>Magister Scientiae - MSc / In South Africa coal combustion constitutes up to 90 % of the country’s energy need. This coal combustion activity is known to contribute to the amount of about 40 % of the total CO2 atmospheric emissions worldwide that are responsible for global warming effects. In addition burning of coal generates a large quantity of fly ash which creates environmental pollution since only a small portion of it is currently used in some applications. In order, on one hand to mitigate and sequester CO2 and on the other hand to reprocess fly ash and reuse it, this study focuses on developing new technologies with cost-effective and less energy consumption in the domain of CO2 capture and sequestration. CO2 has priority attention for being the largest contributor to global warming. Various techniques have been used for CO2 capture and sequestration, such as aqueous alkylamine absorption or adsorption onto a solid adsorbent such as zeolites. In this study NaA zeolite adsorbent was hydrothermally synthesised from South African fly ash. This fly ash based NaA zeolite was then used as starting material to prepare LiA, CaA, and MgA zeolite catalysts via ion-exchange for comparative CO2 adsorption capacity. A systematic design of the ion-exchange procedure was undertaken at either 30 °C or 60 °C for a contact time of 1 hr, 4 hrs, and 8 hrs with 1, 2 and 3 consecutive exchanges in each case in order to determine the optimum conditions for loading each cation exchanged. The adsorption of CO2 on the ion- exchanged fly ash based zeolite-A catalysts was carried out at 40 °C similar to the temperature of flue gas since the catalysts obtained in this study were also prepared with a view to their applications in flue gas system. The CO2 desorption temperature ranged between 40-700 °C. All materials used in this study, starting from fly ash feedstock, werecharacterized using various techniques to monitor the mineral and structural composition, the morphology, surface area and elemental composition and the adsorption capacity. The techniques included mainly Fourier transform infra-red, X-ray diffraction, Scanning electron microscopy, Transmission electron microscopy, Energy dispersive spectroscopy, X-ray fluorescence, Temperature programmed desorption.The results obtained from both Fourier transform infra-red and the X-raydiffraction spectroscopy for samples exchanged at either 30° C or 60 °C showedlower crystallinity in CaA and MgA zeolite samples. This decrease in crystallinitymainly affected the D4R (0-20° 2) and was demonstrated in the study to beinversely proportional to the increase of the atomic radius of cations (Li+ > Mg2+ >Ca2+). In the Fourier transform infra-red, the vibration band at 677 cm-1 attributedto the extra-framework cation, also proportionally increased with the decrease ofthe atomic radius or size of the cations, and was intense in LiA zeolite samples.

Thesis (M. Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2008.

Aprotic solvents are organic solvents which do not easily react with a substance dissolved in it and they do not exchange protons despite of their high ion and polar group dissolving power. Therefore, this characteristic property makes aprotic solvents very suitable intermediates in many industries producing pharmaceuticals, textile auxiliaries, plasticizers, stabilizers, adhesives and ink. Dehydration of these mixtures and recirculation of valuable materials are substantial issues in industrial applications. The conventional method for recovery of aprotic solvents has been distillation, which requires excessive amount of energy to achieve desired recovery. Hydrophilic pervaporation, which is a membrane based dehydration method with low energy consumption, may become an alternative. Because of high dissolving power of aprotic solvents only inorganic membranes can be employed for this application. In this study three types of inorganic membranes (NaA zeolite, optimized silica and HybSi) were employed. Main objective of this studys to investigate effect of membrane type and various operationg parameters (feed composition at a range of 50-5% and temperature at a range of 50-100oC) on pervaporative dehydration of aprotic solvents / dimethylacetamide, dimethylformamide and n-methylpyrrolidone. During the experiments, feed samples were analyzed with Karl Fischer Titration Method / permeate samples were analyzed with Gas Chromatography. Experiments showed that proper dehydration of aqueous aprotic solvent mixtures was succeded with all three membranes investigated. In the target feed water content range (50 to 20%wt), permeate water contents were higher than 98%wt which was quite acceptable for all membranes. Moreover, NaA zeolite membrane performed higher fluxes than optimized silica and HybSi in composition range of 50 to 15% water at 50oC. It was also observed that HybSi membrane had higher fluxes and permeate water contents than optimized silica membrane for all solvents. On the other hand, the rates of decrease in permeate fluxes changed depending on the type of solvent for optimized silica and HybSi membranes. With both membranes, permeate flux of dimethylformamide decreased much slower than that of n-methylpyyrolidone. Furthermore, the results showed that permeate fluxes of HybSi membrane increased with increasing operation temperature due to the change of solvent activity in mixture. In addition, an Arrhenious type equation was used to describe changes in fluxes with changing temperature. It was also found that activation energy of water for diffusion through HybSi membrane was calculated as 8980 cal/mol.

In this study, the feasibility of a NaA zeolite membrane for the gas phase separation of steam and hydrogen mixtures was determined. The Fischer-Tropsch (FT) process, which produces high value fuels and chemicals from coal and natural gas, can be greatly improved upon by the selective removal of water from the FT reactor product stream. According to the FT reaction kinetics, the rate of reaction increases with the partial pressure of hydrogen but is adversely affected the presence of water in the reactor product stream. Chemisorbed water on the surface of the metal catalysts also enhances deactivation due to sintering and fouling. The use of a zeolite membrane reactor is well equipped to serve the purpose of in-situ water removal as it can facilitate the separation of chemical components from one another in the presence of catalytic reactions. The LTA type zeolite membrane NaA or zeolite 4A, in particular, is well suited for the separation of polar (H2O) from non-polar (H2) molecules because of its high hydrophilicity. NaA has also been identified as an excellent candidate for selective water removal applications due its high adsorption affinity and capacity for water. The NaA membrane used in this study was manufactured by means of the in-situ crystallisation method where the growth of crystals on the inside surface of a centrifugally casted a-alumina support was favoured. Scanning electron microscopy (SEM) analyses performed on the membrane after a double hydrothermal synthesis indicated that the surface topology was rough and that the zeolite crystals formed were not uniform in size. Overall, the membrane thickness varied between 6.5 and 8.0 flm. An evaluation of the membrane quality was made possible through permeation experiments involving SF6 and Hz. The calculated Hz/SF6 permselectivity in this study was found to be 9.78, which despite being higher than the Knudsen diffusion selectivity of 8.54, confirmed the presence of intercrystalline defects or non-zeolitic pores in the membrane. Experiments concerning pure component and binary mixture permeation of steam and hydrogen through the supported NaA membrane were conducted over a temperature range of 115°C to 160 °c for binary hydrogen/steam mixtures, 25°C to 160°C for pure hydrogen and 130°C to 170°C for pure steam. For the permeation of pure component hydrogen, a local maximum in its permeance having a value of 224 x 10'°8 mol.m,z.s'!.Pa'! was reached at a system pressure and temperature of 6.875 bar and 75°C respectively. For the permeation of pure component steam through NaA, the effects of capillary condensation in the pores and defects of the zeolite membrane resulted in a decrease in steam permeance as a function of absolute pressure for temperatures lower than 160 °c. Once the effects of capillary condensation had receded, maxima in the steam permeances as a function of temperature corresponding to values of 70 x 10,08, 65 X 10,08 and 75 x 10,08 mol.m•2.s'I.Pa'l were found for the 182.5, 197.5 and 222.5 kPa isobars respectively. These observations collaborated well with the description of surface diffusion with permeation taking place in the Langmuir (strong adsorption) regime. Permeation experiments through NaA as function of temperature were conducted for a 90 mol% steam -10 mol% hydrogen (90-10) binary mixture as well as for a 60-40 mixture of these two. At low temperatures the permeation of hydrogen was completely suppressed by the condensed steam resulting in an almost perfect separation. The Kelvin equation was used to estimate the pore size of the defects which was found to range between 1.86 and 2.45 nm. The temperature range over which these defects in the membrane were assumed to become unblocked (i.e. assuming when the first breakthrough of hydrogen occurred), were determined to be between 140 to 148 °c and between 128 to 130 °c for the 90-10 and 60-40 mixtures respectively. The mixture selectivities (towards water) between 115 °c and 130 °c were found to be immensely high (much greater than 1000) for both the 90-10 and 60-40 mixtures, while the ideal selectivities were calculated to be less than lover the same temperature range. At 140 °c, the selectivity towards water for the 9010 mixture was still greater than 1000; however for the 60-40 mixture at this temperature, an inversion of selectivity towards H2 had already taken place. The breakthrough in H2 permeance occurs at a much lower temperature when the feed mixture contains a lower concentration of water. Since the partial pressure of steam will be reduced, larger pores will become unblocked at lower temperatures according to the Kelvin equation. / Thesis (M. Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2008.

In this study, the feasibility of a NaA zeolite membrane for the gas phase separation of steam and hydrogen mixtures was determined. The Fischer-Tropsch (FT) process, which produces high value fuels and chemicals from coal and natural gas, can be greatly improved upon by the selective removal of water from the FT reactor product stream. According to the FT reaction kinetics, the rate of reaction increases with the partial pressure of hydrogen but is adversely affected the presence of water in the reactor product stream. Chemisorbed water on the surface of the metal catalysts also enhances deactivation due to sintering and fouling. The use of a zeolite membrane reactor is well equipped to serve the purpose of in-situ water removal as it can facilitate the separation of chemical components from one another in the presence of catalytic reactions. The LTA type zeolite membrane NaA or zeolite 4A, in particular, is well suited for the separation of polar (H2O) from non-polar (H2) molecules because of its high hydrophilicity. NaA has also been identified as an excellent candidate for selective water removal applications due its high adsorption affinity and capacity for water. The NaA membrane used in this study was manufactured by means of the in-situ crystallisation method where the growth of crystals on the inside surface of a centrifugally casted a-alumina support was favoured. Scanning electron microscopy (SEM) analyses performed on the membrane after a double hydrothermal synthesis indicated that the surface topology was rough and that the zeolite crystals formed were not uniform in size. Overall, the membrane thickness varied between 6.5 and 8.0 flm. An evaluation of the membrane quality was made possible through permeation experiments involving SF6 and Hz. The calculated Hz/SF6 permselectivity in this study was found to be 9.78, which despite being higher than the Knudsen diffusion selectivity of 8.54, confirmed the presence of intercrystalline defects or non-zeolitic pores in the membrane. Experiments concerning pure component and binary mixture permeation of steam and hydrogen through the supported NaA membrane were conducted over a temperature range of 115°C to 160 °c for binary hydrogen/steam mixtures, 25°C to 160°C for pure hydrogen and 130°C to 170°C for pure steam. For the permeation of pure component hydrogen, a local maximum in its permeance having a value of 224 x 10'°8 mol.m,z.s'!.Pa'! was reached at a system pressure and temperature of 6.875 bar and 75°C respectively. For the permeation of pure component steam through NaA, the effects of capillary condensation in the pores and defects of the zeolite membrane resulted in a decrease in steam permeance as a function of absolute pressure for temperatures lower than 160 °c. Once the effects of capillary condensation had receded, maxima in the steam permeances as a function of temperature corresponding to values of 70 x 10,08, 65 X 10,08 and 75 x 10,08 mol.m•2.s'I.Pa'l were found for the 182.5, 197.5 and 222.5 kPa isobars respectively. These observations collaborated well with the description of surface diffusion with permeation taking place in the Langmuir (strong adsorption) regime. Permeation experiments through NaA as function of temperature were conducted for a 90 mol% steam -10 mol% hydrogen (90-10) binary mixture as well as for a 60-40 mixture of these two. At low temperatures the permeation of hydrogen was completely suppressed by the condensed steam resulting in an almost perfect separation. The Kelvin equation was used to estimate the pore size of the defects which was found to range between 1.86 and 2.45 nm. The temperature range over which these defects in the membrane were assumed to become unblocked (i.e. assuming when the first breakthrough of hydrogen occurred), were determined to be between 140 to 148 °c and between 128 to 130 °c for the 90-10 and 60-40 mixtures respectively. The mixture selectivities (towards water) between 115 °c and 130 °c were found to be immensely high (much greater than 1000) for both the 90-10 and 60-40 mixtures, while the ideal selectivities were calculated to be less than lover the same temperature range. At 140 °c, the selectivity towards water for the 9010 mixture was still greater than 1000; however for the 60-40 mixture at this temperature, an inversion of selectivity towards H2 had already taken place. The breakthrough in H2 permeance occurs at a much lower temperature when the feed mixture contains a lower concentration of water. Since the partial pressure of steam will be reduced, larger pores will become unblocked at lower temperatures according to the Kelvin equation. / Thesis (M. Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2008.