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Les zéolites, aluminosilicates cristallisés microporeux, sont largement utilisés en raffinage, en pétrochimie et en conversion de la biomasse. En raison du faible diamètre des micropores, limitations diffusionnelles et effets de confinement peuvent favoriser la formation de sous-Produits non désirés. L'introduction de mésopores par désalumination et/ou désilication ("zéolites hiérarchisées") peut diminuer ces phénomènes. Cependant, les mécanismes ces réactions restent méconnus à l'échelle moléculaire. Par calculs quantiques périodiques, au niveau de la théorie de la fonctionnelle de la densité (DFT) et selon une approche hybride QM/QM, nous avons pu mettre en évidence l'importance de l'attaque de la molécule d'eau sur l'atome d'aluminium, qui se fait en anti par rapport au site acide de Brønsted. Des structures d'Al penta ou tetra coordinées ont aussi été suggérées expérimentalement comme précurseurs de la désalumination. Malgré une forte hétérogénéité structurale des sites T, l'élucidation des chemins réactionnels et les énergies d’activation des étapes d’hydrolyse des liaisons Al-O (70-100 kJ/mol) dans les systèmes zéolitiques investigués (MOR, FAU, MFI, CHA) nous a permis d'établir des corrélations du type Brønsted-Evans-Polanyi. Ces corrélations permettent d'estimer et prédire des énergies d'activation par le biais de la thermodynamique, donne ainsi une prédiction aisée des sites T sensibles à la désalumination. Un autre facteur clé pour la compréhension de la désalumination est l'effet de confinement sur l'espèce aluminique extra-Réseau générée (EFAL), exercé par les cavités. Finalement nous avons pu montrer que le chemin réactionnel de désalumination et désilication, consécutif ou simultané, , est thermodynamiquement plus favorable qu'une simple désalumination ce qui est en accord avec les propositions mécanistiques de la littérature sur la genèse de mésopores par démétallation. / Zeolites are crystalline microporous aluminosilicates widely used in refining, petrochemistry and biomass conversion. However, diffusion limitation and confinement effect can promote the formation of undesired products. The introduction of mesopores by dealumination and/or desilication ("hierarchical zeolites") is a possible solution widely used experimentally. Nevertheless, the mechanisms of these demetallation reactions are poorly described at the molecular scale. We determine the mechanisms of the formation of extraframework Al species (EFAL) for zeotypes MOR, FAU, MFI and CHA occurring during the dealumination process, possibly associated with desilication. First-Principles periodic density functional theory (DFT) and hybrid QM/QM calculations have been employed in order to analyze full reaction paths leading to extraframework species and to quantify the activation energies of the determining steps. It has been demonstrated that the initiation of an Al-O(H) bond break takes place via water adsorption on the Al atom in anti-Position to the Brønsted acid site, via a penta- or tetra-Coordinated Al species. Such species are shown to be at the initiation of the Al dislodgement from the zeolitic framework. Despite a strong structural heterogeneity of T sites, we determined Brønsted-Evans-Polanyi (BEP) relationships for the entire dealumination pathway. Moreover, it is shown that not only the initiation and propagation mechanisms are primordial for the understanding of an Al extraction, but also the confinement effect on EFAL species within the zeolites cavities. Finally, from the energy profile of combined dealumination/desilication pathways, we show that it is thermodynamically favoured to extract extraframework Si species (EFSI) in the course of dealumination.

Despite comprehensive studies addressing the chemical kinetics of butanol isomers, relevant uncertainties associated with the emissions of relevant pollutants persists. Also, a lack of chemistry knowledge of processes designed to produce biofuels limits their implementation at industrial scales. Therefore, the first objective of this thesis was to use cutting-edge kinetic theories to calculate rate constants of propen-2-ol, 1-pronenol, and vinyl alcohol keto-enol tautomerizations, which account for the production of the harmful carbonyl species. The second objective was to use the predictive capabilities of dynamic theories to reveal new chemistry of syngas oxy-combustion in supercritical CO2 and complexities of the zeolite dealumination, two processes involved in coal and biomass conversion. Rate constants computations considered transition state theory with variational effects, tunneling correction, and multistructural torsional anharmonicity. The study also included pressure effects by using and improving the system-specific quantum Rice-Ramsperger-Kassel/modified strong collision model. The atomistic simulations used ReaxFF force fields in hydrogen/oxygen/carbon monoxide/ carbon dioxide mixtures to represent the syngas system and an MFI zeolite with different water loading to model the dealumination. The results show that the studied assisted tautomerizations have much lower energy barriers than the unimolecular process. However, the “catalytic” effect is efficient only if the partner molecule is at high concentrations. Pressure effects are pronounced in the chemically activated tautomerizations, and the improved algorithm to compute pressure-dependent rate constants overcomes the initial difficulties associated with its application to C3 or larger molecules at temperatures above 800-1000 K. Reactive molecular dynamics simulations revealed the role of CO2 as an initiator in the syngas oxy-combustion and a new step involving the formation of formic acid. Those simulations for the zeolite dealumination process also showed that proton transfer, framework flexibility, and aluminum dislodging mediated by silicon reactions are complex dynamic phenomena determining the process. These aspects complement the dealumination theory uncovered so far and establish new paths in the study of water-zeolite interactions. Overall, the rate constants computed in this work reduce relevant uncertainties in the chemical kinetic mechanisms of alcohol oxidation, and the molecular dynamics simulations broaden the chemical knowledge of processes aimed at the utilization of alternative energy resources.

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No. of bitstreams: 1 DissHRAD.pdf: 15161052 bytes, checksum: e10c4924acc9cc8afc5ecbec12ee85aa (MD5) Previous issue date: 2015-03-13 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Nowadays, the Brazilian petroleum is extracted from very deep fields and possesses a high naphthenic hydrocarbons composition, which imposes new challenges to refineries and specially to the catalytic cracking process. In that process, the catalyst must act maximizing the production of the highly demanded gasoline, diesel and light olefins from heavy fractions. Taking into consideration the above discussed context, this work aimed to evaluate the effect of basic or acid treatments applied on ZSM-5 zeolites (Si/Al=12 or 23) in the activity to cyclohexane or methylcyclohexane transformation. XRD and 27Al-NMR showed that the dealuminated zeolites presented an increase in their crystallinity due to the extra-framework aluminum lixiviation. On the other hand, in the desilicated zeolites occurred a decrease in their crystallinity as a consequence of the extra-framework aluminum generation. MEV images do not evidence any morphological change that could have been produced by the acid or basic treatments, however, the desilicated ZSM-5 zeolites treated under harder conditions presented significant textural modifications. As expected, the chemical ICP analyses showed a decrease in the Si/Al ratio in the desilicated zeolites and an increase of that ratio for those dealuminated ones, being the last variation more significative in the external surface of the zeolite crystals, as was evidenced by XPS analyses. Data from NH3-TPD showed that the acid treatment resulted in a higher ratio of strong acid sites, which suffered more deactivation during reaction. N2 fisisorption analyses of the ZSM-5 zeolites, showed that the desilication done at higher temperature was more efficient to mesopore generation. In the cyclohexane and methylcyclohexane transformation, the dealuminated zeolites were less active due to their lower aluminum content, nevertheless were more stable and presented a small increase to light olefins selectivity. The desilicated ZSM-5 zeolites presented higher activity and higher yield to light olefins that were supported by their lower Si/Al ratio and mainly by the presence of mesoporosity that enhanced the reagents and products internal diffusivity. / A produção nacional de petróleo, extraído de jazidas cada vez mais profundas, possui um elevado teor de hidrocarbonetos naftênicos, o que impõe novos desafios às refinarias brasileiras e, em particular, ao processo de craqueamento catalítico. Nesse processo, o catalisador deve maximizar a transformação das frações pesadas em produtos de alta demanda como gasolina, diesel e olefinas leves. Nesse contexto, esta dissertação objetivou avaliar o efeito de tratamentos de lixiviação ácida ou básica em zeólitas ZSM-5 (Si/Al=12 ou 23), na atividade para a transformação de cicloexano ou metilcicloexano. Dados de DRX e 27Al-RMN mostraram que as zeólitas desaluminizadas apresentaram um aumento da sua cristalinidade devido à remoção de átomos de alumínio extra-rede, por outro lado, nas zeólitas dessilicalizadas ocorreu uma redução da cristalinidade devido à geração de alumínio extra rede. As micrografias de MEV não evidenciaram modificação morfológica devido aos tratamentos, entretanto nas amostras dessilicalizadas sob condições mais severas, houve significativa mudança das propriedades texturais. Como esperado, as análises químicas por ICP mostraram uma redução na razão Si/Al para as amostras dessilicalizadas e um aumento dessa razão para as zeólitas desaluminizadas, sendo essa variação mais significativa na superfície externa dos cristais, como mostraram resultados de XPS. As análises de DTP-NH3 mostraram que o tratamento ácido resultou numa maior proporção de sítios ácidos fortes, os quais sofreram maior desativação durante a reação. Dados de fisissorção de N2 das zeólitas mostraram que a dessilicalização em temperatura mais elevada foi mais eficiente na geração de mesoporos. Na transformação do cicloexano e do metilcicloexano, as zeólitas desaluminizadas apresentaram menor conversão como resultado da diminuição do teor de alumínio, entretanto tiveram maior estabilidade e apresentaram um ligeiro aumento na seletividade a olefinas leves. As amostras dessilicalizadas apresentaram maiores conversões e rendimentos a olefinas leves, que se justificaram em função da diminuição da razão Si/Al, mas principalmente, como resultado da presença de mesoporosidade, que melhorou a difusão interna de reagentes e produtos.