ZSM-5 is an aluminosilicate zeolite with high Si/Al ratio with suitable properties for catalysis, ion exchange, adsorption and membrane applications. The main goal of this thesis was to study the growth of ZSM-5 zeolite crystals from inexpensive natural sources of silica and alumina, as well as n-butylamine (NBA) as a low-cost structure directing agent. The first objective of this work was to develop pathways to synthesize ZSM-5 crystals from kaolin clay or diatomaceous earth, two inexpensive natural sources of silica and alumina (Paper I). In the case of kaolin, a heat treatment was used in order to form amorphous metakaolinite. Subsequently, dealumination of the raw materials by acid leaching made it possible to reach appropriate Si/Al ratios and to reduce the amount of impurities. Finally, leached metakaolinite or diatomaceous earth was reacted with sodium hydroxide and NBA. After synthesis optimization, both sources of aluminosilicates were found to behave differently during the course of synthesis and to lead to slightly different reaction products. The final products exhibited Si/Al ratios in the range 10-20. The use of leached diatomaceous earth allowed to reach higher yield of ZSM-5 crystals within comparable synthesis times. However, low amounts of mordenite were inevitably formed as a by-product, which was related to the high calcium content of diatomaceous earth. Therefore, the rest of the thesis focused on the kaolin system. In order to study the growth mechanism of ZSM-5 from leached metakaolinite, a proper methodology to gain local compositional data by energy dispersive spectroscopy (EDS) on aluminosilicates was developed (Paper II). Zeolite A was used as a model system that could be ion-exchanged with various elements. In order to evaluate the reliability of the measurements, inductively coupled plasma-sector field mass spectrometry (ICP-SFMS) and EDS were compared. The EDS method developed in this work resulted in molar ratios very close to theoretical values and was therefore found more reliable than ICP-SFMS. Therefore, the method developed for zeolite A was applied in the rest of the thesis work to study the formation and growth of ZSM-5 crystals. The second part of this work focused on the kaolin system in order to understand the nucleation and growth processes of the ZSM-5 crystals. This system was heterogeneous, due to the formation of a gel upon heating of the synthesis mixture. First, the internal structure of the gel was investigated (Paper III). Second, a kinetic study was performed and compared with microstructural observations (Paper IV). Finally, the mechanisms leading to Al-zoning and dendritical growth of the zeolite crystals were investigated (Paper V). The characterization of the intermediate phases during the different stages of the hydrothermal synthesis were analyzed by different analytical techniques, such as inductively coupled plasma-sector field mass spectrometry (ICP-SFMS), dynamic light scattering (DLS), extreme high resolution-scanning electron microscopy (XHR-SEM), energy dispersive spectroscopy (EDS), high resolution-transmission electron microscopy (HR-TEM), X-ray diffraction (XRD) and nitrogen gas adsorption. These investigations led to several important conclusions: 1) The walls of the gel were shown for the first time to be inhomogeneous and to possess a biphasic internal structure consisting of a mesoporous skeleton of aluminosilicate nanoparticles embedded in a silicate-rich soluble matrix of soft matter. 2) The kinetic study and microstructural evidences indicated that the early crystals were fully embedded inside the gel phase and that crystal growth was retarded, as the formation of the gel occurred simultaneously with the early growth of the crystals. Hence, nucleation and growth appeared to be solution mediated.  3) Finally, the Al zoning of the crystals was related to the biphasic internal structure of the gel, since the silicate-rich matrix was preferentially consumed first. 4) The dendrites present at the surface of the crystals during most of the growth process were shown to be caused by the presence of a web of nanoparticles, most likely originating from the mesoporous skeleton inside the gel. In the future, these findings are expected to lead to optimized synthesis pathways of catalysts with homogeneous properties and to contribute to the development of poor regions in Bolivia.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / This work aims the synthesis and study of ZSM-5 catalysts for the conversion of ethanol to light olefins, especially, using an alternative and inexpensive route. The ethanol emerges as a renewable source for the production of olefins and the ZSM-5 catalyst has important characteristics for this type of reaction such as acidity, surface area and particle size. The synthesis was carried out in hydrothermal treatment at 170 °C. Were performed two conventional synthesis with templates, using n-Butylamine and tetrapropylammonium hydroxide (TPAOH), and an third and alternative route using a nucleating gel. The catalyst characterization was performed using several techniques (XRD, BET, XRF, SEM and TGA) and was observed the formation of the ZSM-5 structure in all the synthesis methods. The catalysts were evaluated in the ethanol to olefins (ETO) reaction, and was evaluated the influence of the reaction temperature (250 to 450 °C) and SAR (SiO2/Al2O2 ratio) in the selectivity for olefins. The products analyses were made with a gas chromatograph with a FID-type detector. The ethylene yield was above to 80 % for all catalysts, and some above 90 %. Lower SAR values provided higher yields for propylene, around to 9 %. The temperature, SAR and template used in the synthesis influenced in the selectivity. In addition, was evaluated the influence of the catalyst mass, dilution and also its modification with different metals. When the mass was increase, the yield for propylene increased. The catalyst dilution with common sand provided, in some concentrations, greater propylene formation. The nucleating gel method showed to be a viable alternative for ZSM-5 synthesis and its use in the ETO reaction. / Este trabalho relata o estudo da síntese e caracterização de catalisadores ZSM-5 para seu posterior uso na reação de conversão de etanol para olefinas, especialmente utilizando uma rota alternativa mais econômica. O etanol surge como uma fonte renovável para a produção de olefinas e o catalisador ZSM-5 possui importantes características para esse tipo de reação, tais como acidez, área superficial e tamanho de partícula. A síntese foi conduzida de maneira hidrotérmica a 170 °C. Foram realizadas duas sínteses convencionais com direcionadores de estrutura, utilizando n-butilamina e hidróxido de tetrapropilamônio (TPAOH), e uma terceira rota alternativa utilizando um gel nucleante. A caracterização dos compostos sintetizados foi realizada com diversas técnicas (DRX, BET, FRX, MEV e TGA) sendo observada a formação da estrutura de ZSM-5 em todas as técnicas de síntese utilizadas. Os catalisadores foram avaliados na reação de conversão de etanol à olefinas (ETO) e foi avaliada a influência da temperatura de reação (250 a 450 °C) e SAR (SiO2/Al2O3 ratio) na seletividade das olefinas. A análise dos produtos formados foi realizada em um cromatógrafo a gás com detector tipo FID. O rendimento para eteno foi superior a 80 % em todos os catalisadores, sendo para alguns acima de 90 %. Baixos valores de SAR proporcionaram maiores rendimentos para propeno, em torno de 9 %. A temperatura, o valor de SAR e os direcionadores empregados na síntese influenciaram na seletividade. Também, foi avaliada a influência da quantidade de massa do catalisador, a diluição e também a modificação com diferentes metais (Ga, La, In) e um não metal (P). Quando a massa foi aumentada, o rendimento para propeno aumentou consideravelmente. A diluição com areia comum, em algumas concentrações, proporcionou maior formação de propeno. O método de síntese via gel nucleante mostrou ser uma alternativa viável para a síntese de ZSM-5 e seu uso como catalisador na reação ETO.

<p>This thesis presents methods for air sampling and determination of isocyanates, amines, aminoisocyanates and anhydrides. These organic compounds are generated during thermal degradation of polymers such as polyurethane (PUR) or epoxy.</p><p>Isocyanates, amines and anhydrides are airway irritants known to cause occupational asthma. Some of the compounds are listed as human carcinogens. Many workers are exposed.</p><p>Isocyanates and anhydrides are reactive and needs to be immediately derivatized during sampling. Methods have been developed for determination of airborne isocyanates, aminoisocyanates and anhydrides using di-n-butylamine (DBA) as reagent to form stabile urea derivatives or amide derivatives. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) enabled detection limits as low as 10 attomoles. A nitrogen-selective LC-detector enabled quantification of DBA-derivatives in reference solutions. </p><p>A novel sampler is presented. The sampler consists of a denuder in series with a three-stage cascade impactor and an end filter. The sampler made it possible to reveal the distribution of isocyanates between gas and different particle size fractions. During thermal degradation of PUR, isocyanates were associated to particle size fractions (<1 µm) that may penetrate to the lower airways. The distribution during 8 minutes changes noticeably. Aromatic isocyanates become associated to small particles (<1 µm). As a reference method, air-sampling was performed using an impinger filled with di-n-butylamine (DBA) in toluene, connected in series with a glass fiber filter. There was a good agreement between the denuder-impactor sampler and the reference method.</p>

This thesis presents methods for air sampling and determination of isocyanates, amines, aminoisocyanates and anhydrides. These organic compounds are generated during thermal degradation of polymers such as polyurethane (PUR) or epoxy. Isocyanates, amines and anhydrides are airway irritants known to cause occupational asthma. Some of the compounds are listed as human carcinogens. Many workers are exposed. Isocyanates and anhydrides are reactive and needs to be immediately derivatized during sampling. Methods have been developed for determination of airborne isocyanates, aminoisocyanates and anhydrides using di-n-butylamine (DBA) as reagent to form stabile urea derivatives or amide derivatives. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) enabled detection limits as low as 10 attomoles. A nitrogen-selective LC-detector enabled quantification of DBA-derivatives in reference solutions. A novel sampler is presented. The sampler consists of a denuder in series with a three-stage cascade impactor and an end filter. The sampler made it possible to reveal the distribution of isocyanates between gas and different particle size fractions. During thermal degradation of PUR, isocyanates were associated to particle size fractions (&lt;1 µm) that may penetrate to the lower airways. The distribution during 8 minutes changes noticeably. Aromatic isocyanates become associated to small particles (&lt;1 µm). As a reference method, air-sampling was performed using an impinger filled with di-n-butylamine (DBA) in toluene, connected in series with a glass fiber filter. There was a good agreement between the denuder-impactor sampler and the reference method.