CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Este trabalho teve como objetivo sintetizar catalisadores metÃlicos de ferro suportados em carbono ativado a base de polÃmeros para sÃntese de Fischer-Tropsch. A preparaÃÃo dos catalisadores foi realizada pelo mÃtodo de impregnaÃÃo a umidade incipiente, utilizando soluÃÃo aquosa de nitrato de ferro nonahidratado para obtenÃÃo de amostras com, aproximadamente, 55% de ferro. Duas amostras foram preparadas (FeCP1 e FeCP2) e caracterizadas por fluorescÃncia de raios-X por energia dispersiva (EDXRF), difraÃÃo de raios-X (DRX), medidas de fisissorÃÃo de nitrogÃnio, espectroscopia fotoeletrÃnica de raio-X (XPS), microscopia eletrÃnica de varredura (SEM-EDS) e reduÃÃo à temperatura programada (TPR). As amostras foram submetidas tambÃm a testes catalÃticos, utilizando-se diferentes condiÃÃes de temperatura (513, 528 e 543 K), pressÃo (20, 25 e 30 atm) e razÃo molar H2:CO de 1 e 0,5. Os dados de EDXRF evidenciaram considerÃvel diferenÃa no teor de metal impregnado entre os dois catalisadores; o FeCP2 apresentou teor prÃximo ao esperado enquanto o catalisador FeCP1 ficou aquÃm do desejado. Os difratogramas obtidos por DRX mostraram um maior grau de cristalinidade da amostra FeCP2, enquanto FeCP1 e os dois suportes (CP1 e CP2) apresentaram-se como semi-cristalinos. Para o catalisador FeCP2, apresentaram-se duas fases ativas presentes, α-Fe2O3 e γ-Fe2O3; jà no FeCP1, hà apenas α-Fe2O3. A anÃlise das caracterÃsticas texturais revelou que, apÃs a introduÃÃo metÃlica no suporte, houve decrÃscimo nos valores de Ãrea especÃfica, volume de poros e diÃmetro de poros, sendo mais perceptÃvel para o catalisador FeCP2. As curvas de XPS expuseram os grupos funcionais oxigenados presentes na superfÃcie dos suportes, bem como a presenÃa do Fe+3 como fase ativa predominante em ambos os catalisadores. O espectro de ambos os catalisadores apresentou tambÃm um pico satÃlite que sugere a presenÃa de um outro estado de valÃncia do ferro semelhante ao que se tem no carbeto de ferro. As imagens obtidas por SEM exibiram forma e superfÃcie irregulares, sendo as partÃculas presentes no FeCP2 maiores que a do FeCP1 devido a sua cristalinidade. Os dados de EDS demonstraram que, aproximadamente, metade do percentual de ferro presente no catalisador encontra-se na superfÃcie. Pode-se inferir tambÃm por essa anÃlise, utilizando-se seu espectro, a presenÃa de carbeto de ferro na superfÃcie do catalisador. As curvas de TPR evidenciaram uma maior estabilidade do catalisador FeCP2 mediante o FeCP1, por este ter apresentado trÃs etapas de reduÃÃo do Ãxido de ferro e nÃo duas, como apresentada para aquele Ãltimo. O teste catalÃtico expÃs a melhor eficiÃncia do catalisador FeCP2 para a produÃÃo de hidrocarbonetos na faixa de C5-C9, para as mesmas condiÃÃes de temperatura, pressÃo e razÃo molar. Entretanto, a diminuiÃÃo da razÃo molar desfavoreceu a obtenÃÃo de hidrocarbonetos pesados. / The aim of this work was to synthesize iron catalysts supported on polymer-based activated carbons, for the Fischer-Tropsch synthesis. The preparation of the catalysts was performed by incipient wetness impregnation method using an aqueous solution of iron nitrate nonahydrate to obtain samples with approximately 55 % of iron. Two samples were prepared (FeCP1 and FECP2) and characterized by energy dispersive X-ray fluorescence (EDXRF), X-ray diffraction (XRD), nitrogen adsorption measurements, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM-EDS) and temperature-programmed reduction (TPR). The samples were also submitted to catalytic tests using different conditions of temperature (513, 528 and 543 K), pressure (20, 25 and 30 atm), and H2:CO molar ratio of 1 and 0.5. EDXRF data showed considerable difference in content of impregnated metal for both catalysts. FeCP2 exhibited an iron load close to the value expected while FeCP1 presented an iron load significantly lower than expected. XRD patterns showed a higher degree of crystallinity of the sample FeCP2, whereas FeCP1 and both supports used (CP1 and CP2) were found to be semi-crystalline. FeCP2 catalyst presented two active phases, α-Fe2O3 and γ-Fe2O3, while FeCP1 showed only one phase, α-Fe2O3. The analysis of the textural characteristics revealed a decrease in the values of the specific area, pore volume and pore diameter after the introduction of the metal into the support, which was more noticeable with the FeCP2 catalyst. XPS patterns indicated oxygen functional groups on the support surface and the presence of Fe+3 as the predominant active phase on both catalysts. The spectrum of both catalysts also showed a satellite peak which shows the presence of another valence state similar to the iron carbide. Images obtained by SEM revealed irregular shape and surface, being the particles present in FeCP2 greater than those on FeCP1 due to the crystallinity of the former. EDS data showed that approximately half of the iron percentage present in the catalyst bulk is on the surface. The presence of iron carbide on the catalyst surface can be inferred by using this spectrum analysis too. TPR graphics demonstrated a higher stability of the FeCP2, due to the three-step reduction of iron oxide instead of two as shown for the FeCP1. According to the results of the catalytic tests FeCP2 exhibited a better efficiency for the production of hydrocarbons in the C5-C9 range, for the same conditions of temperature, pressure and molar ratio. However, the decrease in the molar ratio disfavors the production of heavy hydrocarbons.

The conversion of biomass to biouel has received considerable attention as a sustainable way to produce energy. As worldwide fossil fuels become depleted these efforts grow in importance. The overall strategy is to transform the parent biomass feedstock to increase C-C bonds while reducing oxygen in the final products. A catalytic approach is often used to achieve good yields of transportation grade liquid hydrocarbons from biomass. Development of novel catalyst systems to aid in the thermochemical conversion of biomass to biouel is the focus of this thesis. Gasification of biomass produces synthesis gas (CO and H2). Synthesis gas can be converted to liquid hydrocarbons using Fischer-Tropsch (FT) synthesis. Mo/ZSM-5 FT catalysts with a potassium (K) promoter are introduced to enhance liquid hydrocarbon production and CO conversion of synthesis gas. Liquid products and CO conversion were determined using GC-MS analysis with respect to changes in K loading from 0-2%. The highest liquid product selectivity (21.7%) was found with 1.0% K loading while largest CO conversion (63%) was found with 1.2% K loading. This catalyst work was extended by introducing Ni and Co into the Mo/ZSM-5 catalysts. A copper based water gas shift catalyst (WGS) was also used in concert with the FT catalyst to improve product selectivity. This WGS catalyst promotes the in-situ production of H2 while decreasing water content. The FT+WGS catalyst were used to convert both 1:1 CO: H2 syngas and bio-syngas at 280 °C and 350 °C. The liquid hydrocarbon selectivity was significantly changed and the CO conversion was remarkably increased compared to the reactions without the dual catalyst at both temperatures. In the fourth chapter, FT+WGS catalysts were studied for upgrading bio-oil model compounds. Guaiacol and furfural were used as the model compounds and upgrading reactions were done under H2, syngas and bio-syngas at 200, 250 and 300 °C. Significant conversion of both guaiacol (85%) and furfural (100%) occurred with syngas at 300 °C. Products upgraded from syngas had a higher combined heat of combustion than the products with pure H2. This suggests the incorporation of some C from CO with model compound upgrading reactions with syngas.

No description available.

A síntese de Fischer-Tropsch é um processo de conversão do gás de síntese (CO + H2) em hidrocarbonetos de cadeias longas. Os catalisadores clássicos para a hidrogenação do CO são, principalmente, o Fe e o Co suportados em diferentes óxidos. O desempenho catalítico do catalisador é influenciado pelo tamanho, dispersão e grau de redução das partículas metálicas. Estudos recentes mostram uma promissora aplicação de materiais à base de nanofibras de carbono na catálise heterogênea. Estes materiais apresentam algumas vantagens em relação aos suportes catalíticos tradicionais, tais como: uma baixa interação metal-suporte, elevada área superficial, ausência de poros fechados, alta condutividade térmica, elevada inércia química e hidrofobicidade. Neste trabalho foram fabricados suportes catalíticos macroscópicos à base de nanofibras de carbono, empregando o método de vapor deposição, a partir da decomposição do etano. Os catalisadores foram preparados pela impregnação incipiente do Co e de promotores na superfície do suporte. Foram empregados os metais nobres, Ir, Pt e Ru, como promotores catalíticos, com o objetivo de incrementar a redutibilidade e a atividade do catalisador. Todos os catalisadores foram caracterizados por Quimissorção de CO, Fisissorção de N2, Redução a Temperatura Programada (TPR), Espectroscopia Fotoeletrônica de Raios X (XPS) e Microscopia Eletrônica de Transmissão (MET). Os catalisadores foram, então, testados na síntese de Fischer-Tropsch, utilizando um reator de leito fixo e fluxo contínuo, com análise simultânea dos produtos gasosos e controle sistemático da temperatura, pressão e vazão dos reagentes. Finalmente, foram analisados os produtos líquidos obtidos na reação com objetivo de conhecer a influência dos promotores na seletividade dos hidrocarbonetos formados. / Fischer-Tropsch synthesis is a process of converting the syngas (CO + H2) to long-chain hydrocarbons. The traditional catalysts for the CO hydrogenation are Fe and Co supported on different oxides. Catalytic performance of the catalyst is influenced by size, dispersion and degree of reduction of metal particles. Recent studies show a promising application of materials based on carbon nanofibers in heterogeneous catalysis. These materials have some advantages compared to traditional catalyst supports, such as a low metal support interaction, high surface area, no closed pores, high thermal conductivity, high chemical resistance, and hydrophobicity. In this work, based on macroscopic carbon nanofiber catalyst supports have been manufactured by employing the method of chemical vapor deposition from ethane decomposition. Catalysts were prepared by incipient wetness impregnation of Co and promoters on the support surface. Noble metals, Ir, Pt and Ru were used as catalytic promoters, with the aim of increasing the reductibility and catalyst activity. All catalysts were characterized by CO Chemisorption, N2 Physisorption, Temperature Programmed Reduction (TPR), X-ray Photoelectron Spectroscopy (XPS), and Transmission Electron Microscopy (TEM). The catalysts were then tested in the Fischer-Tropsch synthesis using a fixed bed reactor, continuous flow, with simultaneous analysis of gaseous products and systematic temperature control, pressure, and flow rate of the reactants. Finally, the liquid products obtained in the reaction were analyzed in order to determine the influence of promoters on the selectivity of hydrocarbons formed.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / A reaÃÃo de sÃntese de Fischer-Tropsch tem merecido grande atenÃÃo pela sua aplicaÃÃo no Ãmbito tecnolÃgico e cientÃfico. Este interesse està associado à conversÃo do gÃs natural em produtos lÃquidos de alta qualidade (gasolina e diesel) e elevado valor agregado. No presente trabalho à descrito a metodologia empregada na sÃntese e caracterizaÃÃo de catalisadores bimetÃlicos, com alto teor da fase ativa de ferro e cobalto, usados na sÃntese de Fischer-Tropsch, suportados em sÃlica promovidos com potÃssio e cobre com diferentes proporÃÃes em base molar. O uso de catalisadores de ferro utilizados na sÃntese de Fischer-Tropsch tem sido estudado por muitos pesquisadores, os resultados tÃm mostrado que estes possuem um desempenho satisfatÃrio na produÃÃo de combustÃveis lÃquidos. Entretanto, pesquisas mostram que os catalisadores de cobalto sÃo mais eficientes na produÃÃo de hidrocarbonetos de cadeia longa e linear em relaÃÃo ao ferro. Contudo, catalisadores a base de cobalto sÃo mais caros comparados aos de ferro. Uma relaÃÃo custo/benefÃcio tem que ser atingida na fabricaÃÃo de catalisadores de tal forma que tenhamos uma otimizaÃÃo da produÃÃo de combustÃveis sintÃticos de elevado peso molecular sem muitos gastos com o catalisador. Pretende-se com esta discussÃo, identificar possÃveis vias para o desenvolvimento de catalisadores mais ativos e seletivos, variando a composiÃÃo do promotor estrutural para fins de otimizar a distribuiÃÃo dos produtos (diesel e graxa). A reaÃÃo foi conduzida em um reator de leito de lama. O estudo seguiu um planejamento experimental do tipo fatorial quadrado com ponto central e os resultados foram analisados baseados na metodologia de anÃlises de superfÃcies de respostas. Os efeitos das diferentes condiÃÃes operacionais (temperatura e pressÃo) e dos diferentes teores de potÃssio e cobre na distribuiÃÃo dos produtos lÃquidos foram comparados baseados nos cromatogramas, nÃmero mÃdio de carbono (Nn). Diante dos testes realizados com os catalisadores bimetÃlicos (Fe/Co) dopados com diferentes teores de potÃssio e/ou cobre, chegou-se a uma melhor relaÃÃo entre os metais (K,Cu) para sÃntese de um catalisador mais eficiente (50Fe/50Co/12K/5Cu/139SiO2). Sendo que o objetivo desta formulaÃÃo bimetÃlica, obter vantagens de possÃveis efeitos sinergÃticos entre os dois metais (Fe/Co) e seus promotores estruturais. / The reaction of Fischer-Tropsch synthesis has received great attention for its application in technology and science. This interest is associated with conversion of natural gas into high quality liquid products (gasoline and diesel) and high added value. In the present paper describes the methodology employed in the synthesis and characterization of bimetallic catalysts with high levels of the active phase of iron and cobalt, used in the synthesis of Fischer-Tropsch, supported on silica promoted with potassium and copper with different ratios on a molar basis. The use of iron catalysts used in the Fischer-Tropsch synthesis has been studied by many researchers, the results have shown that these have a satisfactory performance in the production of liquid fuels. However, studies have shown that cobalt catalysts are most effective in producing long-chain hydrocarbons and linear with respect to iron. However, the cobalt-based catalysts are more expensive compared to iron. A cost / benefit ratio has to be reached in the manufacture of catalysts which have such an optimization of production of synthetic fuels of high molecular weight inexpensively with the catalyst. The intention with this discussion, identify possible pathways for the development of more active and selective catalysts, varying the composition of the promoter structure for purposes of optimizing the distribution of products (diesel and grease). The reaction was conducted in a reactor bed of mud. The study followed an experimental planning factorial central square and the results were analyzed based on the methodology of the analysis of response surfaces. The effects of different operating conditions (temperature and pressure) and different concentrations of potassium and copper in the distribution of liquid based on the chromatograms were compared, average carbon number (Nn). Before the tests with the bimetallic catalysts (Fe / Co) doped with different concentrations of potassium and / or copper, it was a better relationship between the metals (K, Cu) for the synthesis of a more efficient catalyst (50Fe/50Co/12K/5Cu/139SiO2). Since the goal of this formulation bimetallic take advantage of possible synergistic effects between the two metals (Fe / Co) and its structural promoters.

A necessidade de produÃÃo de combustÃveis lÃquidos, principalmente diesel com baixos teores de enxofre para atender recentes legislaÃÃes ambientais, impulsionou a pesquisa sobre a reaÃÃo de sÃntese de Fischer-Tropsch (SFT), que utiliza a polimerizaÃÃo entre monÃxido de carbono (CO) e hidrogÃnio (H2) em diversos tipos de reator e de catalisador. Foram realizadas vÃrias simulaÃÃes da reaÃÃo de sÃntese de Fischer-Tropsch em reator tubular de leito fixo com catalisador de ferro avaliando-se o efeito de determinadas condiÃÃes operacionais na distribuiÃÃo de produtos, de acordo com o modelo desenvolvido para a distribuiÃÃo das massas moleculares dos hidrocarbonetos formados. As condiÃÃes operacionais foram avaliadas de modo favorecer a formaÃÃo de diesel e graxa, que por sua vez podem ser craqueadas visando à produÃÃo de combustÃveis lÃquidos. Um planejamento experimental e uma posterior anÃlise estatÃstica foram executados de forma a apontar as condiÃÃes operacionais que mais influenciam na formaÃÃo de produtos especÃficos como gasolina, diesel e graxas, assim como na conversÃo do gÃs de sÃntese em hidrocarbonetos. Os resultados obtidos mostraram a adequaÃÃo da modelagem adotada com dados experimentais existentes na literatura / In this work, a fixed-bed tubular reactor was modeled and simulated for the Fischer-Tropsch synthesis carried out using iron-based catalysts. The model has considered the fluid-dynamics of the fixed-bed reactor and the polymerization reaction of the Fischer-Trospch synthesis. Several simulations were carried out with the mathematical model to study the effects of the operating conditions on the product distribution and on the yield into hydrocarbons. The simulations were analyzed aiming the optimization of the system toward the production of diesel and wax fractions, which can be later cracked to produce a higher amount of liquid products. The simulations were carried out following a factorial design to identify the operating conditions that most influence the production of each specific product fraction, as gasoline, diesel and waxes, and in the yield of synthesis gas into hydrocarbon

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / A reaÃÃo de sÃntese de Fischer-Tropsch tem merecido grande atenÃÃo pelo seu interesse tecnolÃgico e cientÃfico. Este interesse està associado a conversÃo do gÃs natural em produtos lÃquidos de alta qualidade (gasolina e diesel) e elevado valor agregado. No presente trabalho à descrito a metodologia empregada na sÃntese e caracterizaÃÃo de catalisadores de ferro usados na sÃntese de Fischer-Tropsch, com Ãnfase nos catalisadores suportados em sÃlica e catalisadores industriais (utilizados na sÃntese de amÃnia) promovidos com potÃssio e cobre. Pretende-se com esta discussÃo, identificar possÃveis vias para o desenvolvimento de catalisadores mais ativos e seletivos, variando a composiÃÃo do promotor estrutural para fins de otimizar a distribuiÃÃo dos produtos em fraÃÃes de hidrocarbonetos especÃficos (gasolina, diesel e graxa). A reaÃÃo foi conduzida em um reator de leito de lama. O estudo seguiu um planejamento experimental do tipo fatorial quadrado com ponto central e os resultados foram analisados baseados na metodologia dos grÃficos de superfÃcie de respostas. Os efeitos das diferentes condiÃÃes operacionais (temperatura e pressÃo) e dos diferentes teores de potÃssio na distribuiÃÃo dos produtos lÃquidos foram comparados baseados nos cromatogramas, nÃmero mÃdio de carbono (Nn) e no grau de dispersÃo dos produtos. Para todos os catalisadores de ferro empregados neste trabalho, observou-se um aumento no Ãndice que representa o comprimento da cadeia de hidrocarboneto (Nn) com o aumento do teor de potÃssio. Indicando um maior grau de polimerizaÃÃo para os catalisadores de ferro suportados com 18K em ralaÃÃo aos outros (12K, 6K e industrial). Os resultados mostram que, para catalisadores suportados, em pressÃes elevadas (25 e 30atm) favorecem a produÃÃo de graxa, enquanto a seletividade para hidrocarbonetos lÃquidos à favorecida a baixa pressÃo (20atm) e baixa temperatura (240ÂC). Para os catalisadores industriais, observou-se um aumento na fraÃÃo graxa em baixas temperaturas (240-255ÂC) e elevadas pressÃes (30atm). Contudo, os resultados de todas as corridas para o catalisador suportado e o industrial promovido e nÃo-promovido apresentaram quantidades significativas de n-parafinas com no mÃximo 35 Ãtomos de carbono que pode ser causados atravÃs das limitaÃÃes geomÃtricas e espaciais dentro dos poros do catalisador que tambÃm podem explicar o motivo pelo qual o Ãndice de dispersÃo da distribuiÃÃo de hidrocarbonetos serem mais baixos para um maior nÃmero de carbonos mÃdio. / The Fischer-Tropsch synthesis has been focus of attention of the scientific and industrial community. This interest is related to the conversion of natural gas into high quality liquid products, such as gasoline and diesel, which have high commercial value. In this work the methodology applied to synthesize and characterize iron-based catalyst used in the Fischer-Tropsch synthesis was described. Emphasis was given to catalysts supported in silica and to industrial catalysts (used in the synthesis of ammonia) impregnated with potassium and copper. The catalysts were tested to identify more active and selective catalysts, changing the amount of structural promoter in order to optimize the product distribution of specific hydrocarbons (gasoline, diesel, wax). The reaction was carried out in a slurry phase reactor. The experiments followed a 22 factorial experimental planning with central point and the results were analyzed based on the surface response methodology. The effects of the operating conditions (temperature and pressure) and of the amount of potassium in the catalyst on the liquid product distribution were compared based on the chromatographs, number average number of carbons (Nn) and distribution dispersion. In all iron based catalyst used in the research, the number average number of carbons (Nn) increased with increasing amount of potassium in the catalyst formulation. This result indicates that the catalyst with 18 K supported in silica showed the highest degree of polymerization in comparison with all other catalysts produced in this research. The results showed that for the catalyst supported in silica high pressures (25 to 30 atm) favor the production of wax, while higher selectivity towards liquid fuels was favored by low pressure (20 atm) and low temperature (240ÂC). For the industrial catalyst, an increase in the wax cat was observed at low temperatures (240-255ÂC) and high pressures (30 atm). The experiments carried out with the both catalysts (silica-supported and alumina-supported) have presented significant amounts of n-paraffins with a maximum of 35 carbons and low dispersion of the product distribution which can be caused by space limitations within the catalyst pores.

A síntese de Fischer-Tropsch é um processo de conversão do gás de síntese (CO + H2) em hidrocarbonetos de cadeias longas. Os catalisadores clássicos para a hidrogenação do CO são, principalmente, o Fe e o Co suportados em diferentes óxidos. O desempenho catalítico do catalisador é influenciado pelo tamanho, dispersão e grau de redução das partículas metálicas. Estudos recentes mostram uma promissora aplicação de materiais à base de nanofibras de carbono na catálise heterogênea. Estes materiais apresentam algumas vantagens em relação aos suportes catalíticos tradicionais, tais como: uma baixa interação metal-suporte, elevada área superficial, ausência de poros fechados, alta condutividade térmica, elevada inércia química e hidrofobicidade. Neste trabalho foram fabricados suportes catalíticos macroscópicos à base de nanofibras de carbono, empregando o método de vapor deposição, a partir da decomposição do etano. Os catalisadores foram preparados pela impregnação incipiente do Co e de promotores na superfície do suporte. Foram empregados os metais nobres, Ir, Pt e Ru, como promotores catalíticos, com o objetivo de incrementar a redutibilidade e a atividade do catalisador. Todos os catalisadores foram caracterizados por Quimissorção de CO, Fisissorção de N2, Redução a Temperatura Programada (TPR), Espectroscopia Fotoeletrônica de Raios X (XPS) e Microscopia Eletrônica de Transmissão (MET). Os catalisadores foram, então, testados na síntese de Fischer-Tropsch, utilizando um reator de leito fixo e fluxo contínuo, com análise simultânea dos produtos gasosos e controle sistemático da temperatura, pressão e vazão dos reagentes. Finalmente, foram analisados os produtos líquidos obtidos na reação com objetivo de conhecer a influência dos promotores na seletividade dos hidrocarbonetos formados. / Fischer-Tropsch synthesis is a process of converting the syngas (CO + H2) to long-chain hydrocarbons. The traditional catalysts for the CO hydrogenation are Fe and Co supported on different oxides. Catalytic performance of the catalyst is influenced by size, dispersion and degree of reduction of metal particles. Recent studies show a promising application of materials based on carbon nanofibers in heterogeneous catalysis. These materials have some advantages compared to traditional catalyst supports, such as a low metal support interaction, high surface area, no closed pores, high thermal conductivity, high chemical resistance, and hydrophobicity. In this work, based on macroscopic carbon nanofiber catalyst supports have been manufactured by employing the method of chemical vapor deposition from ethane decomposition. Catalysts were prepared by incipient wetness impregnation of Co and promoters on the support surface. Noble metals, Ir, Pt and Ru were used as catalytic promoters, with the aim of increasing the reductibility and catalyst activity. All catalysts were characterized by CO Chemisorption, N2 Physisorption, Temperature Programmed Reduction (TPR), X-ray Photoelectron Spectroscopy (XPS), and Transmission Electron Microscopy (TEM). The catalysts were then tested in the Fischer-Tropsch synthesis using a fixed bed reactor, continuous flow, with simultaneous analysis of gaseous products and systematic temperature control, pressure, and flow rate of the reactants. Finally, the liquid products obtained in the reaction were analyzed in order to determine the influence of promoters on the selectivity of hydrocarbons formed.

In this work, carbonaceous deposits on spent HTFT catalysts were investigated. This research was required in order to better understand the observed loss in productivity observed in the industrial reactors, with the aim of improving the economy of the HTFT process. A host of complementary techniques were employed to systematically determine the composition of a typical catalyst recovered from a reactor. Spent HTFT catalysts are comprised of magnetite and a mixture of iron carbides as well as adsorbed hydrocarbon products (soft carbon) and hard carbon. Reaction initiates at the particle surface and along the promoter-rich grain boundaries toward the core of the grains. A partially reacted particle would therefore have a core-shell structure, with magnetite representing the unreacted region of the catalyst. The reacted region consists of a porous carbonaceous matrix with soft carbon and carbide crystallites nestled in this matrix. The hard carbonaceous species is a mixture of polymeric carbon and polycyclic aromatic hydrocarbons. The particle structure is linked to the sample preparation method and an alternative method yielding catalyst particle with uniformly distributed promoter elements could be beneficial. Investigating carbonaceous species is a complex process, and development of a fresh methodology would aid in the quest for insight into the nature of carbonaceous species in various systems. A new approach which entails a combination of the traditional techniques combined with MALDI-TOF MS enabled a deeper investigation. Additional aspects such as the molecular weight distributions along with known information about crystallinity and morphology of the catalyst provide a comprehensive study of carbonaceous material. Polymeric carbon and very large polycyclic aromatic hydrocarbons constitute hard carbon and can be observed with minimal sample preparation procedures. The evolution of the HTFT catalysts was investigated as a function of time-on-stream. This enabled us to study the effects of increasing amounts of hard carbon on the activity and the chemical and physical properties of the catalysts. The catalyst activity was found to decrease with increasing hard carbon content, although the effect of carbon deposition cannot be distinguished from phase transformation (oxidation) which occurs simultaneously. A method to quantify the amount of hard carbon, which progressively builds up on the catalyst, was demonstrated. This required a great deal of method development, which provides a platform for future investigations of these catalysts. Importantly, it allows predictions of the amounts of carbon that will be deposited after a certain reaction time. This allows more efficient regulation of catalyst replacement. The production of fine carbon-rich particles in the industrial reactor poses a major problem in the process. Carbon deposition leads to an increase in particle diameter with time on-stream. Permissible levels of hard carbon were identified, beyond which the mechanical strength of the catalyst particles deteriorate. This leads to break-up of the particles and therefore fines formation. The surface area and pore volume generally increase with progressive deposition of hard carbon, while the bulk density of the catalyst material exhibits a linear decrease with carbon build-up. A mechanism is proposed for hard carbon formation which apparently occurs through the dissociative adsorption of CO to form a carbon monolayer. This is followed by polymerisation of the carbon atoms. Meta-stable interstitial carbides are formed at the iron-carbon interface. Owing to a carbon concentration gradient between the top of the surface and the bottom of the metal or carbide particle, carbon diffusion across the crystal (carbide decomposition) and grows as a PAH molecule lifting the iron carbide away from the particle. As this corrosion process is intrinsic to iron-based catalysts, a catalyst that contains sulphur is proposed for future development.

In the Fischer-Tropsch (FT) synthesis, CO and H2 (synthesis gas) are converted into hydrocarbons that can be further upgraded to high-quality fuels and chemicals. Different carbon sources such as natural gas, coal and biomass can be used as feed-stocks for the synthesis gas. In commercial applications, supported cobalt catalysts are commonly used in the FT synthesis, especially when the synthesis gas emanates from natural gas and when the desired final product is diesel. The activity and selectivity of a cobalt catalyst is dependent on several parameters, one of them being the support. The present thesis is focused on the design, synthesis and characterization of alumina and silica materials (with and without Ce and Zr promoters) with non-conventional morphology, and evaluation of their feasibility as cobalt supports in the FT synthesis. Ce- and Zr-alumina nanoparticles were synthesized by co-precipitation in water-in-oil microemulsion. The obtained product is amorphous alumina with highly dispersed promoters, resulting in strong cobalt-support interactions and low cobalt reducibility. By increasing the calcination temperature of the Ce-promoted support, crystalline CeO2 is obtained which apparently increases the cobalt reducibility and thereby the catalytic activity (per gram catalyst). The small pore size of the materials may induce diffusion limitations on the reactants arrival and/or result in very small cobalt particles, which favour methane over long-chain hydrocarbons.  Successful preparations of pore expanded mesoporous silicas with 1D, 2D and 3D pore structures via the atrane route, combined with the addition of swelling agents, have been demonstrated. The advantage of this method is that pore expansion can be achieved at mild conditions and there is no need for a post-synthesis process using an autoclave system. In larger silica support pores, larger cobalt particles will be formed and the weaker the cobalt-support interactions will be. This generally results in a higher cobalt reducibility for larger-pore supports and thereby a higher catalytic activity. / <p>QC 20171004</p>