quartz, and had poor physical and chemical properties compared to a commercial H-ZSM-5 zeolite. The treatment of the as-received fly ash with H₂SO4 resulted in fly ash-based ZSM-5 zeolite products with better physical and chemical properties than those of ZSM-5 zeolite products that were synthesised from the as-received fly ash. Moreover, the post-synthesis treatment of the fly ash-based ZSM-5 zeolite products with oxalic acid resulted in an increase in the Si/Al ratio, offering a post-synthesis route to adjust the acidity of the catalysts. However, mullite and quartz phases were still present in the synthesised products. Alternatively, high purity ZSM-5 zeolite was synthesised from the fused and oxalic treated fly ash extracts without additional silica and with TPABr, HDA or PA as structure directing agent. Moreover, these synthesised fly ash-based ZSM-5 zeolite products had similar physical and chemical properties to the commercial H-ZSM-5 zeolite. The synthesised fly ash-based ZSM-5 zeolite products were used as solid catalysts in the Methanol-to-Olefins (MTO) and Nazarov reactions. The ZSM-5 zeolite products that were synthesised from the H₂SO4 treated fly ash as well as fused and oxalic treated fly ash were successfully used as solid catalysts in the MTO and Nazarov reactions. The ZSM-5 zeolite products that were synthesised from the H₂SO₄ treated fly ash presented a similar trend in MTO and Nazarov reactions depending on the structure directing agent that was used, and the ZSM-5 zeolite that was synthesised with HDA as structure directing agent had the highest MTO and Nazarov conversion. However these catalysts deactivated more quickly compared to the commercial H-ZSM-5 zeolite. On the other hand, the zeolites that were synthesised from the fused and oxalic acid treated fly ash had a high initial MTO conversion equivalent to the commercial H-ZSM-5 zeolite. However, they deactivated after 5 h of time on stream due to diffusional constraints, because of their large crystal sizes. This study developed novel routes in the synthesis of high value zeolites from fly ash. ZSM-5 zeolite was synthesised from fly ash with structure directing agents other that TPA+ cation and had acceptable Brønsted acidity and high initial conversion in MTO and Nazarov reactions. This has not been yet reported in the literature. Moreover, for the first time a high purity ZSM-5 zeolite was synthesised from fly ash without additional silica and had similar properties to a commercial H-ZSM-5 zeolite. This constituted a breakthrough in the fly ash-based ZSM-5 zeolite synthesis procedure, which will promote the valorisation of fly ash through ZSM-5 synthesis due to avoiding the addition of silica source in the hydrothermal gel and preventing the presence of fly ash mineral phases in the final products. This study can have a significant economic and environmental impact in South Africa if the synthesis process is scaled up as it provides a potentially cheap and innovative way of using waste for making a high value green and acid catalyst, namely ZSM-5 zeolite that has several catalytic applications; and it promotes the valorisation of South African coal fly ash that is considered by many as waste material. / National Research Foundation (NRF)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior, CAPES.

The development of an appropriate solid-state kinetic model which represents the leaching process of phlogopite was investigated. Phlogopite samples were leached with nitric acid solutions of different concentrations, at different temperatures and for different reaction times. Leach liquors were analysed by ICP-OES for concentration, while the raw phlogopite and the acid-leached solid residues were analysed by XRF, XRD, ATR-FTIR, BET, TGA-DTG and SEM-EDS for characterisation to support the reaction rate model selection. It was found that the reaction was diffusion-controlled and the model which represents onedimensional diffusion through a flat plate (model D1) most accurately predicts the leaching behaviour. The observed activation energies and preexponential constants varied with initial acid concentration. The observed activation energies decreased from 98.8 – 88.9 kJ mol-1 as the initial acid concentration increased from 2 – 4 M, while the observed preexponential constants decreased from 3.30 x 10+12 – 2.30 x 10+11 min-1. Additional experiments were conducted at different temperatures, using different initial acid concentrations and over different reaction times to test the model. The experimental data points obtained (“testing data”) were in agreement with the predicted values. Analyses of the solid residues also revealed complementary results with respect to the leaching model selection. The raw phlogopite was found to be highly crystalline (XRD). Therefore, the absence of defects in the lattice means that the motion of H+ ions permeating into the lattice is restricted (Ropp, 2003; Schmalzried, 1995). This confirms that the leaching is internal diffusion-controlled since the mobility of constituents into the system is the controlling factor, and since the phlogopite particles are plate-like (SEM-EDS, BET) in shape, the use of the D1 model for one-dimensional diffusion through a flat plate is the recommended model to represent the leaching process. Furthermore, results obtained from the different analytical techniques were supportive of each other. It was also found that the amount of acid consumed is inequivalent to the amount theoretically required. Using the theoretically required acid concentration (2.45 M) results in incomplete conversion (< 80 % according to Kgokong (2017)). When initial acid concentrations between 2.4 – 2.6 M were used, only 88 – 91 % conversion was obtained after 6 hours of leaching at 65 °C, leaving behind excess H+ in solution. If fertiliser is the desired end product, it would be favourable to minimise the H+ concentration of the leach liquor. Therefore, the leaching process should be optimised so that the acidity of the leach liquor is minimised while obtaining complete leaching of all cations from the phlogopite particles into solution. Furthermore, since the SiO2 by-product is highly porous (surface area of 517 m2 g-1), its application in industrial adsorbents, catalysts, polymers, pigments, cement, etc. should be further explored. / Dissertation (MEng (Chemical Engineering))--University of Pretoria, 2020. / Chemical Engineering / MEng (Chemical Engineering) / Unrestricted

The thesis deals with the issue of increasing the whiteness index of kaolin raw material. The research was focused on floating the kaolin suspension and the subsequent processes related to increasing the whiteness index. Increasing the whiteness of the kaolin raw material took place on the basis of acid leaching. The eluents were based on sulfuric acid, phosphoric acid, oxalic acid and sodium bisulfite. The leaching process was influenced by the temperature and concentration of the leaching agent. Floated and leached kaolin samples were characterized by several methods. The XRD method investigated the mineralogical composition and the kaolinite structure order. The distribution of chromogenic components was monitored by SEM-EDS. Residues of organic matter was determined by COD test and the concentration of chromogenic components in the extract was monitored by the ICP-OES method. Last but not least, the index of whiteness was measured, the increase of which is the aim of the diploma thesis, using a UV-VIS spectrometer with reflective extension.

The objective of this work was the development of an efficient adsorbent for irreversible immobilization of heavy metals in contaminated soils. The adsorbent was prepared by pillaring of montmorillonite with silica followed by grafting of a chelate ligand on its surface. Obtained adsorbent was mesoporous with high content of adsorption sites. Its structure was studied by BET adsorption of N2, dynamic light scattering, and scanning electron microscopy. The adsorption capacity of the organoclay was measured by its mixing with contaminated kaolin and soil samples and by analysis of heavy metal contents in leachate. Deionized water and 50% acetic acid were used for leaching of metals from the samples. As it was demonstrated by the experiments, the adsorbent was efficient in immobilization of heavy metals not only in neutral aqueous media but also in the presence of weak acid. As a result, the adsorbent can be used for reduction of heavy metal leaching from contaminated sites.

The objective of this work was the development of an efficient adsorbent for irreversible immobilization of heavy metals in contaminated soils. The adsorbent was prepared by pillaring of montmorillonite with silica followed by grafting of a chelate ligand on its surface. Obtained adsorbent was mesoporous with high content of adsorption sites. Its structure was studied by BET adsorption of N2, dynamic light scattering, and scanning electron microscopy. The adsorption capacity of the organoclay was measured by its mixing with contaminated kaolin and soil samples and by analysis of heavy metal contents in leachate. Deionized water and 50% acetic acid were used for leaching of metals from the samples. As it was demonstrated by the experiments, the adsorbent was efficient in immobilization of heavy metals not only in neutral aqueous media but also in the presence of weak acid. As a result, the adsorbent can be used for reduction of heavy metal leaching from contaminated sites.

No description available.

No description available.