Proefschrift Universiteit van Amsterdam. / Met lit. opg. - Met samenvatting in het Nederlands.

Proefschrift Universiteit van Amsterdam. / Met bibliogr., lit opg. - Met samenvatting in het Nederlands en Italiaans.

Proefschrift Universiteit van Amsterdam. / Auteursnaam op omslag: Léonie Raamsdonk. Met bibliogr., lit. opg. - Met samenvatting in het Nederlands.

South Africa is a land blessed with an abundance of mineral deposits. Yet, despite this, very little value adding of minerals exists. Most of the mined minerals are exported, where it is reworked into valued items. The country subsequently imports the valuable items at a much higher cost. In the 2006/7 financial year, the government made the decision to support several projects aimed at adding value to the mined minerals and by so doing, creating job opportunities. One such project was identified for the mineral Fluorite (CaF2). Fluorite is exposed to a controlled burn in a plasma reactor, producing an array of different fluorocarbon gases used in the electronics industry and for commercial polymers like Teflon®. Currently, fluorocarbon gases are separated using a series of cryogenic distillation columns. Although this technique has proven to be successful, it has several negative aspects such as the high cost involved when operating at cryogenic conditions as well as difficulty handling the gases at these sub–zero temperatures. It was proposed to study the possibility of using membranes to separate fluorocarbon gases at ambient conditions. Several membranes were screened to determine which one is best suited for this application. Two Teflon® based membranes were selected from this data. One of the membranes had a PAN support, while the other had a PEI support. Pure gas data for both membranes showed promising results. It yielded the highest flux for C3F6, followed by N2 and CF4. c–C4F8 was not used because it was demonstrated that the gas tends to condensate at low pressures. It is recommended to rather use pressure swing condensation to remove this gas from the mixture before the remainder is purified using membranes. Both membranes behaved similarly, with selectivity between C3F6 and CF4, and N2 and CF4; all above 10. By including the permeate pressure in the Solution–diffusion model, it was possible to model the pure gas data Binary feed gas mixture experiments showed a large amount of coupling existing between the feed gas mixtures. The result is a decrease in the selectivity as well as the total flux of the gas mixture. Partial fluxes were modelled by introducing a thermodynamic factor that was shown to follow a power law equation. The PAN–supported membrane outperformed the PEI–supported one; it was decided to use this membrane from this point onwards. Analysis of the ternary feed mixtures showed a strong selectivity towards the gas abundant in the feed blend. The existence of convective diffusion was proven, and included in the modelling, as well as a breakthrough pressure constant. This is indicative of strong interaction between the different gases and the membrane. Throughout the study it became clear that the difference in surface charge between the gases and the membrane were decisive. Opposite charges between a gas (C3F6) and the membrane aided in gas permeation. Membrane separation of fluorocarbon gases at ambient conditions is possible. Teflon® based membranes are recommended. It will be advantageous to study the effect of elevated temperatures on the separation efficiency of such a system. / Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2012.

South Africa is a land blessed with an abundance of mineral deposits. Yet, despite this, very little value adding of minerals exists. Most of the mined minerals are exported, where it is reworked into valued items. The country subsequently imports the valuable items at a much higher cost. In the 2006/7 financial year, the government made the decision to support several projects aimed at adding value to the mined minerals and by so doing, creating job opportunities. One such project was identified for the mineral Fluorite (CaF2). Fluorite is exposed to a controlled burn in a plasma reactor, producing an array of different fluorocarbon gases used in the electronics industry and for commercial polymers like Teflon®. Currently, fluorocarbon gases are separated using a series of cryogenic distillation columns. Although this technique has proven to be successful, it has several negative aspects such as the high cost involved when operating at cryogenic conditions as well as difficulty handling the gases at these sub–zero temperatures. It was proposed to study the possibility of using membranes to separate fluorocarbon gases at ambient conditions. Several membranes were screened to determine which one is best suited for this application. Two Teflon® based membranes were selected from this data. One of the membranes had a PAN support, while the other had a PEI support. Pure gas data for both membranes showed promising results. It yielded the highest flux for C3F6, followed by N2 and CF4. c–C4F8 was not used because it was demonstrated that the gas tends to condensate at low pressures. It is recommended to rather use pressure swing condensation to remove this gas from the mixture before the remainder is purified using membranes. Both membranes behaved similarly, with selectivity between C3F6 and CF4, and N2 and CF4; all above 10. By including the permeate pressure in the Solution–diffusion model, it was possible to model the pure gas data Binary feed gas mixture experiments showed a large amount of coupling existing between the feed gas mixtures. The result is a decrease in the selectivity as well as the total flux of the gas mixture. Partial fluxes were modelled by introducing a thermodynamic factor that was shown to follow a power law equation. The PAN–supported membrane outperformed the PEI–supported one; it was decided to use this membrane from this point onwards. Analysis of the ternary feed mixtures showed a strong selectivity towards the gas abundant in the feed blend. The existence of convective diffusion was proven, and included in the modelling, as well as a breakthrough pressure constant. This is indicative of strong interaction between the different gases and the membrane. Throughout the study it became clear that the difference in surface charge between the gases and the membrane were decisive. Opposite charges between a gas (C3F6) and the membrane aided in gas permeation. Membrane separation of fluorocarbon gases at ambient conditions is possible. Teflon® based membranes are recommended. It will be advantageous to study the effect of elevated temperatures on the separation efficiency of such a system. / Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2012.

Proefschr. Rijksuniversiteit Groningen. / Auteursnaam op omslag: Fresia Alvarado.

With the increasing global energy demand and the decreasing availability of good quality coals, a better understanding of the important properties that control the behaviour of low–grade coals and the subsequent chars in various utilisation processes, becomes pertinent. An investigation was therefore undertaken, to study the effects of chemical and physical properties imparted on chars during pyrolysis on the subsequent gasification reaction kinetics of typical South African inertinite–rich, high ash Highveld coals. An attempt was made at following these changes in the transition from coals to chars by a detailed characterisation of both the parent coals and the respective chars. These changes were determined using various conventional and advanced techniques, which included among others, carbon crystallite analysis using XRD and char carbon forms analysis using petrography. Three of the four original coals were characterised as Bituminous Medium rank C (coals B, C and C2), while coal D2 was found to be slightly lower in rank (Bituminous Medium rank D). The coals were rich in inertinites (> 54 vol. %, mmb with coal C2 having as high as 79 vol. %, mmb) and high in ash content (> 26.7 wt. %, db) and cabominerite and minerite contents (26 – 39 vol. %, mmb). The inertinitevitrinite ratios of the coals were found to range from 1.93 to 26.3. Characterization results show that both volatile matter and inherent moisture content decreased, while ash, fixed carbon and elemental carbon contents increased from coals to chars, indicating that the pyrolysis process was efficient. Elemental hydrogen, oxygen and nitrogen contents decreased, whereas total sulphur contents increased from coals to chars. This reveals that the total sulphur contained in the char samples was associated with the char carbon matrix and the minerals. Hydrogen–carbon and oxygen–carbon ratios decreased considerably from coals to chars showing that the chars are more aromatic and denser products than the original coals. Despite the fact that mineral matter increased from coals to chars, the relative abundance of the different mineral phases and ash components did not exhibit significant variation amongst the samples. The alkali index was, however, found to vary considerably among the subsequent chars. Petrographic analysis of the coals and char carbon forms analysis of the chars reveal that total reactive components (TRC) decrease while the total inert components (TIC) increase from coals to chars. The 0% gain in TIC observed in char C2 was attributed to its relatively high partially reacted maceral char carbon forms content. Total maceral reflectance shifted to higher values in the chars (4.43 – 5.28 Rsc%) relative to the coals (1.15 – 1.63 Rsc%) suggesting a higher structural ordering in the chars. Carbon crystallite analyses revealed that the chars were condensed (smaller in size) relative to the parent coals. Lattice parameters: interlayer spacing, d002, increased, while the average crystallite height, Lc, crystallite diameter, La, and number of aromatic layers per crystallite, Nave, decreased from coals to chars. Carbon aromaticity generally increased whereas the fraction of amorphous carbon and the degree of disorder index decreased from parent coals to the respective chars. Both micropore surface area and microporosity were observed to increase while the average micropore diameter decreased from coals to chars. This shows that blind and closed micropores were “opened up” during the charring process. Despite the original coal samples not showing much variation in their properties (except for their maceral content), it was generally observed that the subsequent chars exhibited substantial differences, both amongst themselves and from the parent coals. The increasing orders of magnitude of micropore surface area, microporosity, fraction of amorphous carbon and structural disorderliness were found to change in the transition, a good indication that the chars’ properties varied from that of the respective parent coals. Isothermal CO2 gasification experiments were conducted on the chars in a Thermax 500 thermogravimetric analyser in the temperature range of 900 – 950 °C with varying concentrations of CO2 (25 – 100 mol. %) in the CO2–N2 reaction gas mixture at ambient pressure (0.875 bar in Potchefstroom). The effects of temperature and CO2 concentration were observed to be in conformity with established trends. The initial reactivity of the chars was found to increase in the order: chars C2 < C < B < D2, with char D2 reactivity greater than the reactivity of the other chars by a factor > 4. Gasification reactivity results were correlated with properties of the parent coals and chars. Except for the rank parameter (the vitrinite reflectance), no significant trend was observed with any other coal petrographic property. Correlations with char properties gave more significant and systematic trends. Major factors affecting the gasification reactivity of the chars as it pertains to this investigation are: parent coal vitrinite reflectance, and: aromaticity, fraction of amorphous carbon, degree of disorder and alkali indices, micropore surface area, microporosity and average micropore diameter of the chars. The random pore model (chemical reaction controlling) was found to adequately describe the gasification reaction experimental data (both conversions and conversion rates). The determined activation energy ranged from 163.3 kJ·mol–1 for char D2 to 235.7 kJ·mol–1 for char B; while the order of reaction with respect to CO2 concentration ranged between 0.52 to 0.67 for the four chars. The lower activation energy of char D2 was possibly due to its lower rank, lower coal vitrinite reflectance and higher alkali index. The estimated kinetic parameters of the chars in this study correspond very well with published results in open literature. It was possible to express the intrinsic reactivity, rs, of the chars (rate of carbon conversion per unit total surface area) using kinetic results, in empirical Arrhenius forms. / Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2011.

With the increasing global energy demand and the decreasing availability of good quality coals, a better understanding of the important properties that control the behaviour of low–grade coals and the subsequent chars in various utilisation processes, becomes pertinent. An investigation was therefore undertaken, to study the effects of chemical and physical properties imparted on chars during pyrolysis on the subsequent gasification reaction kinetics of typical South African inertinite–rich, high ash Highveld coals. An attempt was made at following these changes in the transition from coals to chars by a detailed characterisation of both the parent coals and the respective chars. These changes were determined using various conventional and advanced techniques, which included among others, carbon crystallite analysis using XRD and char carbon forms analysis using petrography. Three of the four original coals were characterised as Bituminous Medium rank C (coals B, C and C2), while coal D2 was found to be slightly lower in rank (Bituminous Medium rank D). The coals were rich in inertinites (> 54 vol. %, mmb with coal C2 having as high as 79 vol. %, mmb) and high in ash content (> 26.7 wt. %, db) and cabominerite and minerite contents (26 – 39 vol. %, mmb). The inertinitevitrinite ratios of the coals were found to range from 1.93 to 26.3. Characterization results show that both volatile matter and inherent moisture content decreased, while ash, fixed carbon and elemental carbon contents increased from coals to chars, indicating that the pyrolysis process was efficient. Elemental hydrogen, oxygen and nitrogen contents decreased, whereas total sulphur contents increased from coals to chars. This reveals that the total sulphur contained in the char samples was associated with the char carbon matrix and the minerals. Hydrogen–carbon and oxygen–carbon ratios decreased considerably from coals to chars showing that the chars are more aromatic and denser products than the original coals. Despite the fact that mineral matter increased from coals to chars, the relative abundance of the different mineral phases and ash components did not exhibit significant variation amongst the samples. The alkali index was, however, found to vary considerably among the subsequent chars. Petrographic analysis of the coals and char carbon forms analysis of the chars reveal that total reactive components (TRC) decrease while the total inert components (TIC) increase from coals to chars. The 0% gain in TIC observed in char C2 was attributed to its relatively high partially reacted maceral char carbon forms content. Total maceral reflectance shifted to higher values in the chars (4.43 – 5.28 Rsc%) relative to the coals (1.15 – 1.63 Rsc%) suggesting a higher structural ordering in the chars. Carbon crystallite analyses revealed that the chars were condensed (smaller in size) relative to the parent coals. Lattice parameters: interlayer spacing, d002, increased, while the average crystallite height, Lc, crystallite diameter, La, and number of aromatic layers per crystallite, Nave, decreased from coals to chars. Carbon aromaticity generally increased whereas the fraction of amorphous carbon and the degree of disorder index decreased from parent coals to the respective chars. Both micropore surface area and microporosity were observed to increase while the average micropore diameter decreased from coals to chars. This shows that blind and closed micropores were “opened up” during the charring process. Despite the original coal samples not showing much variation in their properties (except for their maceral content), it was generally observed that the subsequent chars exhibited substantial differences, both amongst themselves and from the parent coals. The increasing orders of magnitude of micropore surface area, microporosity, fraction of amorphous carbon and structural disorderliness were found to change in the transition, a good indication that the chars’ properties varied from that of the respective parent coals. Isothermal CO2 gasification experiments were conducted on the chars in a Thermax 500 thermogravimetric analyser in the temperature range of 900 – 950 °C with varying concentrations of CO2 (25 – 100 mol. %) in the CO2–N2 reaction gas mixture at ambient pressure (0.875 bar in Potchefstroom). The effects of temperature and CO2 concentration were observed to be in conformity with established trends. The initial reactivity of the chars was found to increase in the order: chars C2 < C < B < D2, with char D2 reactivity greater than the reactivity of the other chars by a factor > 4. Gasification reactivity results were correlated with properties of the parent coals and chars. Except for the rank parameter (the vitrinite reflectance), no significant trend was observed with any other coal petrographic property. Correlations with char properties gave more significant and systematic trends. Major factors affecting the gasification reactivity of the chars as it pertains to this investigation are: parent coal vitrinite reflectance, and: aromaticity, fraction of amorphous carbon, degree of disorder and alkali indices, micropore surface area, microporosity and average micropore diameter of the chars. The random pore model (chemical reaction controlling) was found to adequately describe the gasification reaction experimental data (both conversions and conversion rates). The determined activation energy ranged from 163.3 kJ·mol–1 for char D2 to 235.7 kJ·mol–1 for char B; while the order of reaction with respect to CO2 concentration ranged between 0.52 to 0.67 for the four chars. The lower activation energy of char D2 was possibly due to its lower rank, lower coal vitrinite reflectance and higher alkali index. The estimated kinetic parameters of the chars in this study correspond very well with published results in open literature. It was possible to express the intrinsic reactivity, rs, of the chars (rate of carbon conversion per unit total surface area) using kinetic results, in empirical Arrhenius forms. / Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2011.

The main objective of this study was to determine the applicability of advanced water treatment processes namely granular activated carbon (GAC) adsorption, ultraviolet (UV) light disinfectant and ozone in the management of deteriorating water quality in the Mid-Vaal River system for drinking purposes. Both the scarcity and the deteriorating quality of water in South Africa can be addressed by investigating advanced water treatment processes such as GAC adsorption, UV light disinfectant and ozone. Previously disregarded water resources have the potential to be purified and advanced treatments can improve water quality where conventional water treatments have failed. In addition, advanced treatment processes can be applied to treat used water. The two sampling sites selected for the study, Rand Water Barrage (RWB) and Midvaal Water Company (MWC), are both located in the Middle Vaal Water Management Area with RWB upstream of MWC. RWB uses GAC adsorption and UV light disinfection and MWC uses ozone as pre- and intermediate treatment process steps for water purification. The quality of the source water at both sampling sites was determined by analysing the physical and chemical characteristics as well as the algal and invertebrate compositions of the source water. The physical and chemical water quality variables measured included pH, conductivity, turbidity, dissolved organic carbon (DOC), total organic carbon (TOC), total photosynthetic pigments (TPP), microcystin and geosmin. The source water of both sites was characterised as hypertrophic on account of high chlorophyll concentrations. The water quality of the two sites was distinctly different and a downstream change was observed. The source water of RWB was characterised by high microcystin, geosmin, DOC, TOC and conductivity measurements and dominated by Bacillariophyceae (diatoms) and Cyanophyceae (blue-green bacteria). Problematic species that were present in the source water of RWB included Aulacoseira sp., other unidentified centric diatoms, Pandorina sp., Anabaena sp., Microcystis sp., Oscillatoria sp., Cryptomonas sp., Ceratium sp. and Trachelomonas sp. The source water of MWC was characterised by high pH, turbidity and TPP measurements and was dominated by Chlorophyceae (green algae) and Bacillariophyceae (diatom) species. Problematic algal species that were present in the source water of MWC included Cyclotella sp., Coelastrum sp., Pediastrum sp. and Scenedesmus sp. The source water of MWC was deemed to be of a better quality due to the lower Cyanophyceae concentrations and lower microcystin levels. The invertebrate composition of both sites was similar with Rotatoria as the dominant invertebrate group. The efficacy of GAC adsorption/UV light disinfection/ozonation on restoring the physical and chemical characteristics of the source water at both sampling sites as well as the algal and invertebrate compositions was determined by ascertaining the nature of the change in or the percentage removal of a water quality variable. The potable water of both sites complied with the standards of water intended for domestic use except for the conductivity at RWB that was slightly elevated. The phytoplankton was removed effectively from the source water of both sites but the removal of invertebrates was unsatisfactory. GAC adsorption and filtration proved to be more effective in the removal of TPP, turbidity, DOC, microcystin and geosmin than ozone. Ozone effected an increase in DOC. UV light disinfection had no or little effect on restoring the water quality variables investigated in this study. / M (Environmental Sciences), North-West University, Potchefstroom Campus, 2015

The main objective of this study was to determine the applicability of advanced water treatment processes namely granular activated carbon (GAC) adsorption, ultraviolet (UV) light disinfectant and ozone in the management of deteriorating water quality in the Mid-Vaal River system for drinking purposes. Both the scarcity and the deteriorating quality of water in South Africa can be addressed by investigating advanced water treatment processes such as GAC adsorption, UV light disinfectant and ozone. Previously disregarded water resources have the potential to be purified and advanced treatments can improve water quality where conventional water treatments have failed. In addition, advanced treatment processes can be applied to treat used water. The two sampling sites selected for the study, Rand Water Barrage (RWB) and Midvaal Water Company (MWC), are both located in the Middle Vaal Water Management Area with RWB upstream of MWC. RWB uses GAC adsorption and UV light disinfection and MWC uses ozone as pre- and intermediate treatment process steps for water purification. The quality of the source water at both sampling sites was determined by analysing the physical and chemical characteristics as well as the algal and invertebrate compositions of the source water. The physical and chemical water quality variables measured included pH, conductivity, turbidity, dissolved organic carbon (DOC), total organic carbon (TOC), total photosynthetic pigments (TPP), microcystin and geosmin. The source water of both sites was characterised as hypertrophic on account of high chlorophyll concentrations. The water quality of the two sites was distinctly different and a downstream change was observed. The source water of RWB was characterised by high microcystin, geosmin, DOC, TOC and conductivity measurements and dominated by Bacillariophyceae (diatoms) and Cyanophyceae (blue-green bacteria). Problematic species that were present in the source water of RWB included Aulacoseira sp., other unidentified centric diatoms, Pandorina sp., Anabaena sp., Microcystis sp., Oscillatoria sp., Cryptomonas sp., Ceratium sp. and Trachelomonas sp. The source water of MWC was characterised by high pH, turbidity and TPP measurements and was dominated by Chlorophyceae (green algae) and Bacillariophyceae (diatom) species. Problematic algal species that were present in the source water of MWC included Cyclotella sp., Coelastrum sp., Pediastrum sp. and Scenedesmus sp. The source water of MWC was deemed to be of a better quality due to the lower Cyanophyceae concentrations and lower microcystin levels. The invertebrate composition of both sites was similar with Rotatoria as the dominant invertebrate group. The efficacy of GAC adsorption/UV light disinfection/ozonation on restoring the physical and chemical characteristics of the source water at both sampling sites as well as the algal and invertebrate compositions was determined by ascertaining the nature of the change in or the percentage removal of a water quality variable. The potable water of both sites complied with the standards of water intended for domestic use except for the conductivity at RWB that was slightly elevated. The phytoplankton was removed effectively from the source water of both sites but the removal of invertebrates was unsatisfactory. GAC adsorption and filtration proved to be more effective in the removal of TPP, turbidity, DOC, microcystin and geosmin than ozone. Ozone effected an increase in DOC. UV light disinfection had no or little effect on restoring the water quality variables investigated in this study. / M (Environmental Sciences), North-West University, Potchefstroom Campus, 2015