Zeolites are microporous hydrated aluminosilicate crystals containing alkali and/or alkali earth metal cations in their frameworks. Due to their molecular size pores, they can separate molecules according to their size and shape. Zeolites are mostly used in ion exchange, adsorption processes and catalytic applications. The hydrophilic/hydrophobic character of zeolites also makes them favorable materials for adsorption based separations. Recently the potential of zeolite/ceramic composite membranes have been shown in the separation of liquid and gas mixtures. Self-supported zeolite membranes with asymmetric structure can be an alternative to the composite zeolite membranes. Because asymmetric structure may eliminate the problems originated from the differences in thermal expansion coefficients of zeolites and ceramics. In this study tubular zeolite A membranes were prepared on binderless zeolite A supports. The supports were perepared by hydrothermal conversion of amorphous aluminosilicate tubes into zeolite A. The amorphous aluminosilicate powder, which was obtained by filtering the homogenous hydrogel with a composition of 2.5Na2O:1Al2O3:1.7SiO2:150H2O, was mixed with an organic binder (HEC-Hydroxyethyl Cellulose) and water to obtain the paste. The paste was then extruded through a home-made extruder into bars and tubes. These extrudates were dried at room temperature for 24 hours, calcined at 600oC for 2 hours to remove organic binder and finally synthesized at 80oC for 72 hours in hydrothermal conditions to convert amorphous aluminosilicate to zeolite. The effect of composition of the synthesis solution on the crystallinity and morphology of zeolite A tubes and bars were investigated. The crystallization field of zeolite A bars has been established and shown on a ternary phase diagram. Tubes were mechanically stable, typically had a crystallinity over 90% and a macroporosity of 35%. The tubes were composed of highly intergrown crystals of zeolite A. The average particle size was 3.5 &micro / m. The asymmetric membranes were synthesized by growing zeolite A films on binderless zeolite A supports with a geometry of disk, bar and tube. Continuous zeolite A films can only be obtained when the supports were saturated with water prior to synthesis. The film thicknesses were approximately 5 &micro / m on disks and approximately 10 &micro / m on tubes. A method was proposed to prepare self-supported tubular zeolite A membranes in this study.

This dissertation investigates the possibility of producing zeolites from municipal solid waste ash, MSW ash, by using hydrothermal treatment alone and by introducing fusion at 550 °C prior to hydrothermal treatment. The study was performed at different treatment conditions where silica/aluminum ratio of 13.9 and 2.5, hydroxide concentrations of 1.5N, 2.5N and 3.5N, temperatures at 100°C and 60 °C and time at 6, 24 and 72 hours were the major variables used to study zeolites synthesis process. The possibility of forming zeolites A, P1 and X was of particular interest in the present study. Factors, mechanism and modeling of zeolite A were investigated thoroughly in the present study. Zeolite synthesis process was evaluated using X-Ray diffraction to study different formed zeolite types and their chemical composition as well as their percentages. Morphological and physical characteristics of the produced zeolitic materials were evaluated by scanning electron microscopy, and cation exchange capacity property, CEC.The findings indicate that hydrothermal process did not succeed in producing significant amounts of zeolites. Consequently, the CEC of the produced zeolitic materials were much below the available commercial zeolite materials.Fusing the ash prior to hydrothermal treatment successfully produced sodium aluminum silicates and sodium silicates precursors to zeolite A formation. Fusion followed by hydrothermal treatment yielded significant amounts of zeolite A, at maximum value of 38.8% with CEC up to 245.0 meq/100g, which is within the range of commercially available zeolites. Experimental design analysis performed on zeolite A synthesis showed that zeolite A formation was reproducible and equation of interaction between different used conditions was established. Mechanism of zeolite A formation was concluded to be solution transport mediated process that involved both gel and solution interaction rather than being pure solution reaction or pu re gel transformation process. Solution super saturation and optimum silica/aluminum ratio were the driving force for nucleation of zeolite A.

Zeolites are highly porous materials that are most commonly used in granular or beaded forms. In general, zeolite granules, beads or monoliths are manufactured by using an inorganic binder which helps to cement zeolite crystals together. However, this inorganic binder decreases the purity of the zeolite structures and accessibility to the zeolite pores. A new and relatively easy method was offered for the production of binderless zeolite A tubes and bars from amorphous alumina silicate extrudates in this study. Amorphous alumina silicate powder, which is obtained by filtering the homogenous hydrogel with a composition of 2.5Na2O:1Al2O3:1.7SiO2:150H2O, is mixed with an organic binder (HEC-Hydroxyethyl Cellulose) to obtain the paste. The paste is then extruded through a die of a home-made extruder into bars and tubes. These extrudates were dried at room temperature for 24 hours, then calcined at 600oC for 2 hours and finally synthesized at 80oC for 72 hours in hydrothermal conditions to convert amorphous alumina silicate to zeolite. The most appropriate amorphous alumina silicate powder (A) / 4wt% HEC solution (H) ratio to prepare paste, hence to prepare bars and tubes was found as 0.82. The crystallinity of bars and tubes was 91% and 97%, respectively, and zeolite A was the only crystalline material. The bars and tubes were composed of highly intergrown zeolite A crystals with high porosity. Porosity of the bars is approximately 39% and porosity of the tubes is 29%, with a narrow pore size distribution. Bars have macropores of 2 &amp / #956 / m, while the macropores of the tubes are 3-4 &amp / #956 / m. The BET surface area of the bars was 411 m2/g and of tubes was 439 m2/g, which are comparable with the commercial zeolite A beads. Bars had a crushing strength of 0.42 MPa, which is sufficiently high to handle. In conclusion, zeolite A bars and tubes, with their high purity, macroporous structure and high mechanical strength, can be used in adsorption and ion exchange processes. The developed synthesis method can be scaled up to prepare honeycomb monoliths that provide higher surface are per unit volume with an appropriate extruder die.

Zeolites and zeolite membranes are two important advanced chemical materials which are widely used in chemical processes. The manufacture of these materials usually involves the use of expensive chemicals. This study involves the use of Ahoko Nigerian kaolin (ANK) as precursor material for the development of zeolites and zeolite membranes. The synthesis of zeolite A, Y and ZSM-5 was successfully obtained following a sequence, collection of the raw clay from Nigeria, metakaolinization, dealumination and actual hydrothermal synthesis of the zeolites. Raw ANK was refined using sedimentation technique and about 97% kaolin was recovered from the raw sample. A novel metakaolinization technique was developed to convert kaolin into a reactive metastable phase. Amorphous metakaolin was obtained at a temperature of 600°C and exposure time of 10 min. This is a significant result because previous studies use higher temperatures and longer exposure times for the metakaolinization step. The metakaolin was used to prepare a number of different zeolites under various conditions. Highly crystalline zeolite A was obtained at an ageing time of 12 h, crystallization time of 6 h and crystallization temperature of 100oC. Zeolite Y was obtained at an ageing time of 3 h, crystallization time of 9 h and crystallization temperature of 100oC. Zeolite Y was also synthesised by using a dealuminated kaolin and highly crystallized zeolite Y with Si/Al ratio of 1.56 and BET surface area was obtained of 630 m2/g. ZSM-5 was synthesised using an ageing period of 36 h, crystallization time of 48 h and temperature of 140oC. The results obtained from zeolite powder synthesis from ANK were then used as guide to prepare supported zeolite films and membranes by a hydrothermal method. The effect of the support surface (stainless steel) was investigated using two synthesis methods namely modified in-situ and secondary (seeded) growth. Zeolite A, Y and ZSM-5 films were successfully prepared from ANK for the first time and on two modified supports, etched and oxidised. The zeolite films and membranes developed showed complete coverage on the two supports with the oxidised showing better adhesion and intergrowth. The separation performance of the three developed zeolite membrane was tested by pervaporation of water/ethanol mixture. The results of pervaporation of ethanol/water mixture showed that zeolite A membrane is highly selective towards water mainly because of hydrophilic properties occasioned by the high aluminium content. Zeolite Y membrane show a similar response when their separation performance was evaluated but with less selectivity because of reduced aluminium content. ZSM-5 showed selectivity towards ethanol because of it hydrophobicity allowing only ethanol to permeate. In all the zeolite membranes, the flux is lower in comparison to commercial zeolite membranes due mainly to the thickness of the zeolite layer. Oxidised support membranes showed better performance because of their better interaction between the oxide surface and the aluminosilicate gel. The results show that ANK can successfully be used to prepare zeolites and zeolite membrane.

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Dehydroaromatization of methane (MDA) reaction was investigated over platinum modified Mo/H-ZSM-5 catalysts which were pre-carbided at 750 oC. The influence of platinum on the catalytic performance and product selectivity of Mo/H-ZSM-5 catalysts for the MDA reaction at 700 oC was studied. The presence of platinum led to a slight decrease in methane conversion. As the platinum loading increased, the methane conversion decreased further and the catalytic stability increased with time-on-stream (TOS) during the MDA reaction. Aromatic selectivities above 90% were obtained with catalysts containing low platinum loadings (0.5 and 1.0 wt.%), with benzene being the most prominent product. A decrease in coke selectivity and coke deposits was noted with the platinum modified Mo/H-ZSM-5 zeolite catalysts. A comparative study was performed to compare platinum, palladium and ruthenium promoted Mo/H-ZSM-5 zeolite catalysts with un-promoted Mo/H-ZSM-5. The ruthenium promoted catalyst proved to be superior in catalytic performance, with a higher methane conversion obtained than found for platinum promoted and palladium promoted Mo/H-ZSM-5 catalysts. Benzene selectivity of about 60% was obtained for ruthenium and palladium promoted Mo/HZSM- 5 catalysts and the total aromatic selectivity was maintained at 90%. TGA results showed a total reduction of 50% by weight of carbon deposited on the promoted Mo/H-ZSM-5 catalyst. Dehydroaromatization of methane was studied over tin modified Pt/Mo/HZSM-5 catalysts and compared to Pt/Mo/H-ZSM-5 catalyst at 700 oC. Addition of tin decreased the activity towards methane aromatization. However, the formation of aromatic compounds was favoured. The CO FT-IR adsorption and CO chemisorption techniques showed that the catalyst preparation method had an effect on the catalytic performance of tin modified Pt/Mo/H-ZSM-5 catalysts. High aromatic selectivity and low coke selectivity were obtained with co-impregnated and sequentially impregnated Pt/Sn catalysts. While a decrease in the formation rate of carbonaceous deposits is mainly dependent on the availability of platinum sites for the hydrogenation of carbon. The order of sequentially loading platinum and tin has an effect on the electronic and structural properties of platinum as shown by XPS and FT-IR studies. CO chemisorption and the FT-IR adsorption studies showed that addition of tin decreased the adsorption capacity of the platinum surface atoms. Catalyst preparation methods and successive calcination treatments affected the location of both tin and platinum atoms in the catalyst. Catalysts prepared by the coimpregnation method showed a good platinum dispersion, better than found for the sequentially impregnated catalysts. The MDA reaction was carried out at 800 oC over manganese modified H-ZSM-5 zeolite catalysts prepared by the incipient wetness impregnation method. The effect of a number of parameters on the catalytic performance and product selectivity was investigated, such as reaction temperature, manganese precursor-type, tungsten as promoter, manganese loading and use of noble metals. The study of the effect of reaction temperature showed that the methane conversion increased linearly with increase in reaction temperature from 700 to 850 oC. The selectivity towards aromatic compounds (of about 65%) was attained for the reactions performed at 750 and 800 oC. Formation rate of carbonaceous deposits increased linearly with increase in reaction temperature. The use of different manganese precursors to prepare Mn/H-ZSM-5 catalysts had an effect on both the catalytic behaviour and the product distribution. High catalytic activities were obtained for the catalysts prepared from Mn(NO3)2 and MnCl2 salts. However, the product distribution was significantly different, with the Mn(NO3)2 catalyst being more selective towards aromatic compounds while the MnCl2 catalyst was more selective toward coke. The effect of manganese loading was studied at 800 oC and an optimum catalyst activity was obtained at 2 and 4 wt.% manganese loadings. The aromatic selectivity above 70% and coke selectivity of 20% were obtained for a 2 wt.% loaded catalyst. Addition of tungsten as a promoter onto the 2 wt.% loaded catalyst (2Mn/H-ZSM-5) lowered the catalytic activity but the catalyst remained fairly stable with increase in TOS. Tungsten modified catalysts favoured the formation of carbonaceous deposits over aromatic compounds. TGA results showed a coke deposit of 164 mg/g.cat, an 88% increase in coke deposit when tungsten was used a promoter. Noble metals were added to reduce the total amount of coke on the tungsten modified Mn/H-ZSM-5 catalysts. The presence of a noble metal favoured the formation of aromatic compounds and suppressed the formation of coke. Platinum and ruthenium promoted catalysts were the active catalysts and aromatic selectivity increased from 12% to 55% and 46% respectively. A reduction in the total amount of coke deposit on the platinum promoted catalyst (42%) and the ruthenium promoted catalyst (31%) was noted.

The effective separation of ammonia from the synthesis loop in ammonia synthesis plants is an important step in its manufacture. This work presents the use of nanocomposite MFI zeolite membranes prepared by a pore-plugging method for this separation process. Performance of a zeolite membrane is highly dependent on the operating conditions. Therefore, the influences of differential pressure, temperature, sweep gas flow, feed gas flow and gas composition are studied experimentally. Transport of NH3 in this membrane is by surface diffusion in the intracrystalline (zeolite) pores in parallel with capillary condensation in the intercrystalline (non-zeolite) pores. The separation of NH3 from a mixture with H2 and N2 is by preferential adsorption of NH3, which hinders the permeation of weakly adsorbed H2 and N2. Differential pressure has only relatively small effects in the pressure range 300kPa – 1550kPa. Increase in sweep flow rate has little effect on NH3 gas permeance, but H2 and N2 permeances increase thereby decreasing the selectivities. Increase in feed flowrate also has little effect on NH3 permeance. However, the N2 and H2 permeances increase and there is a subsequent decrease in selectivities. Membrane performance was found to be highly dependent on temperature. NH3 permeance in the mixture increases linearly with temperature. NH3 selectivity was found to increase with temperature up to 353K after which it starts to decrease due to N2 and H2 permeances increasing with temperatures beyond 353K (αNH3/N2 = 46 and αNH3/H2 = 15) and is therefore the optimum temperature for separation. A potential barrier model is developed to describe the hindering effect of NH3 on H2 and N2 permeance. The model fails to predict correctly H2 and N2 permeances in the ternary mixture using pure gas (H2 and N2) permeances. Binary mixture permeation H2/N2 studies showed that there are diffusion effects (single file diffusion) that have not been taken into account in the potential barrier model. When permeances of the individual components in the binary mixture are used in the model instead of the pure gas permeances, there is an improved agreement between experimental and predicted results.

N-Nitrosodimethylamine (NDMA), which is a carcinogenic and toxic N-nitrosamine, can be found in water resources associated with a multitude of processes in various industrial facilities or merely as a by-product of water or wastewater treatment. Therefore, the removal of NDMA from drinking water represents an important human safety and public health concern. The present paper presents a density functional theory study of NDMA adsorption in all-silica MFI, Na-ZSM-5 and H-ZSM-5 zeolites. The stability of NDMA inside the zeolite pores was investigated by calculating the amount of energy released during adsorption. Various configurations of adsorbed NDMA to the zeolites were investigated, predominantly at the intersection of straight and sinusoidal channels. The strength of the adsorption energies followed the order H-ZSM5 > Na-ZSM-5 > all-silica MFI. NDMA has a dipole moment and the strongest binding of NDMA occurred through the interactions of the negatively charged O atom of the molecule to positive atoms of the zeolite. Similar calculations were performed for water adsorption in these three zeolites. The adsorption energy of water to these three structures followed the order Na-ZSM5 > H-ZSM-5 > all-silica MFI. We also incorporated van der Waals corrections in the simulations, which had the effect of stabilizing NDMA within the zeolite channels, but did not significantly change the relative stability of the different adsorption geometries. It was concluded that H-ZSM-5 is the best choice to remove NDMA because it is strong enough to adsorb NDMA and it is not too strong in adsorption of water molecules.

Philosophiae Doctor - PhD / Persistent root canal pathogens are one of the main causes of endodontic treatment failure. These pathogens are usually isolated in areas within the root canals that are inaccessible to mechanical instrumentation, chemical irrigants and medicaments resulting in incomplete sterilization of the root canal system. Furthermore, the development of resistant microbial species renders it difficult to disinfect the root canal system using commonly available root canal irrigants and intra-canal medicaments. Intra-canal medicaments are antimicrobial agents that are placed inside the root canal system in order to eliminate the remaining microorganisms that persist after mechanical instrumentation and irrigation. However, their antimicrobial efficacy is effective only against some of the root canal pathogens. Furthermore, the presence of tissue inhibitory factors such as dentine powder and serum albumine within the root canal system inhibits their antimicrobial activity. The use of nanoparticles as antimicrobial agents has recently attracted considerable attention especially in the medical field as a result of their unique antibacterial properties. These properties include their ability to use multiple mechanisms to eradicate microbial cells and their low potentiality to produce microbial resistance. Polymeric nanoparticles such as chitosan nanoparticles (Ch-Np) gained significant interest as a result of their biocompatible and antimicrobial properties. In medicine, several vehicles were designed to carry these antibacterial nanoparticles. Zeolites (Ze) are microporous crystalline hydrated sodium aluminosilicate material that is utilized in the chemical sciences as a carrier for various nanoparticles.