The research determined that the improved heat transfer characteristics of a fluidized bed reactor (FBR) will allow the use of cobalt catalyst for high temperature Fischer-Tropsch synthesis (HTFT). Cobalt was loaded onto a gamma alumina support, the catalyst was characterized using TPR, BET/BJH, XRD, and PSA to track changes in the catalyst morphology. The reactor was characterized to determine the minimum fluidization velocity and the maximum velocity prior to entering lean phase fluidization with pneumatic transport of the catalyst. The highest minimum fluidization velocity was found to be about 2800 sccm, there was no maximum velocity found for the reactor setup. Once characterized, the reactor was operated at pressures of 145, 217.6, and 290.1 psig, a syngas flow rate of 4000 sccm, and at temperatures of 330 and 350 °C. The optimal conditions found in this study were 330 °C and 217 psig. At these conditions CO conversion was 83.53 % for a single pass. Methane, CO2, and light gases (C2 - C4) selectivities were at low rates of 31.43, 5.80, and 3.48 % respectively. Alcohol selectivity at these conditions was non-existent. The olefin and wax selectivities were the lowest of the data set at 7.05 and 3.18 % respectively. Liquid transportation fuels selectivity was the highest at 56.11 %.

Le faible coût du glycérol sur le marché a conduit à des études approfondies sur la conversion du glycérol en dérivés à valeur ajoutée. Ce travail se concentre sur l'estérification catalytique du glycérol, avec l'acide oléique, réaction d’intérêt industriel en raison de la grande valeur commerciale des produits obtenus. Dans ce travail, un nouveau catalyseur acide hétérogène présentant une surface hydrophobe a été développé sur le support ZrO2-SiO2 car un catalyseur acide solide tolérant à l'eau est essentiel pour les réactions d'estérification en milieu biphasique produisant de l'eau. Le catalyseur synthétisé (ZrO2-SiO2-Me&Et-PhSO3H) a été préparé par silication et modification de surface en utilisant du triméthoxyméthylsilane (TMMS) et du 2-(4- chlorosulfonylphényl) éthyltriméthoxysilane. La morphologie de surface, les propriétés physicochimiques et texturales, l'acidité et l'hydrophobicité ont été caractérisées. Le mécanisme de modification de la surface du catalyseur est proposé en fonction des résultats de caractérisation complets. Une nouvelle technique pour contrôler le niveau d'acidité et d'hydrophobicité du catalyseur conçu est décrite dans ce travail. L'acidité et l'hydrophobicité du catalyseur ont été réglées en contrôlant la quantité d'agents de modification de surface. Il a pu être montré que l'hydrophobicité du catalyseur était diminuée à mesure que son acidité augmentait. Le catalyseur ZrO2-SiO2-Me & Et-PhSO3H_70 avec 70% molaire de TMMS et 0,62 mmol/g d'acidité est le catalyseur optimal pour l'estérification du glycérol avec l'acide oléique. Enoutre, le rôle de l'hydrophobicité dans la réaction catalytique a été étudié ici. Ce travail a montré qu'à acidité constante du catalyseur, le catalyseur le plus hydrophobe présentait un meilleur rendement. La conversion en utilisant le catalyseur préparé (ZrO2-SiO2-Me et EtPhSO3H_70) est de 88,2% avec une sélectivité en monooléate de glycérol de 53,5% et une sélectivité en dioléate de glycérol de 40,0% (sélectivité combinée de 94% en monooléate et dioléate de glycérol) pour un rapport équimolaire d'acide oléique/glycérol, une température de réaction de 160°C, une concentration massique du catalyseur de 5% par rapport à la masse d’acide oléique introduit, en conditions de réaction sans solvant et avec un temps de réaction de 8 h. Ce travail révèle que l'hydrophobicité et le volume des pores du catalyseur conçu affectent significativement la sélectivité en produit. De plus, les performances du catalyseur hydrophobe ZrO2-SiO2-Me&Et- PhSO3H_70, ont été comparées à celles de la zircone sulfatée (SO42-/ZrO2) et des catalyseurs commerciaux (Amberlyst 15 et Aquivion). Les résultats de corrélation ont montré que le volume moyen des pores (taille des pores) influençait la sélectivité du produit lorsque le catalyseur ZrO2- SiO2-Me&Et-PhSO3H_70 était comparé à trois catalyseurs SO42-/ZrO2 développés à partir de différents précurseurs de zirconium. Ainsi, le catalyseur à volume de pores le plus élevé est favorable à la production de dioléate de glycérol dans des conditions réactionnelles identiques. On peut conclure que le volume et la taille des pores peuvent être utilisés pour contrôler la sélectivité en produit. En outre, cette étude a également révélé que la propriété d'hydrophobicité améliorait la vitesse de réaction initiale. / The low market value of glycerol has led to extensive investigations on glycerol conversion to value-added derivatives. This work focuses on industrially important catalytic esterification of glycerol with oleic acid due to the high commercial value of the resulting products. In this work, a novel heterogeneous acid catalyst featuring hydrophobic surface was developed on ZrO2-SiO2 support as water tolerant solid acid catalyst is vital for biphasic esterification reactions producing water. The synthesized catalyst (ZrO2-SiO2-Me&Et-PhSO3H) was prepared through silication and surface modification using trimethoxymethylsilane (TMMS) and 2-(4-chlorosulfonylphenyl) ethyltrimethoxysilane. The surface morphology, physiochemical and textural properties, acidity and hydrophobicity were characterized. The mechanism of the catalyst surface modification is thereof proposed according to comprehensive characterization results. A novel technique to control acidity and hydrophobicity level of the designed catalyst is disclosed in this work. The acidity and hydrophobicity of the catalyst were tuned by controlling the amount of surface modification agents. It was found that the hydrophobicity of the catalyst decreased as its acidity increased. ZrO2-SiO2-Me&Et-PhSO3H_70 catalyst with 70 mol% of TMMS and 0.62 mmol/g acidity is the optimal catalyst for glycerol esterification with oleic acid. Furthermore, the role of hydrophobicity in catalytic reaction was investigated herein. It was found that at constant catalyst acidity, the more hydrophobic catalyst showed better yield. The conversion using the designed catalyst (ZrO2-SiO2-Me&EtPhSO3H_70) is 88.2% with 53.5% glycerol monooleate selectivity and 40.0% glycerol dioleate selectivity (combined 94% selectivity of glycerol monooleate and dioleate) at equimolar oleic acid-to-glycerol ratio, 160 oC, reaction temperature, 5 wt% catalyst concentration with respect to weight of oleic acid, solvent-less reaction conditions and 8 h reaction time. This work reveals that the hydrophobicity and the pore volume of the designed catalyst significantly affect the product selectivity. In addition, the performance of the hydrophobic designed ZrO2-SiO2-Me&Et-PhSO3H_70 catalyst was used to benchmark with catalytic activity of sulfated zirconia (SO42-/ZrO2) and commercial catalysts (Amberlyst 15 and Aquivion). The correlation results showed that the average pore volume (pore size) influenced the product selectivity when ZrO2-SiO2-Me&Et-PhSO3H_70 catalyst was compared to three SO42-/ZrO2 catalysts that were developed from different zirconium precursors. Whereby, the higher pore volume catalyst is favourable to glycerol dioleate production at identical reaction conditions. It can be concluded that pore volume and size can be used to control the product selectivity. In addition, this study also revealed that hydrophobicity characteristic facilitated initial reaction rate effectively.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O vapor dágua está presente na exaustão veicular em quantidades significativas e, nas condições de operação do catalisador automotivo, essa espécie pode promover uma série de fenômenos térmicos que podem reduzir a vida útil do sistema. Dentro desse contexto, essa dissertação tem como objetivo estudar os efeitos da desativação hidrotérmica nas propriedades físico-químicas e estruturais, e no desempenho de três catalisadores automotivos comerciais à base de Pd/Rh, designados A, C e E. Esses sistemas foram submetidos a tratamento térmico a 1000C por 12 horas, sob três tipos de correntes gasosas, com a seguinte composição: N2, 14% H2O/N2 e 18% H2O/N2. A caracterização dos catalisadores consistiu das seguintes técnicas: FRX, ICP-OES, ATG-ATD, fisissorção de N2, TPD-H2 e TPR. A partir dos resultados obtidos para as amostras envelhecidas, foram constatados vários fenômenos característicos da degradação térmica, como sinterização da alumina e do óxido misto CeO2-ZrO2, transições de fases cristalina na alumina e segregação de fases no óxido misto. A avaliação da atividade catalítica foi realizada com base na reação de redução do NO pelo CO, e nas reações de oxidação do CO e do C3H8. Para os catalisadores C e E, os envelhecimentos acarretaram em perda de atividade, e os resultados da avaliação catalítica apresentaram uma boa correlação com as propriedades texturais e a redutibilidade desses catalisadores. Em contrapartida, para o catalisador A, os tratamentos térmicos o ativaram para todas as reações. Apesar de os três sistemas terem apresentado boa atividade frente à redução do NO pelo CO, foi observada, para todas as amostras, a formação indesejável de N2O em quantidades significativas, indicando que eles foram pouco seletivos na faixa de temperatura analisada / Water vapor is present in vehicular exhaust in significant amounts and may promote a series of thermal phenomena in the operating conditions of the automotive catalyst, reducing its lifetime. Thus, this dissertation aims to study the effects of hydrothermal deactivation in physicochemical and structural properties, and in catalytic performance of three Pd/Rh-based commercial automotive catalysts nominated A, C and E. These systems were subjected to heat treatment at 1000 C for 12 hours under three types of gas streams with the following composition: N2, 14% H2O/N2 and 18% H2O/N2. The catalysts characterization consisted of the following techniques: XRF, ICP-OES, TGA-DTA, N2 physisorption, TPD-H2 and TPR. The results obtained for the aged samples showed various phenomena characteristic of thermal degradation like sintering of alumina and CeO2-ZrO2 mixed oxide, alumina phase transitions and mixed oxide demixing. The evaluation of the catalytic activity was based on the reduction of NO by CO and the oxidation of CO and C3H8. For catalysts C and E, the aging process resulted in loss of activity, and results of the catalytic evaluation showed a good correlation with the textural properties and reducibility of these catalysts. On the other hand, the heat treatments activated catalyst A for all reactions. Although the three systems showed good activity in the reduction of NO by CO, the undesirable formation of N2O in significant amounts was observed for all samples, indicating that they lacked selectivity in the examined temperature range

No processo de hidrocraqueamento para a produção de lubrificantes ocorre a formação de uma corrente rica em compostos parafínicos que possuem alto ponto de fluidez, apesar dos mesmos apresentarem excelentes desempenhos em termos de estabilidade térmica e oxidativa. A transformação das n-parafinas obtidas nestas correntes em isoparafinas e compostos naftênicos, os quais possuem menores pontos de fluidez, se faz necessária a fim de enquadrar esta propriedade. Uma das rotas catalíticas mais importantes neste sentido é a hidroisodesparafinação ou HIDW (hydroisodewaxing) que consiste na conversão de n-parafinas nas respectivas isoparafinas, onde são empregados catalisadores bifuncionais zeolíticos com a ocorrência de seletividade de forma. No caso dos catalisadores industriais, se faz necessária a dispersão da fase metálica e da zeólita em uma matriz amorfa para viabilizar sua conformação e melhorar a resistência mecânica do catalisador final. Neste cenário, o objetivo deste trabalho foi preparar e analisar o desempenho de uma série de catalisadores à base de zeólita beta inseridos numa matriz de alumina, variando-se o teor de zeólita e o tipo de precursor de Pt utilizado. Os catalisadores foram avaliados na reação de hidroisomerização de um composto modelo, no caso, n-hexadecano. Os testes realizados para avaliação da atividade e seletividade foram conduzidos em um reator de fluxo contínuo em alta pressão e fase líquida em unidade de laboratório. Os catalisadores foram testados em condições operacionais que proporcionassem uma ampla faixa de conversões do n-C16. Verificou-se que as atividades dos catalisadores foram proporcionais ao teor de zeólita no catalisador, indicando que a função ácida, neste catalisador bifuncional, é a etapa limitante do processo. Quanto à natureza do precursor de Pt, o catalisador preparado com ácido cloroplatínico foi sensivelmente mais ativo que os preparados com o complexo aminplatina. No entanto, para todos os catalisadores, a distribuição de produtos em função da conversão foi similar, independente do teor de zeólita e da natureza do precursor de platina. Foi também determinado o ponto de fluidez de uma série de produtos de reação, obtendo-se valores entre 17,5 C (n-hexadecano) e - 41 C (produto com 98% de conversão). Obteve-se uma boa correlação entre o ponto de fluidez e a composição dos produtos, considerando-se a presença de isômeros mono, di e tri-substituídos e compostos de menor peso molecular que C16 / The residual oil of hydrocracking process is a useful stream for the production of lubricants. This product is rich in paraffinic compounds which have a high pour point despite having the excellent performances in terms of thermal and oxidation stability. The conversion of the heavy n-paraffins or long alkyl chains into isoparaffins and naphthenic compounds, which have lower pour points, is necessary in order to lower the pour point to adequate values for lubricants formulation. One of the most important catalytic routes in this direction is hydroisodewaxing or HIDW, which consists in the conversion of n-paraffins in the respective isoparaffins with minimum formation of cracked products. For this objective, zeolitic bifunctional catalysts are employed, using zeolites presenting shape selectivity properties in order to avoid n-paraffin cracking. In the case of industrial catalysts, it is necessary to disperse the metallic phase and the zeolite in an amorphous matrix for obtaining adequate shape and mechanical strength. In this work, we studied the performance of a series of catalysts prepared with beta zeolite embedded in a alumina based matrix and varying the content of zeolite and the type of platinum precursor. The catalyst performance was evaluated in the hydroisomerization of a model compound, in this case, n-hexadecane, using a continuous flow reactor at high pressure and liquid phase in laboratory unit. Operating conditions were selected in order to provide a broad range of n-C16 conversions. Catalyst activities were proportional to the zeolite content in the support indicating that the acid function is the limiting one in these catalysts. Moreover,a catalyst prepared with chloroplatinic acid was more active than the one prepared with amine-platinum complex, for the same zeolite content. In despite of the different conversions, all catalysts presented similar isomerized and cracked product distributions as function of the overall n-C16 conversion. Pour points of a series of reaction products were measured and values between 17.5 C (n-hexadecane) and -41 C (98 % conversion) were obtained. A good correlation with pour point and product composition was obtained, taking in account the concentrations of mono, di and tri-branched isoparaffins and cracked products

This thesis documents the development of rhodium-catalyzed traceless chelation-controlled hydroacylation reactions for the synthesis of a variety of ketone products. <strong>Chapter 1</strong> provides an overview of rhodium-catalyzed hydroacylation chemistry, focusing on the origin of chelation-controlled strategies and the benefits thereof. <strong>Chapter 2</strong> describes a sequential reaction involving alkene hydroacylation, sulfide elimination and boronic acid conjugate addition, which affords products with the initial sulfide coordinating group replaced by a stereochemically defined aryl group. <strong>Chapter 3</strong> demonstrates a sequential process involving alkyne hydroacylation, boronic acid conjugate addition and sulfide elimination, which provides enantioenriched β'-arylα,β-unsaturated ketones in a highly efficient and selective manner. <strong>Chapter 4</strong> illustrates a versatile chelating group, triazene, for hydroacylation reactions. Subsequent functionalization of aromatic C-H bonds, promoted by the same chelating unit, offers highly substituted phenyl ketone products. <strong>Chapter 5</strong> documents experimental procedures and data.

abstract: Carboxylic acids are an abundant and reactive species present throughout our solar system. The reactions of carboxylic acids can shape the organic abundances within oil field brines, carbonaceous chondrites, and different ranks of coal. I have performed hydrothermal experiments with model aromatic carboxylic acids in the presences of different oxide minerals to investigate the reactions available to carboxylic acids in the presence of mineral surfaces. By performing experiments containing one organic compound and one mineral surface, I can begin to unravel the different reactions that can occur in the presence of different minerals. I performed experiments with phenylacetic acid (PAA), hydrocinnamic acid (HCA) and benzoic acid (BA) in the presence of spinel (MgAl2O4), magnetite (Fe3O4), hematite (Fe2O3), and corundum (Al2O3). The focus of this work was metal oxide minerals, with and without transition metal atoms, and with different crystal structures. I found that all four oxide minerals facilitated ketonic decarboxylation reactions of carboxylic acids to form ketone structures. The two minerals containing transition metals (magnetite and hematite) also opened a reaction path involving electrochemical oxidation of one carboxylic acid, PAA, to the shorter chain version of a second carboxylic acid, BA, in experiments starting with PAA. Fundamental studies like these can help to shape our knowledge of the breadth of organic reactions that are possible in geologic systems and the mechanisms of those reactions. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2017

Made available in DSpace on 2016-06-02T19:55:30Z (GMT). No. of bitstreams: 1 3665.pdf: 6614955 bytes, checksum: 38fe505ba234583972871c7ff274e981 (MD5) Previous issue date: 2011-04-28 / Universidade Federal de Sao Carlos / Colloidal Pt nanoparticles were synthesized according to an adapted procedure from Song and co-workers [1], which it was based on the reduction of dihydrogen hexachloroplatinate by ethylene glycol in a basic solution, but using two PVP/Pt = 0,2 and 10 ratio. Both the ratio lead to monodisperse platinum nanoparticles with similar sizes (2.0 and 2.8 nm). Colloidal Pt nanoparticles solutions were incorporated into alumina during sol-gel synthesis and showed different stabilities when submitted to thermal treatment in synthetic air, He and H2 atmospheres. PVP/Pt ratio added to nanoparticles after synthesis was the main parameter considered to the stability of the particles on the support. Using a minor PVP/Pt ratio lead to particles agglomerates during calcinations step in synthetic air. On the other hand, when an excess of PVP was used stable and disperse particles were obtained during a severe thermal treatment. The anchoring of particles into support during incorporation stage could be the most plausible explanation for this. Platinum nanocatalysts supported on alumina and ceriaalumina showed catalytic activity for the water gas shift reaction. CO conversion data indicated that the increasing of CeO2 loading of 12 to 20% lead to an improvement in the catalytic activity. XPS measurements after pre-treatment in H2 confirmed the presence of Pt+&#61540;&#61472;on the catalyst surface containing ceria, suggesting some metal-support interaction. In situ characterization techniques allowed to a better understanding of species involved into water gas shift reaction mechanism. Through X-ray absorption near edge structure in the Pt edge measurements showed reduced Pt during reaction for all catalysts, suggesting that similar electronic density of sites was present. This was also observed in CO adsorbed DRIFTS measurements. Nevertheless, XANES spectra in the Ce edge showed some changes in oxidation state of Ce during the reaction, indicating the occurrence of redox mechanism, mediated by ceria. In situ DRIFTS experiments showed little concentrations of formates and carbonates species on the catalyst surface during the reaction, suggesting that more than one mechanism may occur simultaneously. / Nanopartículas de Pt foram preparadas seguindo um procedimento adaptado de Song e colaboradores [1], cuja metodologia consistiu na redução química do ácido hexacloroplatinico pelo etilenoglicol em meio básico, porém utilizando duas razões PVP/Pt = 0,2 e 10. Ambas as razões levaram a nanopartículas de Pt com tamanho similar (2,0 e 2,8 nm) e monodispersas. As soluções coloidais de nanoparticulas de Pt foram incorporada à alumina durante a síntese sol-gel e mostraram diferentes estabilidades quando submetidas a tratamentos térmicos em ar sintético, He e H2. A razão PVP/Pt utilizada na síntese das partículas foi o fator determinante na estabilidade das partículas no suporte. A adição de uma menor razão PVP/Pt levou a aglomeração das partículas durante a calcinação em ar sintético. Por outro lado, quando um excesso de PVP foi utilizado durante a síntese das partículas as mesmas se mostraram estáveis e dispersas no suporte quando submetidas ao mais severo tratamento. Isto foi relacionado ao ancoramento das partículas ao suporte durante a etapa de incorporação. Nanocatalisadores de Pt suportados em alumina e cério-alumina apresentaram atividade catalítica para a reação de deslocamento gás-água. Dados de conversão do CO indicaram que o aumento no teor de CeO2 de 12 para 20% levou a um aumento na atividade catalítica. Medidas de XPS após a etapa de pré-tratamento em H2 confirmaram a presença de Pt+&#61540;&#61472;na superfície dos catalisadores contendo ceria, sugerindo alguma interação metal-suporte. Técnicas de caracterização in situ possibilitaram um melhor entendimento do mecanismo das espécies envolvidas no mecanismo da reação de deslocamento gás-água. Medidas de XANES in situ na borda da Pt confirmaram a presença de Pt reduzida durante o curso da reação para todos os catalisadores, o que sugere a presença de sítios de Pt com densidade eletrônica similar. Isto também foi observado nas medidas de DRIFTS do CO adsorvido para os catalisadores estudados. No entanto, os espectros de XANES na borda do Ce confirmaram mudanças no estado de oxidação do Ce no decorrer da reação, indicando a ocorrência do mecanismo de reação redox, mediado pela ceria. Experimentos utilizando DRIFTS in situ identificaram pequenas concentrações de espécies do tipo formiatos e carbonatos na superfície dos catalisadores durante a reação, sugerindo que mais de um mecanismo pode ocorrer simultaneamente. Palavras chave: nanoparticulas, Platina, catalisador, reação de deslocamento gás-água, PVP.

Submitted by MARIA BEATRIZ ALVES AFONSO null (mbaafonso@hotmail.com) on 2017-06-12T21:05:33Z No. of bitstreams: 1 Dissertação_ Maria Beatriz Alves Afonso.pdf: 2111821 bytes, checksum: 42668991264b1d02752d3be1fc9cc953 (MD5) / Approved for entry into archive by Luiz Galeffi (luizgaleffi@gmail.com) on 2017-06-13T17:19:35Z (GMT) No. of bitstreams: 1 afonso_mba_me_sjrp.pdf: 2111821 bytes, checksum: 42668991264b1d02752d3be1fc9cc953 (MD5) / Made available in DSpace on 2017-06-13T17:19:35Z (GMT). No. of bitstreams: 1 afonso_mba_me_sjrp.pdf: 2111821 bytes, checksum: 42668991264b1d02752d3be1fc9cc953 (MD5) Previous issue date: 2017-05-12 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A investigação de sistemas catalíticos duais capazes de mediar as reações de polimerização por abertura de anel via metátese (ROMP) e de polimerização radicalar por transferência de átomo (ATRP) simultaneamente é de grande interesse e importância na obtenção de novos materiais com potencial de aplicação. Neste estudo, novos complexos de rutênio(II) coordenados a diferentes bases de Schiff derivadas de cicloalquilaminas (ciclopentil 1a, cicloexil 1b, cicloheptil 1c e ciclooctil 1d) foram sintetizados: [RuCl(CyPen-Salen)(PPh3)2] 2a, [RuCl(CyHex-Salen)(PPh3)2] 2b, [RuCl(CyHep-Salen)(PPh3)2] 2c e [RuCl(CyOct-Salen)(PPh3)2] 2d. As bases de Schiff e seus respectivos complexos de rutênio foram caracterizados por FTIR, UV-Vis, RMN e voltametria cíclica. Os complexos planejados foram avaliados como precursores catalíticos em reações de ROMP de norborneno (NBE) e em reações de ATRP de metacrilato de metila (MMA). As sínteses de polinorborneno (poliNBE) via ROMP com os complexos 2a-d como pré-catalisadores foram avaliadas sob diferentes condições de reação ([HCl]/[Ru], [EDA]/[Ru], [NBE]/[Ru] e temperatura). Os melhores rendimentos de poliNBE foram obtidos a 50 °C com razão molar [NBE]/[HCl]/[Ru] = 5000/25/1 na presença de 5 µL de EDA por 60 minutos. A polimerização de MMA via ATRP foi conduzida usando os complexos 2a-d na presença de etil-α-bromoisobutirato (EBiB) como iniciador. Os testes catalíticos foram avaliados em função do tempo de reação usando a razão molar [MMA]/[EBiB]/[Ru] = 1000/2/1. Todos os experimentos via ATRP foram conduzidos à 85 °C. A correlação linear do ln([MMA]0/[MMA]) em função do tempo na ATRP de MMA mediada pelos complexos 2a-d indica que a concentração de radicais permanece constante durante a polimerização. As massas moleculares aumentaram linearmente com a conversão com a diminuição dos valores de IPD, no entanto, as massas moleculares experimentais foram maiores do que as massas moleculares teóricas. / The investigation of dual catalytic systems able to mediate simultaneously ring-opening metathesis polymerization (ROMP) and atom-transfer radical polymerization (ATRP) reactions is of great interest and importance in obtaining new materials with potential for application. In the study, ruthenium(II) complexes of Schiff base derived from cycloalkylamines (cycloalkyl = cyclopentyl 1a, cyclohexyl 1b, cycloheptyl 1c and cyclooctyl) 1d were synthesized: [RuCl(CyPen-Salen)(PPh3)2] 2a, [RuCl(CyHex-Salen)(PPh3)2] 2b, [RuCl(CyHep-Salen)(PPh3)2] 2c and [RuCl(CyOct-Salen)(PPh3)2] 2d. The Schiff bases 1a-d and their respective RuII complexes 2a-d were characterized by FTIR, UV-Vis, NMR, and cyclic voltammetry. The complexes 2a-d were evaluated as catalytic precursors for ROMP of norbornene (NBE) and for ATRP of methyl methacrylate (MMA). The syntheses of polynorbornene (polyNBE) via ROMP with complexes 2a-d as pre-catalysts were evaluated under different reaction conditions ([HCl]/[Ru], [EDA]/[Ru], [NBE]/[Ru], and temperature). The highest yields of polyNBE were obtained with [NBE]/[HCl]/[Ru] = 5000/25/1 molar ratio in the presence of 5 µL of EDA for 60 minutes at 50 °C. MMA polymerization via ATRP was conducted using the complexes 2a-d in the presence of ethyl-α-bromoisobutyrate (EBiB) as initiator. The catalytic tests were evaluated as a function of the reaction time using the initial molar ratio of [MMA]/[EBiB]/[Ru] = 1000/2/1 at 85 °C. The linear correlation of ln([MMA]0/[MMA]) and time clearly indicates that the concentration of radicals remains constant during the polymerization and that the ATRP of MMA mediated by 2a-d proceeds in a controlled manner. Molecular weights increased linearly with conversion, however, the experimental molecular weights were higher than the theoretical ones.

Submitted by José Henrique Lazaro de Carvalho (jose.carvalho@fc.unesp.br) on 2018-04-26T14:52:46Z No. of bitstreams: 1 merged.pdf: 3543516 bytes, checksum: 94a6da42fee42b5469644d670ca0dddc (MD5) / Approved for entry into archive by Minervina Teixeira Lopes null (vina_lopes@bauru.unesp.br) on 2018-04-26T17:33:49Z (GMT) No. of bitstreams: 1 carvalho_jhl_me_bauru.pdf: 3133645 bytes, checksum: 07b206851bb163d2aab65e55f0340aea (MD5) / Made available in DSpace on 2018-04-26T17:33:49Z (GMT). No. of bitstreams: 1 carvalho_jhl_me_bauru.pdf: 3133645 bytes, checksum: 07b206851bb163d2aab65e55f0340aea (MD5) Previous issue date: 2018-02-26 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Os hidrocarbonetos se constituem na função mais simples da química orgânica. Mesmo sendo formados apenas por carbono e hidrogênio, esta classe é uma das mais diversas, onde se destacam os hidrocarbonetos alquil aromáticos (HAA) e os hidrocarbonetos aromáticos policíclicos (HAP). Por possuírem baixa reatividade e serem lipossolúveis, os HAA e HAP tendem a se acumular na natureza e nos tecidos vivos podendo levar a mutações genéticas e ao câncer. Funcionalizações oxigenadas nestes hidrocarbonetos ampliam suas aplicações industriais e auxiliam na sua remediação ambiental. A oxidação radicalar utilizando radicais hidroxila via TBHP (t-butil-hidroperóxido) é uma rota promissora devido à ausência de resíduos metálicos nocivos no processo. Paralelamente, o uso de metais do bloco-d, como o nióbio, como catalisadores heterogêneos, que são conhecidos por apresentarem boa estabilidade térmica, porosidade, maior superfície de contato e podendo ser recuperado e reutilizado, vem sendo descrito como bons catalisadores para a reação, permitindo rendimentos maiores e condições reacionais mais brandas. O nióbio tem despertado o interesse de muitos grupos de pesquisa devido às suas propriedades e aplicabilidades na metalurgia, supercondutores e supercapacitores, e na síntese orgânica. Este trabalho focou no estudo da aplicação do óxido de nióbio como catalisador heterogêneo em reações de oxidação de HAA e HAP usando o TBHP como oxidante. Diferentes variáveis reacionais como o solvente, a concentração e morfologia do catalisador, temperatura, dentre outras, foram investigadas a fim de otimizar a reação para a melhor conversão no derivado oxigenado. A melhor condição obtida foi utilizando Nb2O5 amorfo em 10% em mol de reagente, em acetonitrila e em refluxo com mais de 40 % de conversão em derivado oxigenado para qualquer substrato de hidrocarboneto estudado. / Hydrocarbons are the simplest function of organic chemistry. Although formed only by carbon and hydrogen, this class is one of the most diverse, in which the alkyl aromatic hydrocarbons (AAHs) and the polycyclic aromatic hydrocarbons (PAHs) stand out. These substances are mostly fossil raw materials widely used in industry in diverse applications. Because they have low reactivity and are liposoluble, AAHs and PAHs tend to accumulate in nature and in living tissues, leading to genetic mutations and cancer. Oxygenated functionalities in these hydrocarbons broaden their industrial applications and assist in their environmental remediation. Radical oxidation using hydroxyl radicals via TBHP (t-butylhydroperoxide) is a promising route due to the absence of noxious metal residues in the process. At the same time, the use of d-block metals, such as niobium, as heterogeneous catalysts, which are known to have good thermal stability, porosity, larger contact surface and be able to be recovered and reused, have been described as good catalysts for the reaction, allowing for higher yields and softer reaction conditions. Niobium has attracted the interest of many research groups because of its properties and applications in metallurgy, superconductors and supercapacitors, and in organic synthesis. This work focused on the study of the application of niobium oxide as a heterogeneous catalyst in oxidation reactions of AAHs and HAP using TBHP as oxidant. Many reactional variables like the solvent, the catalyst concentration and morphology, as well as temperature have been investigated in order to optimize the reaction for the better conversion to oxygen derivatives. The best obtained condition was using 10 % in mol amorphous Nb2O5 in acetonitrile under reflux with a conversion yield of more than 40 % for any studied hydrocarbon substrate.

No processo de hidrocraqueamento para a produção de lubrificantes ocorre a formação de uma corrente rica em compostos parafínicos que possuem alto ponto de fluidez, apesar dos mesmos apresentarem excelentes desempenhos em termos de estabilidade térmica e oxidativa. A transformação das n-parafinas obtidas nestas correntes em isoparafinas e compostos naftênicos, os quais possuem menores pontos de fluidez, se faz necessária a fim de enquadrar esta propriedade. Uma das rotas catalíticas mais importantes neste sentido é a hidroisodesparafinação ou HIDW (hydroisodewaxing) que consiste na conversão de n-parafinas nas respectivas isoparafinas, onde são empregados catalisadores bifuncionais zeolíticos com a ocorrência de seletividade de forma. No caso dos catalisadores industriais, se faz necessária a dispersão da fase metálica e da zeólita em uma matriz amorfa para viabilizar sua conformação e melhorar a resistência mecânica do catalisador final. Neste cenário, o objetivo deste trabalho foi preparar e analisar o desempenho de uma série de catalisadores à base de zeólita beta inseridos numa matriz de alumina, variando-se o teor de zeólita e o tipo de precursor de Pt utilizado. Os catalisadores foram avaliados na reação de hidroisomerização de um composto modelo, no caso, n-hexadecano. Os testes realizados para avaliação da atividade e seletividade foram conduzidos em um reator de fluxo contínuo em alta pressão e fase líquida em unidade de laboratório. Os catalisadores foram testados em condições operacionais que proporcionassem uma ampla faixa de conversões do n-C16. Verificou-se que as atividades dos catalisadores foram proporcionais ao teor de zeólita no catalisador, indicando que a função ácida, neste catalisador bifuncional, é a etapa limitante do processo. Quanto à natureza do precursor de Pt, o catalisador preparado com ácido cloroplatínico foi sensivelmente mais ativo que os preparados com o complexo aminplatina. No entanto, para todos os catalisadores, a distribuição de produtos em função da conversão foi similar, independente do teor de zeólita e da natureza do precursor de platina. Foi também determinado o ponto de fluidez de uma série de produtos de reação, obtendo-se valores entre 17,5 C (n-hexadecano) e - 41 C (produto com 98% de conversão). Obteve-se uma boa correlação entre o ponto de fluidez e a composição dos produtos, considerando-se a presença de isômeros mono, di e tri-substituídos e compostos de menor peso molecular que C16 / The residual oil of hydrocracking process is a useful stream for the production of lubricants. This product is rich in paraffinic compounds which have a high pour point despite having the excellent performances in terms of thermal and oxidation stability. The conversion of the heavy n-paraffins or long alkyl chains into isoparaffins and naphthenic compounds, which have lower pour points, is necessary in order to lower the pour point to adequate values for lubricants formulation. One of the most important catalytic routes in this direction is hydroisodewaxing or HIDW, which consists in the conversion of n-paraffins in the respective isoparaffins with minimum formation of cracked products. For this objective, zeolitic bifunctional catalysts are employed, using zeolites presenting shape selectivity properties in order to avoid n-paraffin cracking. In the case of industrial catalysts, it is necessary to disperse the metallic phase and the zeolite in an amorphous matrix for obtaining adequate shape and mechanical strength. In this work, we studied the performance of a series of catalysts prepared with beta zeolite embedded in a alumina based matrix and varying the content of zeolite and the type of platinum precursor. The catalyst performance was evaluated in the hydroisomerization of a model compound, in this case, n-hexadecane, using a continuous flow reactor at high pressure and liquid phase in laboratory unit. Operating conditions were selected in order to provide a broad range of n-C16 conversions. Catalyst activities were proportional to the zeolite content in the support indicating that the acid function is the limiting one in these catalysts. Moreover,a catalyst prepared with chloroplatinic acid was more active than the one prepared with amine-platinum complex, for the same zeolite content. In despite of the different conversions, all catalysts presented similar isomerized and cracked product distributions as function of the overall n-C16 conversion. Pour points of a series of reaction products were measured and values between 17.5 C (n-hexadecane) and -41 C (98 % conversion) were obtained. A good correlation with pour point and product composition was obtained, taking in account the concentrations of mono, di and tri-branched isoparaffins and cracked products