Excessive greenhouse gas emissions, like carbon dioxide, contribute to global warming and climate change. Methanol is hydrogenated from syngas and can react to produce hydrocarbons in a reaction known as methanol to hydrocarbons (MTH). Catalysts are vital in this reaction and are largely of zeolite origin. The zeolite typology, acidity, and reaction conditions donate the products produced and catalytic stability. Further, previous work shows increased catalytic stability and higher desired product selectivity when metal is incorporated onto the zeolite’s framework. We study the role of varying silica/alumina ratio (SAR) of beta zeolite via dealumination and incorporating titanium to understand their effect on product distribution, catalytic lifetime, and deactivation in the MTH reaction The samples maintained their structural integrity following the dealumination and metal incorporation. Techniques like XRD, N2 physisorption, ICP–OES, FTIR, and Raman spectroscopy are shown and discussed. They confirm the preservation of the zeolite structure following dealumination and metal incorporation. Pyridine-FTIR and ammonia TPD are used to understand the acidity character of the samples. Both show decreased acidity as the SAR increases. 27Al NMR and 1H NMR show the removal of extra framework 27Al as SAR increases and the presence of silanol nests in the dealuminated samples, respectively. A packed bed reactor in a PID setup with a UV-vis probe is used to test the catalytic activity and study the neutral and charged species formation, respectively. The catalytic activity results show a decrease in conversion as the SAR increases for the dealuminated samples. High propylene/ethylene ratio reaching up to 41.5 is observed for the 13M sample. Further, the UV-vis analysis shows the higher formation of bulkier hydrocarbons, like polyaromatics, as the reaction progresses. It is found that the parent sample deactivates quicker than the dealuminated samples as it presents stagnant UV-vis bands at the end of the reaction. The higher accumulation of polyaromatics and lower product formation of ethylene, in higher SARs, is related to the aromatic cycle hindrance and the dominance of the olefinic cycle products.

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.

The diesel engine is growing in popularity due to its energy efficiency and solving the emissions issues associated with diesel engine exhaust would clear the way for further growth. The key pollutants are NOx, particulate matter and unburned hydrocarbons. Selective catalytic reduction (SCR) catalysis is likely the best choice for NOx control. In SCR, NH3 selectively reacts with NOx to form N2 – the selectivity refers to NH3 reacting with NOx instead of the abundant O2. Urea is used as the NH3 source, being injected into the exhaust as an aqueous solution where the urea decomposes and NH3 is generated. Spatial resolution characterization techniques have been gaining attention in the catalysis field because of the higher level of information provided. In this thesis, a new spatial resolution technique, called SpaciFTIR (spatially-resolved, capillary-inlet Fourier transform infra-red spectroscopy), was developed, which overcomes the interference of water in the detection of NH3 in an earlier developed technique, SpaciMS (spatially-resolved, capillary-inlet mass spectrometry). With the new test method, three SCR topics were addressed. First, the three key SCR reactions were spatially resolved. These are the standard SCR reaction (2NO + 2NH3 + 1/2O2 = 2N2 + 3H2O), the fast SCR reaction (NO + NO2 + 2NH3 = 2N2 + 3H2O), and NO2-SCR, (6NO2 + 8NH3 = 7N2 + 12H2O). Results show that in the presence of NO2, but at a NO2/NOx ratio < 0.5, the fast SCR reaction proceeds followed by the standard SCR reaction, i.e. in series. If the NO2/NOx ratio exceeds 0.5, the NO2-SCR and fast SCR reactions occur in parallel. Compared to the standard integral test method, this spatial resolution technique clearly showed such trends. Secondly, the spatial resolution technique was used to characterize the effects of thermal aging on catalyst performance. It was found that for a highly aged catalyst, there was a radial activity profile due to an inhomogeneous temperature distribution in the process of aging. Aging effects on various key SCR reactions, i.e. NO oxidation, NH3 oxidation, and the reduction reactions, were studied. Last but not least, for the purpose of passive SCR system development, transient NH3 storage profiles along the monolith channel were measured with SpaciFTIR. Passive SCR is a system where the NH3 is generated on an upstream catalyst, such as a three-way catalyst or lean-NOx trap, instead of via urea injection. In such a system, NH3 is therefore not constantly being fed to the SCR catalyst, but “arrives” in pulses. Factors such temperature, NH3 concentration, pulsing time, flow rate and thermal aging were investigated. For the first time, NH3 migration was observed and its effect on SCR reactions along the length of catalyst was studied.

Zeolites are a well-known class of crystalline oxide materials with tunable compositions and nanoporous structures, and have been used extensively in catalysis, adsorption, and ion exchange. The zeolite MFI is one of the well-studied zeolites because it has a pore size and structure suitable for separation or chemical conversion of many industrially important molecules. Modification of zeolite structures with organic groups offers a potential new way to change their properties of zeolites, beyond the manipulation of the zeolite framework structure and composition. The main goals of this thesis research are to study the organic-modification of the MFI pore structure, and to assess the effects of such modification on the adsorption and transport properties of zeolite MFI sorbents and membranes. In this work, the internal pore structure of MFI zeolite particles and membranes has been modified by direct covalent condensation or chemical complexation of different organic molecules with the silanol defect sites existing in the MFI structure. The organic molecules used for pore modification are 1-butanol, 1-hexanol, 3-amino-1-propanol, 1-propaneamine, 1,3-diaminopropane, 2-[(2-aminoethyl)amino]ethanol, and benzenemethanol. TGA/DSC and 13C/29Si NMR characterizations indicated that the functional groups were chemically bound to the zeolite framework, and that the loading was commensurate with the concentration of internal silanol defects. Gas adsorption isotherms of CO2, CH4, and N2 on the modified zeolite materials show a range of properties different from that of the bare MFI zeolite. The MFI/3-amino-1-propanol, MFI/2-[(2-aminoethyl)amino]ethanol, and MFI/benzenemethanol materials showed the largest differences from bare MFI. These properties were qualitatively explained by the known affinity of amino- and hydroxyl groups for CO2, and of the phenyl group for CH4. The combined influence of adsorption and diffusion changes due to modification can be studied by measuring permeation of different gases on modified MFI membranes. To study these effects, I synthesized MFI membranes with [h0h] out-of-plane orientation on α-alumina supports. The membranes were modified by the same procedures as used for MFI particles and with 1-butanol, 3-amino-1-propanol, 2-[(2-aminoethyl)amino]ethanol, and benzenemethanol. The existence of functional groups in the pores of the zeolite was confirmed by PA-FTIR measurements. Permeation measurements of H2, N2, CO2, CH4, and SF6, were performed at room temperature before and after modification. Permeation of n-butane, and i-butane were measured before and after modification with 1-butanol. For all of the studied gases, gas permeances decreased by 1-2 orders of magnitude compared to bare MFI membranes for modified membranes. This is a strong indication that the organic species in the MFI framework are interacting with or blocking the gas molecule transport through the MFI pores. A detailed fundamental study of the CO2 adsorption mechanism in modified zeolites is necessary to gain a better understating of the adsorption and permeation behavior of such materials. Towards this end, an in situ FTIR study was performe.For the organic molecules with only one functional group (1-butanol, benzenemethanol, and 1-propaneamine), physical adsorption was found - as intuitively expected - to be the only observed mode of attachment of CO2 to the modified zeolite material. Even in the case of MFI modified with 1,3-diaminopropane, only physical adsorption is seen. This is explained by the isolated nature of the amine groups in the material, due to which only a single amine group can interact with a CO2 molecule. On the other hand, chemisorbed CO2 species are clearly observed on bare MFI, and on MFI modified with 3-amino-1-propanol or 2-[(2-aminoethyl)amino]ethanol. Specifically, these are carbonate-like species that arise from the chemisorption of CO2 to the silanol group in bare MFI and the alcohol groups of the modifying molecule. The possibility of significant contributions from external surface silanol groups in adsorbing CO2 chemisorbed species was ruled out by a comparative examination of the FTIR spectra of 10 μm and 900 nm MFI particles modified with 2-[(2-aminoethyl)amino]ethanol.

Zeolite A-type membranes are usually synthesized from hydrogels and rarely synthesized from clear solutions mostly in batch systems. Few studies were carried out using semi-continuous systems for zeolite A membrane synthesis. Zeolite A membranes are mainly used in pervaporation processes for separation of water from water/organic mixtures because of their hydrophilic property. In this study, zeolite A membranes were synthesized on -alumina supports from a clear solution with a molar composition of 49Na2O: 1Al2O: 5SiO2: 980H2O. Synthesis was done both in a batch system and in a flow system in which solution was circulated through the support under atmospheric pressure. Effects of synthesis temperature, time, flow rate and seeding on membrane formation were investigated. The membranes were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), single gas permeation measurements and pervaporation tests. In batch system, pure zeolite A membranes having cubic form of zeolite A was obtained for the syntheses carried out at 60&deg / C for 24 h and 80&deg / C for 8 h. Thicknesses of the membranes synthesized at 80&deg / C and 60&deg / C were about 2 &micro / m and 4 &micro / m, respectively. N2 permeances were 2*10-8 mol/m2sPa and 8*10-8 mol/m2sPa for of the membranes synthesized in the batch system at 60&deg / C and 80&deg / C, respectively. When synthesis was carried out in flow system pure and continuous zeolite A membranes were obtained for all conditions. Membranes synthesized at 60&deg / C and 80&deg / C had thicknesses of about 1.5 and 2 &micro / m, respectively. Lower N2 permeations were obtained for the membranes synthesized in flow system. It was observed that flow rate and seeding did not significantly affect the thickness of the membrane layer. The membranes synthesized in this study are significantly thinner than the membranes reported in the literature. Single gas permeation tests at 25&deg / C for the membranes showed that comparable membranes with the ones in literature were obtained in this study. For a double layer membrane synthesized in flow system at 80&deg / C for 8h separation factor about 3700 was obtained for the separation of 92:8 (wt.%) ethanol/water mixture at 45&deg / C.

Zeolites are microporous crystallines with well defined structures. Zeolites are used in variety of applications because of their properties such as high temperature stability, ion-exchange capacity, adsorption capacity and stability to harsh conditions. Some major applications of zeolites are ion-exchange, catalysis, adsorption and separation. Synthetic zeolites are normally produced as fine crystalline powder. Prior to their use, the powder is usually formed into spheres, tablets and extrudates by addition binder. Since binders present in the zeolite can block the pores and decrase the adsorption properties, preparation binderless zeolite agglomerates with high mechanical stability has great technological importance. Objective of the study is to synthesize binderless zeolite X tubular macrobodies by using the developed methods for the synthesis of zeolite A bars and tubes. Main steps of the study are synthesis of the tubular binderless zeolite X macrobodies, characterization of the macrobodies, determination the effect of hydrogel composition on zeolite phase and analyzing effect of time on the crystallinity of macrobodies. Experimental method for synthesizing the binderless tubular zeolite X macrobodies includes the following steps / preparing hydrogel by mixing sodium aluminate and sodium silicate solutions, filtration of the hydrogel, paste preparation from solid phase of the hydrogel, extrusion of green tubes from paste, calcination of green tubes and crystallization of calcined tubes in filtered liquid of the hydrogel. In this study, synthesis of binderless tubular pure zeolite X macrobodies with high crystallinity was achieved. Micropore volume and BET surface area of the zeolite X tubular macrobody I&Ccedil / S-18, which has 99.9 % crystallinity were determined as 0.178 cm3/g and 631.2 m2/g, respectively. Pure zeolite X, pure zeolite A and zeolite A, X mixtures were obtained after the crystallization of the calcined extrudates which were obtained from different hydrogel compositions. Ternary diagram which was based on the hydrogel compositions and the obtained zeolite phases was plotted.

Zeolite A membranes have great potential in pervaporation separation of ethanol/water mixtures with high flux and selectivity. Zeolite membranes usually synthesized from hydrogels in batch systems. In recent years, zeolite membranes are prepared in semicontinuous, continuous and recirculating flow systems to allow the synthesis of zeolite membranes with enlarged surface areas and to overcome the limitations of batch system at industrial level production. The purpose of this study is to develop a synthesis method for the preparation of good quality zeolite A membranes in a recirculated flow system from hydrogels and to test the separation performance of the synthesized membranes by pervaporation of ethanol/water mixture. In this context, three different experimental synthesis parameters were investigated with zeolite A membranes synthesized in batch system. These parameters were the composition of the starting synthesis hydrogel, silica source and the seeding technique. Syntheses were carried out using hydrogels at atmospheric pressure and at 95 &deg / C. The membranes were characterized by X-ray diffraction, scanning electron microscopy and pervaporation of 90 wt% ethanol-10 wt% water mixtures. v Pure zeolite A membranes were synthesized both in batch and flow systems. The membranes synthesized in batch system have fluxes around 0.2-0.3 kg/m2h and selectivities in the range of 10-100. Membranes with higher selectivities were obtained in batch system by using waterglass as silica source, seeding by dip-coating wiping method, and with a batch composition of 3.4Na2O:Al2O3:2SiO2:155H2O. The membranes prepared in flow system have higher pervaporation performances than the ones prepared in batch system in considering both flux and the selectivity. Fluxes were around 0.3-3.7 kg/m2h and selectivities were in the range of 102-104 for the membranes prepared in flow system which are comparable with the data reported in literature for batch and flow systems. A high quality zeolite A membrane was also synthesized from 3.4Na2O:Al2O3:2SiO2:200H2O hydrogel at 95 &deg / C for 17 hours in flow system. Pervaporation flux of this membrane was 1.2 kg/m2h with a selectivity &gt / 25,000 at 50&deg / C. Although the synthesis method is resulted with high quality membrane, reproducibility of the synthesis method is poor and it should be improved.

The diesel engine is growing in popularity due to its energy efficiency and solving the emissions issues associated with diesel engine exhaust would clear the way for further growth. The key pollutants are NOx, particulate matter and unburned hydrocarbons. Selective catalytic reduction (SCR) catalysis is likely the best choice for NOx control. In SCR, NH3 selectively reacts with NOx to form N2 – the selectivity refers to NH3 reacting with NOx instead of the abundant O2. Urea is used as the NH3 source, being injected into the exhaust as an aqueous solution where the urea decomposes and NH3 is generated. Spatial resolution characterization techniques have been gaining attention in the catalysis field because of the higher level of information provided. In this thesis, a new spatial resolution technique, called SpaciFTIR (spatially-resolved, capillary-inlet Fourier transform infra-red spectroscopy), was developed, which overcomes the interference of water in the detection of NH3 in an earlier developed technique, SpaciMS (spatially-resolved, capillary-inlet mass spectrometry). With the new test method, three SCR topics were addressed. First, the three key SCR reactions were spatially resolved. These are the standard SCR reaction (2NO + 2NH3 + 1/2O2 = 2N2 + 3H2O), the fast SCR reaction (NO + NO2 + 2NH3 = 2N2 + 3H2O), and NO2-SCR, (6NO2 + 8NH3 = 7N2 + 12H2O). Results show that in the presence of NO2, but at a NO2/NOx ratio < 0.5, the fast SCR reaction proceeds followed by the standard SCR reaction, i.e. in series. If the NO2/NOx ratio exceeds 0.5, the NO2-SCR and fast SCR reactions occur in parallel. Compared to the standard integral test method, this spatial resolution technique clearly showed such trends. Secondly, the spatial resolution technique was used to characterize the effects of thermal aging on catalyst performance. It was found that for a highly aged catalyst, there was a radial activity profile due to an inhomogeneous temperature distribution in the process of aging. Aging effects on various key SCR reactions, i.e. NO oxidation, NH3 oxidation, and the reduction reactions, were studied. Last but not least, for the purpose of passive SCR system development, transient NH3 storage profiles along the monolith channel were measured with SpaciFTIR. Passive SCR is a system where the NH3 is generated on an upstream catalyst, such as a three-way catalyst or lean-NOx trap, instead of via urea injection. In such a system, NH3 is therefore not constantly being fed to the SCR catalyst, but “arrives” in pulses. Factors such temperature, NH3 concentration, pulsing time, flow rate and thermal aging were investigated. For the first time, NH3 migration was observed and its effect on SCR reactions along the length of catalyst was studied.

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.

Made available in DSpace on 2014-12-17T14:07:07Z (GMT). No. of bitstreams: 1 AlexandreFMC_DISSERT.pdf: 2018035 bytes, checksum: dd77e9d37e80465172d8dc362ca0200a (MD5) Previous issue date: 2011-11-25 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The synthesis of zeolites from natural sources of silicon and aluminum are promising alternative routes to obtain porous or zeolite MCM family. Such materials are typically used in catalytic processes and / or adsorption is to obtain new products or for separation and purification processes thereof. Environmental legislation is becoming stricter and requires the use of materials more efficient, aiming to achieve pollution prevention, by gas or liquid contaminants in the environment. In order to obtain a material with environmentally friendly features, this study aimed at the synthesis of zeolite A, from an amorphous sediment, diatomite, which is found in abundance in the northeast region of Brazil, may be substituted for conventional products the production of zeolite, involving higher costs. The methodology for obtaining the "Zeolite A" using as a source of silica and alumina diatomite is simple, since this is a source of silicon, not requiring therefore a structural driver, but also by heat treatment, only drying conventional to remove water. The "zeolite A" was obtained from diatomite, but as an intermediate step we obtained the sodalite. The characterization was made by the following techniques: EDX, XRD, FT-IR, SEM and determining a specific area by the BET method and the BJH method for checking the diameter of pores. By characterization of the obtained material was first demonstrated the achievement of sodalite and after modification of the same, there was obtained zeolite A / A s?ntese de ze?litas a partir de fontes naturais de Sil?cio e Alum?nio s?o rotas alternativas promissoras para a obten??o de materiais porosos da fam?lia MCM ou ze?litas. Tais materiais normalmente s?o usados em processos catal?ticos e/ou adsortivos seja para obten??o de novos produtos ou para processos de purifica??o e separa??o dos mesmos. A legisla??o ambiental ? cada vez mais rigorosa e exige o uso de materiais cada vez mais eficientes, com intuito de realizar preven??o de polui??o, por gases ou a l?quidos contaminantes do meio ambiente. Visando a obten??o de um material com caracter?sticas ambientalmente corretos, esse estudo teve como objetivo a s?ntese de ze?lita A, a partir de um sedimento amorfo, diatomita, o qual ? encontrado em abund?ncia na regi?o nordeste do Brasil, podendo vir a substituir produtos convencionais para a produ??o de ze?lita, envolvendo custos mais altos. A metodologia utilizada para obten??o da ze?lita A usando como fonte de s?lica e alumina a diatomita ? simples, uma vez que esta ? uma fonte de sil?cio, n?o necessitando, portanto de um direcionador estrutural, como tamb?m de um tratamento t?rmico, apenas secagem convencional para retirada da ?gua. A ze?lita A foi obtida a partir da diatomita, por?m como etapa intermedi?ria obteve-se a sodalita. As caracteriza??es foram feitas pelas seguintes t?cnicas: EDX, DRX, FT-IR, MEV e determina??o de ?rea espec?fica pelo m?todo BET e o m?todo BJH para verifica??o do di?metro de poros. Atrav?s da caracteriza??o do material obtido comprovou-se primeiramente a obten??o da sodalita e ap?s modifica??o da mesma, obteve-se a ze?lita A