Zeolite beta has been synthesized using hydrothermal methods. In order to synthesize zeolite beta an aqueous gel having a molar batch composition of 2.2 Na2O&amp / #8729 / Al2O3&amp / #8729 / x SiO2&amp / #8729 / 4.6 (TEA)2O&amp / #8729 / 444 H2O was utilized. The synthesis parameters were SiO2/Al2O3 ratio (20 &amp / #8804 / x &amp / #8804 / 50) and crystallization time (6 &amp / #8804 / t &amp / #8804 / 16 days). Pure zeolite beta was crystallized from the experiments which were performed with the batch composition having SiO2/Al2O3 of 20 and 30 in 6 to 16 days period. For SiO2/Al2O3 of 20 and 30, the highest yield was obtained for 12 days. Therefore, the rest of the experiments, in which SiO2/Al2O3 was 40 and 50, were carried out keeping the synthesis time constant (12 days). Pure zeolite beta was also synthesized for SiO2/Al2O3 of 40 and 50. The highest yield and the most crystalline zeolite beta sample were obtained from the experiment performed at SiO2/Al2O3 of 50 with a synthesis time of 12 days. The morphology and crystal size of the zeolite beta samples were identified by using scanning electron microscope (SEM). It was observed that, zeolite beta samples had spheroidal morphology with the crystal size of about 0.5 &amp / #956 / m. According to the thermogravimetric analyses (TGA), it was found that template molecules and moisture constituted nearly 18 % by weight of the zeolite beta samples. The surface area of the calcined zeolite beta sample was determined by N2 adsorption and was found to be 488 m2/g. Gravimetric sorption analyses yield that, the limiting sorption capacity of Na-Beta for methanol, ethanol, isopropanol and n-butanol at 0&deg / C was about the same with a value of 0.25 cm3/g. For o-xylene, m-xylene and p-xylene that value was 0.21 cm3/g, 0.22 cm3/g and 0.24 cm3/g, respectively.

In this work, zeolite Beta was synthesized experimentally in order to be used as filler in fuel cell membranes in order to assess the proton conductivity of composite membranes. Effects of the Si/Al ratio, and synthesis time on yield, relative crystallinity, crystal size, and proton conductivity were investigated. Zeolite Beta with Si/Al ratio between 10 and 30 was synthesized with a batch formulation of 2.2Na2O:1Al2O3:ySiO2:4.6(TEA)2O:tH2O (where TEA&amp / #8801 / tetraethylammonium) at 150&deg / C for 5-15 days of synthesis time. Sodium aluminate, tetraethylammonium hydroxide (TEAOH) solution, sodium hydroxide pellets (NaOH), and deionized water were used for the preparation of the batch solution. Zeolite Na-Beta was calcined and treated with sulfuric acid solution at different concentrations in order to have zeolite H-Beta. Polyetherether ketone (PEEK) was sulfonated in order to have a proton conductive membrane and than zeolite H-Beta was incorporated resulting in a composite or nanocomposite membrane. X-ray diffraction (XRD) analysis helped to understand whether the synthesized material was zeolite Beta or not. The morphology and the crystal size of the crystals were observed as a result of the scanning electron microscopy (SEM) analysis. In order to see the effect of sulfuric acid treatment on the sodium (Na) content of the zeolite Beta, inductively coupled plasma (ICP) analysis was performed. Synthesis results indicate that as Si/Al ratio and synthesis time increased the yield of zeolite Beta increased. It was observed that Si/Al ratio from 10 to 30, and synthesis time between 5 to 15 days did not affect the crystal size significantly. For the sulfonation of PEEK, sulfuric acid was used. Sulfonated polyetherether ketone (SPEEK) was dissolved in a solvent that was dimethyl acetamide (DMAC), incorporated with zeolite Beta, and then solvent was removed in the vacuum oven. The proton conductivity was measured with a 2-probe impedance spectrometer. Initial results indicate that zeolite Beta at 10 and 20 wt % loadings did not affect the proton conductivity of the SPEEK membrane at 100 % relative humidity and room temperature.

Made available in DSpace on 2014-12-17T15:42:09Z (GMT). No. of bitstreams: 1 AnaCRM_TESE.pdf: 3734770 bytes, checksum: 59720290841ee6807d60b116e21f2090 (MD5) Previous issue date: 2010-12-06 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Microporous materials zeolite type Beta and mesoporous type MCM-41 and AlMCM-41 were synthesized hydrothermally and characterized by methods of X-ray diffraction, Fourier transform infrared, scanning electron microscopy, surface acidity, nitrogen adsorption, thermal analysis TG / DTG. Also we performed a kinetic study of sunflower oil on micro and mesoporous catalysts. The microporous material zeolite beta showed a lower crystallinity due to the existence of smaller crystals and a larger number of structural defects. As for the mesoporous materials MCM-41 and AlMCM-41 samples showed formation of hexagonal one-dimensional structure. The study of kinetic behavior of sunflower oil with zeolite beta catalysts, AlMCM-41 and MCM-41 showed a lower activation energy in front of the energy of pure sunflower oil, mainly zeolite beta. In the thermal cracking and thermocatalytic of sunflower oil were obtained two liquid fractions containing an aqueous phase and another organic - organic liquid fraction (FLO). The FLO first collected in both the thermal cracking as the thermocatalytic, showed very high level of acidity, performed characterizations of physicochemical properties of the second fraction in accordance with the specifications of the ANP. The second FLO thermocatalytic collected in cracking of sunflower oil presented results in the range of diesel oil, introducing himself as a promising alternative for use as biofuel liquid similar to diesel, either instead or mixed with it / Os materiais microporosos tipo ze?lita beta e mesoporosos tipo MCM-41 e AlMCM-41 foram sintetizados hidrotermicamente e caracterizados pelos m?todos de difra??o de raios X, infravermelho por transformada de Fourier, microscopia eletr?nica de varredura, acidez superficial, adsor??o de nitrog?nio, an?lise t?rmica via TG/DTG. Ainda foi realizado um estudo do comportamento cin?tico termogravim?trico do ?leo de girassol sobre os catalisadores micro e mesoporosos citados. Usando curvas integrais da TG e o m?todo cin?tico de Vyazovkin, foram estimados a energia de ativa??o, as taxas de convers?o e o tempo degrada??o do ?leo em fun??o da temperatura. O material microporoso ze?lita beta apresentou menor cristalinidade, devido ? exist?ncia de cristais menores e um maior n?mero de defeitos estruturais. Quanto aos materiais mesoporosos MCM-41 e AlMCM-41 apresentaram amostras com forma??o da estrutura hexagonal unidimensional. O estudo do comportamento cin?tico do ?leo de girassol com os catalisadores ze?lita beta, AlMCM-41 e MCM-41, mostrou uma menor energia de ativa??o frente a energia do ?leo de girassol puro, principalmente a ze?lita beta. No craqueamento t?rmico e termocatal?tico do ?leo de girassol foram obtidas duas fra??es l?quidas contendo uma fase aquosa e outra org?nica fra??o l?quida org?nica (FLO). A primeira FLO coletada, tanto no craqueamento t?rmico quanto no termocatal?tico, apresentou ?ndice de acidez muito elevado, sendo assim foi realizada as caracteriza??es das propriedades f?sico-qu?micas da segunda fra??o de acordo com as especifica??es da ANP. As segundas FLOs coletadas no craqueamento termocatal?tico do ?leo de girassol apresentaram resultados na faixa adequada ao diesel de petr?leo, apresentando-se como uma alternativa promissora para utiliza??o como biocombust?vel l?quido similar ao diesel, seja em substitui??o, ou misturado a este

Submitted by Kátia Oliveira (katiadionisio@yahoo.com.br) on 2017-10-11T14:01:46Z No. of bitstreams: 1 Tese (Oliveira, KD).pdf: 7712617 bytes, checksum: c39a9ee83f33d05d99d354f6a524019f (MD5) / Rejected by Ronildo Prado (producaointelectual.bco@ufscar.br), reason: Faltou inserir a carta de aprovação on 2017-10-11T18:32:06Z (GMT) / Submitted by Kátia Oliveira (katiadionisio@yahoo.com.br) on 2017-10-11T18:41:31Z No. of bitstreams: 2 Tese (Oliveira, KD).pdf: 7712617 bytes, checksum: c39a9ee83f33d05d99d354f6a524019f (MD5) Carta comprovante.pdf: 149973 bytes, checksum: 67927f9413f2368fa8bac2ceb19f248d (MD5) / Approved for entry into archive by Ronildo Prado (bco.producao.intelectual@gmail.com) on 2018-01-18T18:52:09Z (GMT) No. of bitstreams: 2 Tese (Oliveira, KD).pdf: 7712617 bytes, checksum: c39a9ee83f33d05d99d354f6a524019f (MD5) Carta comprovante.pdf: 149973 bytes, checksum: 67927f9413f2368fa8bac2ceb19f248d (MD5) / Approved for entry into archive by Ronildo Prado (bco.producao.intelectual@gmail.com) on 2018-01-18T18:52:44Z (GMT) No. of bitstreams: 2 Tese (Oliveira, KD).pdf: 7712617 bytes, checksum: c39a9ee83f33d05d99d354f6a524019f (MD5) Carta comprovante.pdf: 149973 bytes, checksum: 67927f9413f2368fa8bac2ceb19f248d (MD5) / Made available in DSpace on 2018-01-18T19:04:18Z (GMT). No. of bitstreams: 2 Tese (Oliveira, KD).pdf: 7712617 bytes, checksum: c39a9ee83f33d05d99d354f6a524019f (MD5) Carta comprovante.pdf: 149973 bytes, checksum: 67927f9413f2368fa8bac2ceb19f248d (MD5) Previous issue date: 2012-09-14 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / This work aimed to apply the Design Of Experiment (DOE) methodology as an auxiliary tool to evaluate the conditions of synthesis of the aluminum-rich zeolite Beta. Bimetallic catalysts with 50% platinum and 50% nickel (50Pt50Ni) supported on zeolites with various Si/Al ratios were synthesized, characterized and evaluated in the isomerization of n-hexane. In the first part of this work, five variables related to the synthesis of zeolite Beta were evaluated by a series of statistical designs, in which the response variables were the relative intensities of the X-ray patterns and the yield of phase BEA. The results of the t-test showed that the ratio TEAOH/SiO2 is not significant for the formation and crystallization of zeolite Beta. However, the interaction of this variable with the Si/Al ratio was statistically significant. In order to obtain the aluminum-rich zeolite Beta, the samples were synthesized with partial substitution of cations TEA+ by cations Na+. The XRD patterns of these samples showed that BEA phase was formed using a Si/Al ratio of 5,0 and 7.5. These low values of Si/Al ratio were confirmed by inductively coupled plasma atomic emission spectroscopy (ICP-AES) and energy-dispersive X-ray spectroscopy (EDS). Information about the main properties of the 50Pt50Ni catalysts such as activity, conversion and selectivity to di-branched isomers in the isomerization of n-hexane were obtained by performing catalytic tests. Concerning these properties, the catalysts supported on the synthesized zeolite Beta (Si/Al = 7.5) showed better catalytic performance compared with catalysts supported on commercial zeolite Beta (Si/Al = 9.0). Additionally to these tests, a study on the kinetics of reduction of ions Pt2+ and Ni2+ on these catalysts was conducted using X-ray absorption spectroscopy (XAS). The combination of XAS analysis and catalytic tests showed the importance of maintaining a bimetallic platinum and nickel system in order to obtain satisfactory performance of catalysts applied to the isomerization of n-hexane. The XAS results suggested that Pt2+ ions are reduced in lower temperatures compared to Ni2+ ions, and that the addition of platinum to the nickel-based samples promoted the reduction of Ni2+ ions. The catalytic results suggested that equilibrium between acid and metal sites exists during the isomerization of n-hexane. The understanding of this equilibrium is of major importance to increase the yield and selectivity to di-branched isomers. / Este trabalho teve como objetivo a utilização da metodologia de planejamento experimental como uma ferramenta auxiliar para avaliar as condições de síntese da zeólita Beta rica em alumínio. Catalisadores bimetálicos com 50% de platina e 50% de níquel (50Pt50Ni) com teor de metal total de 130 μmol gcat-1 e suportados em zeólitas com diferentes razões Si/Al foram sintetizados, caracterizados e avaliados na reação de isomerização do n-hexano. Na primeira parte do trabalho, cinco variáveis da síntese da zeólita Beta foram avaliadas por uma série de planejamentos estatísticos, nos quais as variáveis respostas analisadas foram a intensidade de difração relativa dos difratogramas de raios X e o rendimento à fase BEA obtida. Os resultados obtidos a partir do teste t demonstraram que a razão TEAOH/SiO2 não foi significativa para o processo de cristalização e formação da zeólita Beta. No entanto, a interação desta variável com a razão Si/Al apresentou significância estatística. Para a obtenção da zeólita Beta rica em alumínio, amostras foram sintetizadas com a substituição parcial dos cátions TEA+ por cátions Na+. Nos difratogramas de raios X destas amostras foi possível identificar a fase BEA para valores de Si/Al de 5,0 e 7,5. Estes baixos valores de Si/Al nas amostras sintetizadas foram confirmados pelas técnicas de espectroscopia por emissão de plasma indutivo (ICP) e análise dispersiva de raios X (EDS). Informações a respeito das principais propriedades dos catalisadores bimetálicos 50Pt50Ni tais como atividade, conversão e seletividade a isômeros birramificados na isomerização do n-hexano, foram obtidas através da realização de testes catalíticos. Com relação a estas propriedades, os catalisadores suportados na zeólita Beta sintetizada (Si/Al = 7,5) apresentaram melhores desempenhos catalíticos quando comparados aos catalisadores suportados na zeólita Beta comercial (Si/Al = 9,0). Paralelamente, um estudo sobre a cinética de redução dos cátions metálicos Pt2+ e Ni2+ destes catalisadores foi realizado através da técnica de espectroscopia de absorção de raios X (XAS). As análises de XAS aliadas aos resultados dos testes catalíticos sugeriram a importância de se manter um sistema bimetálico de platina e níquel de maneira a se obter um desempenho satisfatório dos catalisadores aplicados à isomerização do n-hexano. Os resultados de XAS sugeriram que temperaturas menores são necessárias para reduzir os cátions metálicos Pt2+ quando comparados aos cátions Ni2+, e que a adição de cátions Pt2+ contribui consideravelmente para a redução dos cátions Ni2+, diminuindo a temperatura de redução deste último. Os resultados apresentados neste trabalho sugeriram a existência de um equilíbrio entre a proporção de sítios ácidos e metálicos durante a isomerização do n-hexano e que o entendimento deste equilíbrio é de fundamental importância para se tentar aumentar o rendimento e a seletividade a isômeros birramificados. / CNPq: 141042/2008-7

De par leur morphologie, les cristaux creux de zéolithe permettent d’étudier les phénomènes de limitations diffusionnelles en catalyse et également d’encapsuler des particules métalliques ; les nano-réacteurs ainsi obtenus ont montré des activités catalytiques originales. Leur synthèse, qui nécessite des caractéristiques structurales particulières, a longtemps été limitée aux zéolithes de structure MFI. Le but de cette thèse était d’étudier différentes voies de synthèse pour préparer des cristaux creux de zéolithe Beta, une des zéolithes les plus utilisées dans l’industrie. Deux voies ont été suivies : l’utilisation d’un zincosilicate de même structure que la zéolithe Beta comme gabarit sacrificiel et une méthode plus classique de désilication sélective. L’encapsulation de nanoparticules de platine dans les cristaux obtenus selon la première voie a été confirmée par l’hydrogénation d’aromatiques substitués. L’’influence de la morphologie sur la diffusion de différentes molécules a été étudiée par ZLC : le temps caractéristique de diffusion a été réduit de 30 à 83 % par rapport à des cristaux conventionnels. Malgré cela, la présence d’une cavité dans les cristaux de zéolithe Beta n’a pas d’effets sur l’activité catalytique dans les réactions d’hydro-isomérisation du nC16 et du craquage du cyclohexane. La thèse discute de la présence/absence de limitations diffusionnelles / Hollow zeolite single crystals have received particular interest in catalysis. The presence of a large cavity in these model zeolites enables the study of diffusional limitation in Catalysis. The cavity also enables the encapsulation of metal nanoparticles. However, their synthesis requires specific structural characteristics and it has been limited for long to zeolites with the MFI structure. The objective of this PhD work was to investigate the synthesis of hollow Beta zeolites (*BEA framework type) and study the impact of the hollow morphology on molecular diffusion and catalysis. Two different strategies have been envisaged: a dissolution/recrystallization approach using CIT-6, a zincosilicate with the same *BEA topology and a selective desilication route. Pt nanoparticles encapsulated in hollow crystals obtained from CIT-6 showed remarkable size-selectivity in the hydrogenation of aromatics. The effect of the hollow morphology in molecular diffusion was studied using the ZLC technique; the characteristic diffusion time of the hollow morphology was reduced by 30-83% compared to the corresponding bulk zeolite. Despite that, the hollow structure had no influence on the catalytic activities for the hydroisomerization of n-C16 and for the cracking of cyclohexane. The presence/absence of diffusional limitation is discussed