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M. Tech. / Gold (Au) mining in South Africa resulted in vast volumes of hazardous waste being generated. Poor management of most of the tailings dams has resulted in the release of acid mine drainage, which caused stream water and soil contamination with their run-offs. The consequence of mine closure has not only been observed in large-scale land degradation, but also in widespread pollution of surface water and groundwater in the Wonderfonteinspruit Catchment Area (WCA). Thus, clean-up methods must be developed in order to remove heavy metals from contaminated water bodies in this area. The efficacy of algae, zeolite and zeolite functionalized with humic acid in reducing the concentration of the heavy metals iron (Fe3+), zinc (Zn2+), manganese (Mn2+) and nickel (Ni2+) to acceptable levels in WCA was investigated in this study. It is also envisaged that the heavy metals to be removed from contaminated water can be useful in various industries. A sampling exercise was undertaken with the aim of identifying the heavy metals that contaminate the water in the catchment, as well as identify the priority heavy metals for laboratory sorption tests. Batch experiments were conducted to study the adsorption behavior of natural zeolite clinoptilolite and algae Desmodesmus sp. with respect to Fe3+, Mn2+, Ni2+, and Zn2+. The data was analysed using the Langmuir and Freundlich isotherms. Two kinetic models namely, pseudo-first order and pseudo second order were also tested to fit the data. It was found that the concentration of Fe3+, Mn2+, Ni2+ and Zn2+ was 115 mg/L, 121 mg/L, 26.5 mg/L and 6.9 mg/L from the sampled water bodies in the WCA, respectively. The Langmuir isotherm was found to correlate the adsorption of Fe3+, Mn2+, Ni2+, and Zn2+ better, with the adsorption capacity of 11.9 mg/g, 1.2 mg/g, 1.3 mg/g, and 14.7 mg/g, for the functionalized zeolite (FZ), respectively. The algae system gave adsorption capacities of 1.523 mg/g, 144 mg/g and 71.94 mg/g for Fe3+, Mn2+ and Ni2+; respectively. Pseudo second-order equation was found to be the best fit for the adsorption of heavy metals by unfunctionalized zeolite (UFZ) and the algae system. Zeolite functionalization with humic acid increased its uptake ability. The best results for kinetic study was obtained in concentration 120 ppm for Fe3+ and Mn2+, whilst for Ni2+ was at 20 mg/L , which is about the same concentrations found in contaminated water in the WCA (Fe3+ 115 mg/L, Mn2+121 mg/L and Ni2+ 26.5 mg/L).

This work examined the effects of thermal and chemical treatments on zeolite reactivity and determined the zeolite properties governing the development of compressive strengths and pozzolanic reactivity. Zeolites are naturally occurring aluminosilicate minerals found abundantly around the world. Incorporation of zeolites in cement mixtures has been shown by past research to increase concrete’s compressive strength and durability. In addition, use of zeolites as SCMs can decrease the environmental impact and energy demands associated with cement production for reinforced concrete structures. Further, in contrast to man-made SCMs such as fly ash, zeolite minerals provide a reliable and readily available SCM source, not affected by the production limits and regulations of unrelated industries such as the coal power industry. In this work, six sources of naturally occurring clinoptilolite zeolite were examined. The zeolites were first characterized using x-ray fluorescence, quantitative xray diffraction, thermal analysis, particle size analysis, pore size distribution and surface area analysis, and scanning electron microscopy. Cation exchange capacity was also tested for one of the zeolites. Following comprehensive material characterization, the six pozzolanic reactivity of the natural zeolites was determined by measuring the quantity of calcium hydroxide in paste after 28 or 90 days, by measuring calcium hydroxide consumption of the zeolite in solution and by tracking the development of strengths of zeolite-cement mortars. Pretreatments that attempted to increase the reactivity of the zeolites, including calcination, acid treatment, milling and cation exchange, were then tested and evaluated using the same methods of material characterization and testing mentioned previously. Last, the results of the reactivity testing were reanalyzed to determine which properties of natural zeolites, including particle size, nitrogen-available surface area, and composition, govern the development of compressive strengths, pozzolanic reactivity and improved cement hydration parameters of pastes and mortars using natural zeolites as SCMs. Pretreatment testing showed that milling and acid treatment successfully increased the reactivity of zeolites used as SCMs. Additionally, particle size was shown to be the dominant property in determining the development of compressive strengths while particle size and surface area of the zeolites contributed to zeolite pozzolanic reactivity. / text

Zeolites are well-known aluminosilicate minerals that have been widely used as adsorbents in separation, purification processes and environmental pollution control. Zeolites are used in various industrial applications due to their high cation-exchange ability, molecular sieve and cataltic properties. In order to reduce the costs of acquisition and minimise the disposal of adsorbents, both modified natural zeolite and synthetic zeolite (derived from kaolinite) were used for the purification of wastewater. The characteristic properties and applications of adsorbents are also discussed including the advantages and disadvantages of each technique. The present work involves the study of the removal of Cu2+, Fe3+, Pb2+ and Zn2+ from synthetic metal solutions using natural zeolite. Laboratory experiments were used to investigate the efficiency of adsorbents in the uptake of heavy metals from industrial wastewater. These include equilibrium tests, kinetic studies and regeneration studies. The physical and chemical characterization of the zeolites was carried out using different analytical techniques such as Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), X - Ray Diffraction (XRD), X - Ray Fluorescence (XRF), Thermogravimetric Analysis (TGA), Fourier Transform Infrared (FT-IR) Spectroscopy and Inductively Coupled Plasma-Optical Emission Spectrometer (ICP-OES). The kinetic study indicated the suitability of the natural zeolite for the removal of Cu2+, Fe3+, Pb2+ and Zn2+ ions from synthetic wastewater. Batch experiments were used to identify the effect of parameters that affect the rate of adsorption such as the effect of adsorbent mass, effect of adsorbent particle size, effect of initial solution pH, effect of initial solution concentration, effect of agitation speed and effect of pre-treatment of adsorbent and evaluated their impact on the efficiency of the zeolite in the removal of heavy metals from industrial wastewater. The kinetic studies showed that the capacity of the adsorbents for the removal of heavy metals increased with a greater mass of absorbent, increased initial solution pH, increased agitation speed, higher solution concentration as well as the application of a pre-treatment. The results from the equilibrium studies positively demonstrated that natural zeolite can be used as an excellent adsorbent for removing heavy metals from multi-component solutions. The equilibrium experiments indicated that the capacities of natural zeolite for the uptake of heavy metals increased when the initial solution pH increased. The results indicated that the maximum removal capacities Q were 22.83, 14.92, 14.49 and 17.54 mg/g natural zeolite for copper, iron, zinc, and lead respectively. Both the Langmuir and Freundlich isotherm models were used to characterize the experimental data and to assess the adsorption behaviour of natural zeolite for copper, iron, lead and zinc. The experimental data were slightly better suited to the Langmuir isotherm than the Freundlinch isotherm. The value of the correlation coefficients r2 ranged from 0.93 to 0.99 for the Langmuir isotherm and from 0.90 to 0.99 for the Freundlich isotherm. The present work also involved the study of synthetic zeolite A, which was derived from natural kaolinite. The conversion of the raw materials into zeolitic materials was carried out in two ways: first, conventional hydrothermal synthesis and second, alkaline fusion prior to hydrothermal synthesis. The results from both routes show that zeolite A was synthesised successfully. Finally, the experiments show that both natural and synthetic zeolites can be available in commercial quantities. Synthetic zeolites are more attractive for some specific applications, while the cheapness of natural zeolite may favour its use.

In this thesis, firstly, the equilibrium adsorption capacity of water on a natural zeolite at several zeolite temperatures and water vapor pressures has been experimentally determined for adsorption and desorption processes. Additionally, the modified Dubinin-Astakhov adsorption equilibrium model has been fitted to experimental data and separate correlations are obtained for adsorption and desorption processes as well as a single correlation to model both processes. Experimental results show that the maximum adsorption capacity of natural zeolite is nearly 0.12 kgw/kgad for zeolite temperatures and water vapor pressures in the range 40-150 C and 0.87-7.38 kPa. Secondly, a thermally driven adsorption cooling prototype using natural zeolite-water as working pair has been built and its performance investigated experimentally at various evaporator temperatures. Under the experimental conditions of 45 C adsorption, 150 C desorption, 30 C condenser and 22:5 C, 15 C and 10 C evaporator temperatures, the COP of the adsorption cooling unit is approximately 0.25 and the maximum average volumetric specific cooling power density (SCPv) and mass specific cooling power density (SCP) of the cooling unit are 5.2 kWm-3 and 7 Wkg-1, respectively. Thirdly, in order to investigate the dynamic heat and mass transfer behavior of the adsorbent bed of an adsorption cooling unit, a transient local thermal non equilibrium model that accounts for both internal and external mass transfer resistances has been developed using the local volume averaging method. Finally, the influence of several design parameters on the transient distributions of temperature, pressure and amount adsorbed inside the cylindrical adsorbent bed of an adsorption cooling unit using silica-gel/water have been numerically investigated for the one and two dimensional computational domains. Moreover, validity of the thermal equilibrium model assumption has been shown under the given boundary and design conditions. Generally, for the conditions investigated, the validity of the local thermal equilibrium and spatially isobaric bed assumptions have been confirmed. To improve the performance of the bed considered, eorts should be focused on reducing heat transfer resistances and intra-particle mass transfer resistances but not inter-particle mass transfer resistances.

This study revealed that ammonium ion exchange of natural zeolite could be a feasible method of nitrogen removal and recovery from permeate from anaerobic membrane bioreactors (AnMBRs). NaCl concentrations optimized for chemical regeneration in batch experiments did not match those in continuous column tests. Instead, the mass ratio of Na+ to Zeolite-NH4+-N was significant for improving regeneration efficiency in column experiments; this mass ratio was 750 g Na+/g Zeolite-NH4+-N required for regeneration efficiency over 90% in 2 hours at pH 9. ???To decrease the NaCl dose in regeneration of exhausted zeolite, a high pH regeneration method was developed using an NaCl concentration of 10 g/L at pH 12 (the mass of Na+ to Zeolite-NH4+-N of 4.2 ) which achieved a regeneration efficiency about 85%. The recovery of ammonium nitrogen from the exhausted zeolite was assessed with air stripping followed by ammonia collection in an acid scrubber. The effects of shaking and air stripping were investigated in batch tests and the results showed the superiority of air stripping over shaking. Liquid circulation and air flow rates were varied for optimization of ammonia recovery in a continuous zeolite-packed column combined with a regeneration chamber and a stripping column. The liquid circulation rate had no significant effect on either the regeneration efficiency or the ammonia transfer efficiency from ammonium nitrogen to ammonia gas, while the ammonia transfer efficiency significantly increased with the air flow rate.??? Furthermore, the effect of pH on ammonia recovery was tested. Both the regeneration efficiency and the ammonia transfer efficiency were significantly improved with increasing pH. When the pH was increased from 9.5 to 12, the regeneration efficiency increased from 9.2% to 84% and the ammonia transfer efficiency increased from 54% to 92%. The nitrogen recovery process that combines zeolite ammonium exchange and air stripping can decrease chemical costs for regeneration of exhausted zeolite and efficiently collect ammonium nitrogen to be reused as fertilizers. Hence, the integrated nitrogen process can resolve the challenge of nitrogen removal in anaerobic membrane bioreactors treating organic wastewater in sustainable manners.

Clinoptilolite is the most abundant zeolite mineral in nature. In this study a reproducible synthesis recipe for clinoptilolite was established and the limits of the crystallization field were developed by changing synthesis parameters such as temperature, composition and the nature of reactants. Clinoptilolite was reproducibly synthesized as a pure phase and in high yield at 140oC using a benchmark batch composition of 2.1 Na2O:Al2O3:10SiO2:110.1 H2O. Clinoptilolite was crystallized from 10wt% or 28wt% seeded systems while it was not formed if no seeds were present. Clinoptilolite was also crystallized as a pure phase when the cation in the benchmark batch composition was Na,K mixture, or when alkali salts such as carbonates or chlorides were used besides alkali hydroxides, or when the SiO2/Al2O3 ratio was in the range of 10-12. Clinoptilolite was still crystallized as a single phase when alkali hydroxides in the batch were reduced by 20%. With the benchmark batch composition, clinoptilolite was crystallized in pure phase form at 100oC, 120oC, 140oC and 160oC while synthesis at 175oC resulted in the formation of pure mordenite. At 140oC clinoptilolite was crystallized together with Linde L when cation in the benchmark composition is only potassium. Phillipsite crystallized together with clinoptilolite at SiO2/Al2O3 ratio of 8 to 9. At SiO2/Al2O3 ratios of 6 or 4, phillipsite or analcime was formed as pure phase respectively. When the alkali hydroxides in the batch was increased by 20%, sanidine was formed. Use of reactive aluminosilicate gels enhanced the formation of clinoptilolite while attempts to use mineral raw materials were unsuccessful. For both Na and (Na,K)-clinoptilolite, Si/Al ratio of products were greater than four. Thermal stability of synthetic clinoptilolites were comparable with natural clinoptilolite and potassium ion increased thermal stability of clinoptilolite.

Treating ammonium pollution in ground water by natural zeolite after being modificated to the Naform (Z-Na) is the new way of research that scientists interested in. The experiment results showed that, at pH 6, the efficient of treating ammonium in ground water is the highest. The efficient of treating increase rapidly in the first 5 minutes and remain stable after that. Higher concentration of the Z-Na will increase the treating coefficient of the process. With a water sample that has CNNH4+= 27 mg/L at first, using CZ-Na=13g/L and after 5 minutes, the concentration of ammonium in water was declined to 1mg/L, passed the Vietnamese standard for ground water (QCVN 09:2015- MT/BTNMT). The treating coefficient is 96.30%, the adsorption capacity is 2.07 mg N-NH4 +/1g ZNa. The loaded Z-Na was regenerated using 2g/L NaOH solution, the ammonium recovery ratio exceeded 92%. This means the reuse of Z-Na for ammonium adsorption is very high. The results of the experiment with groundwater samples in Phu Xuyen district, Ha Noi have a concentration of 53 mg/L. In conclusion, Z-Na material is perfectly fit for purpose of treating ammonium in ground water because of it low price, safety, easily to imitate and high efficiency. / Xử lí ô nhiễm amoni trong nước ngầm bằng vật liệu zeolite tự nhiên được biến tính bằng muối ăn (Z-Na) là một hướng nghiên cứu mới, được các nhà khoa học rất quan tâm. Kết quả thí nghiệm cho thấy, tại pH 6 thì hiệu quả xử lí amoni trong nước là tốt nhất. Hiệu quả xử lí amoni trong nước tăng rất nhanh trong 5 phút đầu tiên xử lý. Càng tăng nồng độ Z-Na thì hiệu quả xử lí amoni càng cao. Với dung dịch nước ban đầu có nồng độ amoni tính theo nitơ (N-NH4 +) nhỏ hơn 27 mg/L và nồng độ vật liệu Z-Na sử dụng là 13g/L thì nước sau xử lí có nồng độ nhỏ hơn 1mg N-NH4 +/L, đạt QCVN 09-MT:2015/BTNMT, hiệu suất xử lí đạt 96,30%, dung lượng hấp phụ cực đại đạt 2,07 mg NNH4 +/1g Z-Na. Vật liệu Z-Na sau khi xử lý được nghiên cứu giải hấp bằng dung dịch NaOH với nồng độ 2g/L cho thấy hiệu quả giải hấp đạt 92% lượng amoni được hấp phụ. Điều này chứng tỏ khả năng tái sử dụng của vật liệu Z-Na cho hấp phụ amoni là khá cao. Kết quả nghiên cứu đã được thử nghiệm xử lý với mẫu nước ngầm tại huyện Phú Xuyên, Hà Nội có nồng độ N-NH4 + là 53 mg/L. Vì vậy, vật liệu Z-Na hoàn toàn có thể ứng dụng vào thực tiễn để xử lý amoni trong nước ngầm rất an toàn, dễ thực hiện và hiệu quả cao.

M. Tech. (Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology / Acid mine drainage (AMD) is a serious problem associated with mining activities, and it has the potential to contaminate surface and ground water. The aim of this study was to evaluate the performance of constructed wetland and photocatalysis in treating AMD. Three identical unvegetated upflow constructed wetlands packed with natural zeolite (clinoptilolite) and coarse silica sand were made of a cylindrical plastic pipe, and the slurry photocatalyst was prepared using quartz material. A hydro-alcohol thermal method was used to prepare an anatase core-void-shell TiO2 photocatalyst. The results showed that the three unvegetated upflow constructed wetlands (CW) had relatively similar percentage removal of heavy metals despite their varying concentrations within the AMD. The removals were: Fe (86.54 - 90.4%); Cr (56.2 - 64.5%); Mg (56.2 - 67.88%); Ca (77.1 - 100%); and 100% removal was achieved for Be, Zn, Co, Ni, and Mn. The removal of sulphate was also 30%. Heavy metals concentration in CW packing material was significantly higher in the outlet of the constructed wetlands than in the inlet. The adsorption isotherms revealed that the experimental data fitted the Langmuir Isotherms better, which suggested a monolayer coverage of heavy metals on the surface of the adsorbents; thermodynamic studies showed that the nature of adsorption taking place was physical; the kinetics models showed that the adsorption was first order reaction. A higher photocatalytic reduction (62%) of Cr(VI) was obtained at pH 2, 30 mg/l Cr(VI) initial concentration, and three hours of irradiation time. It was also found that the presence of Fe(III) enhanced the reduction of Cr(VI). The core-void-shell TiO2 photocatalyst showed a better activity than the commercial P25 Degussa for the reduction of Cr(VI) to Cr(III). The kinetic studies showed that the reduction of Cr(VI) was first order reaction. Photocatalytic reduction of Cr(VI) in real AMD sample was achieved only for the Douglas North Discharge (DND) sample (68%), and the Fe(III) reduction was found to be 83%. Therefore it was concluded that the combination of constructed wetland and UV/ TiO2 photocatalysis employing anatase core-void-shell TiO2 as a photocatalyst has a potential to reduce the toxicity of Cr(VI)-laden acid mine drainage.