Thesis (M.S.)--University of Wisconsin--Madison. / Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 60-68).

Thesis (M.S.)--Brigham Young University. Dept. of Geology, 2005. / Includes bibliographical references (leaves 36-39).

Thesis (Ph. D.)--West Virginia University, 2001. / Title from document title page. Document formatted into pages; contains xii, 170 p. : ill. (some col.). Includes abstract. Includes bibliographical references.

In a study to investigate the fate of the applied P in soils, a red-sandy clayey soil (Ferric Luvisols) from Rustenburg (high P fixing) and a red-sandy loam soil (Ferric Acrisols) from Loskop (low P fixing) were used. Sequential P fractionations were used to determine the content of the different P pools to show which pool the applied P was transformed to. The soils treatments consisted of different Prates (0, 25, 50, 100, 150, and 200 mg kg-1), and incubation periods (1, 60, 120, 180, and 240 days) under a laboratory conditions. The sequential P fractionation procedure consisted of extraction with hydrous ferric oxide in a dialysis membrane tube (DMT-HFO), 0.5M NaHC03, O.1M NaOH-P, 1.0M HCI, concentrated HCI, and concentrated H2S04 + H2O2. Approximately 30 to 60 % of the added P were transformed into less labile P pools within one day and 80-90 % after 60 days. This transformation was faster in the Rustenburg than in the Loskop soil showing a higher P fixation capacity. A major part of the P transformation was to the -OH-P1 pool with a recovery of about 30%. In the second experiment an attempt was made to determine P desorption rates by successive DMT-HFO extractions (1, 7, 14, 28, and 56 days) after the transformations of the applied P. This was followed by the sequential extractions to determine the changes and distribution of the added P into different P pools as well as which pools the P was des orbed from. The Rustenburg and Loskop soils were treated to different Prates (0, 25, 50, 100, and 200 mg P kg-1) and incubation periods (1, 120, and 240 days). The cumulative DMT -HFO extraction curves for 56 days showed that desorption could continue for a much longer period. This property is important in the economical management of fertilizer applications rates. Results showed the transformations and distribution of the applied P during incubation periods and proved that all the stable soil P pools contributed to the labile P pool by different proportions after prolonged successive DMT-HFO extractions. Although Rustenburg soil is considered a high P fixing soil, the P release rates under laboratory conditions were high enough to meet the requirements of cotton and tobacco crops. Root systems of these crops do not exploit 100 % soil volume as this laboratory method, which could explain why these crops experience P deficiencies. It is envisage that by using this method the P releasing properties of a soil could be used to develop a P desorption model to determine how much extractable P, with a specific extractant, in a particular soil, should be available at the beginning of a growing season to sustain a high enough P releasing rate to meet the requirements of a certain crop up to the end of the growing season. To do this, a model to describe root development that represents the percentage of the soil exploited P desorption rates that simulate P uptake by plant roots will be necessary. / Thesis (DPhil (Plant Production: Horticulture))--University of Pretoria, 2006. / Plant Production and Soil Science / unrestricted

M.Sc. / The metallurgical industrial losses of base metals with waste solutions are an environmental threat to water sources, hence these metal ions must be removed prior to discharge into receiving bodies. In this study, Southern African clinoptilolite’s capability as an ion-exchanger with respect to Cu2+ and Co2+ was investigated in order to consider its application in metal cation removal from aqueous solutions. The clinoptilolite was characterised with X-ray powder diffraction (XRD), X-ray fluorescence (XRF), FTIR, thermogravimetric analyser (TGA) and SEM-EDS. The clinoptilolite was found to be a thermally stable alumino-silicate with calcite, dolomite and quartz as the main minerals. Investigations of Co2+ and Cu2+ uptake were first performed on non-mixed solutions of these cations. It was found that Cu2+ was removed faster than Co2+ with removal efficiencies of 79% and 63% respectively. The column method was used in the cation-exchange processes with synthetic solutions of 0.0020 M, 0.0698 M and 0.2000 M of Co2+ and Cu2+ concentrations which were measured using atomic absorption spectroscopy (AAS). The effects of Co2+ and Cu2+ ions on one another’s removal efficiency were investigated on Co/Cu mixed synthetic solutions by varying their concentration ratios in solution. The Cu2+ was generally found to be removed at lower rates than the Co2+. Investigations on added impurities in the form of Si4+ and Fe2+ in the mixed Co/Cu synthetic solutions were carried out to determine their effect on the removal efficiencies of the targeted metals. It was found that both Si4+ and Fe2+ greatly reduced the removal efficiency of Cu2+, especially with increased amounts of Si4+ in the Co/Cu solution.

The potential of non-viable Azalia filiculaides for the removal of Cu and Ni from aqueous solutions and the possibility of scaling up existing lab scale Azalia column systems was investigated. The effects of factors such as metal starting concentration, pH and two metals in solution on the removal of Ni and Cu from aqueous solution by dried and crushed Azalia biomass were studied in batch systems. Aqueous solutions of Ni with starting concentrations between 1000 and 2000J.lmolll gave the most efficient Ni removal by Azalla biomass. For Cu the optimum starting concentration for adsorption was 50J.lmol/l. The adsorption capacity of both eu and Ni increased as the starting pH of the sorption media increased. The optimum pH for Ni adsorption was found at pH 7 and for Cu, at pH 5. - Awlla biomass had a higher. maximum binding capacity (qrnax) for Cu than for Ni at pH 5. The removal of both Cu allct Ni showed little or no variation with the presence another metal in solution. Kinetic studies show that both Cu and Ni adsorbed rapidly onto the Azalia biomass. The removal of Cu and Ni from aqueous solutions using non-viable Azalia biomass was investigated in a lab scale fixed-bed column and an upscaled 4L column system. The nonviable Azalla filiculaides biomass when dried and used in a column for adsorption of Cu and Ni showed good physical stability under many different conditions. Preparation of the biomass before it could be used in the columns was very simple and did not involve any significant pretreatment steps. Prolonged exposure to UV light decreases Azalia biomass capacity for Ni and Cu adsorption. Column adsorption of Cu and Ni from aqueous solutions was successfully upscaled approximately 100 times. Relative to the lab scale column, the 4L column performed better for the uptake of Cu and Ni per gram of biomass. The larger column was also able to operate at relatively higher flow rates. The biomass showed good reusability with little change in the amount of Ni adsorbed in 10 consecutive cycles. Electron micrographs showecf little or no change in the physical structure and integrity of the Azolla biomass after exposure to mineral acids, Ni solution and high flow rates over 10 consecutive adsorption and desorption cycles. As much as 80% Ni and 70 % Cu was recovered when desorption profiles were generated using O.lMHCI as a desorption agent. The 4L column system was also tested using a highly concen~rat:~ Ni plating bath solution.(Nicrolyte 1). Only 18 % of the Ni could be removed from the expended Nicrolyte 1 pla~Jng solution after treating only 25L, indicating that Azolla biomass is more suited for removal of metals from more dilute industrial effluents.

Gas absorption rates were experimentally determined for a number of tworphase gas-liquid systems in co-current horizontal flow through circular tubes. Sparingly soluble gases were used in order to determine the liquid phase resistance to mass transfer. A series of experiments was designed to separate the effects of gas density, liquid-phase diffusivity, viscosity, surface tension, and tube diameter, on the mass transfer rates. The gas-liquid systems employed, in a single tube 1.757 cm. in diameter, were CO₂-water, He-water, CO₂-ethanol, and CO₂-ethylene glycol. Two additional tube sizes, 1.228 and 2.504.cm. in diameter were employed with the C02-water system to determine the effect of tube diameter. The gas and liquid flow rates used produced four different flow regions, bubble, plug, slug, and annular flow. The gas, and liquid, superficial velocities ranged from 0.1 to 40 fps, and 0.5 to 3.6 fps, respectively. Two correlations were developed for predicting mass transfer rates in two-phase flow. The first, based on a theory that each bubble represents a "mixing stage", is applicable to the bubble and plug regions of flow, and correlates the experimental' data for a wide range of liquid physical properties, as well as gas and liquid flow rates, with a probable error of approximately 15%. The second correlation, applicable to slug flow, empirically correlates the data for this region, over the same wide range of physical properties and flow rates, with a probable error of approximately 10%. The surface renewal or "penetration theory" mechanism of transfer is shown to be consistent with the experimental results obtained in the bubble and plug regions. In the slug region, on the other hand, evidence is available to indicate that another mechanism (probably that proposed by Kishinevskii), becomes increasingly important as the degree of turbulence increases. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

Thesis (M. Sc. (Chemistry)) -- University of Limpopo, 2016 / In this study, the use of synthetic hierarchical MFI zeolites as supports for palladium hydrocracking catalysts was investigated. Hierarchical zeolites were synthesised through two different routes, viz., (i) the indirect and (ii) direct routes. In (i) pristine ZSM-5 zeolites with different SiO2/Al2O3 ratios (SARs) were synthesised hydrothermally using tetrapropylammonium bromide as structure-directing agent (SDA), followed by a brief desilication of its calcined form in 0.2 M NaOH solution at 65 °C for 0.5 h. Procedure (ii) involved prior synthesis of three polyquaternary ammonium surfactants (containing 2 - 4 ammonium centres), followed by their use as SDAs in the hydrothermal synthesis of hierarchical MFI zeolites. The resulting materials were characterised by XRD, FT-IR, SEM and N2 adsorption isotherms (including BET surface area measurements). Successful synthesis of different classes of the hierarchical MFI zeolites was confirmed by XRD patterns, while successful synthesis of polyquaternary ammonium surfactants was confirmed by both their 1H NMR spectra and their ability to direct the MFI structure. On the basis of IR, peak intensities in the OH region between 3500 and 3800 cm-1, the surfactant-templated zeolites were inferred to be more acidic than zeolites prepared through the desilication route. Significant changes in crystal morphology were observed upon desilication of ZSM-5(50), while the ZSM-5(77) and ZSM-5(100) retained their agglomerated morphology upon a similar treatment. The micrograph pristine of ZSM-5(50) showed a predominant morphology of large and small spheroids, together with some ill-defined cubic shapes. After desilication, the zeolite did not retain the original morphology entirely, showing hexagonal prismatic crystals with twinning occurring in other areas and large spheroids “hatching” to reveal their contents upon treatment. Desilicated zeolites exhibited improved textural properties (i.e., increased SBET, pore volumes and pore diameters) and minor structural readjustments compared to their pristine counterparts. Textural properties of surfactant-templated zeolites were superior to those of desilicated zeolites, and improved with increasing number of quaternary ammonium centres in the surfactant template. These materials were generally more crystalline than the conventional zeolites. Hydrocracking catalysts containing 0.9 wt.% Pd loading on different MFI supports were prepared by the incipient wetness impregnation method. The n- v hexadecane hydrocracking conditions used were typical of LTFT process (i.e., Temperature = 215 - 310 °C, WHSV = 1 h-1, Pressure = 20 bar, in addition to the H2 /n-C16 ratio of 10). The catalytic activity in all catalyst systems increased with increasing reactor temperature and displayed C4/C12 ratios ≠ 1, evidence of the occurrence of secondary cracking (i.e., a non-ideal hydrocracking behaviour). This was also supported by the shapes of their product distribution profiles, which showed dominant C3 - C7 n-paraffins. Co-feeding H2O with n-C16 into the reactor was found to be detrimental to n-C16 conversion, but promoted the selectivity to iso-paraffins in the product spectrum. Simultaneous introduction of CO and H2O aggravated secondary cracking. Amongst the pristine ZSM-5 zeolite-based catalysts, Pd/P-ZSM-5(77) showed the best catalytic performance. Upon desilication, the performance order changed to favour Pd/D-ZSM-5(50*). For the surfactant-templated supports, Pd/HSZ(N4) showed the most superior hydrocracking performance. Comparison of catalytic activities of the best performing catalyst systems derived from the conventional and surfactant-templated zeolites in the hydrocracking of n-hexadecane, follow the order Pd/D-ZSM-5(50*) > Pd/P-ZSM-5(77) > Pd/HSZ(N4). That is, the pristine and desilicated zeolite-based catalysts performed better than their surfactant-templated zeolite-based counterparts. Therefore, the post-synthesis generation of mesoporosity through desilicating ZSM-5 with a SAR of 50 has proven beneficial for the resulting catalyst system. One of the possible reasons for the relatively inferior hydrocracking performance of the Pd/HSZ(N4) catalyst may be the aluminium-richness of the support (SAR = 40) compared to the conventional ZSM-5-based supports. In summary, catalysts Pd/D-ZSM-5(50*), Pd/P-ZSM-5(77) and Pd/HSZ(N4) are promising for diesel-selective catalysis and need further refinements and exploration.

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