Lower C2–C4 olefins are important commodity chemicals usually produced by steam cracking of naphtha or fluid catalytic cracking of vacuum gas oil. The Fischer–Tropsch synthesis of lower olefins (FTO) with iron-based catalysts uses synthesis gas as an alternative feedstock. Nanostructured carbon materials are widely applied as supports for the iron nanoparticles due to their weak interaction with the metal species, facilitating the formation of catalytically active iron carbide. Numerous synthetic approaches towards carbon-supported FTO catalysts with various structures and properties have been published in recent years but structure-performance relationships remain poorly understood. We apply ordered mesoporous carbon (CMK-3) as a support material with well-defined pore structure to investigate the relationships between calcination/activation conditions and catalytic properties. After loading of iron and sodium/sulfur as the promoters, the structures and properties of the FTO catalysts are varied by using different calcination (300–1000 °C) and activation (350 or 450 °C) temperatures followed by FTO testing at 1 bar, 350 °C, H2/CO = 1. Carbothermal reduction of iron oxides by the support material occurs at calcination temperatures of 800 or 1000 °C, leading to a higher ratio of catalytically active iron(carbide) species but the catalytic activity remains low due to particle growth and blocking of the catalytically active sites with dense graphite layers. For the samples calcined at 300 and 500 °C, the formation of non-blocked iron carbide can be enhanced by activation at higher temperatures, leading to higher catalytic activity. Olefin selectivities of ∼60%C in the formed hydrocarbons with methane of ∼10%C are achieved for all catalysts under FTO conditions at low CO conversion. The influence of the calcination temperature is further investigated under industrially relevant FTO conditions. Promoted CMK-3-supported catalysts obtained at low calcination temperatures of 300–500 °C show stable operation for 140 h of time on stream at 10 bar, 340 °C, H2/CO = 2.

Biomass to Liquids via Fischer-Tropsch synthesis (BTL-FT) is regarded as one of the most promising routes for providing alternative solution to growing demand for energy and environmental protection. In Chapter I, the development and key issues of BTL-FT process (especially Fischer-Tropsch synthesis) were reviewed and identified. In Chapter II, Mo/HZSM-5 catalyst was synthesized using Incipient Wetness Impregnation method and tested in nitrogen rich model bio-syngas. Different operation parameters (temperature, pressure, and GHSV) were tested to investigate their influence on the catalytic performance. Those parameters were found to affect the performance significantly. Liquid samples from conversion were mainly composed of C8 to C10 range hydrocarbons. The catalyst characterization revealed that molybdenum species were well distributed on the catalyst support, while dealumination, agglomeration and coke deposition were observed in spent catalyst. The top layer of the spent catalyst had the most coke deposition. A Three-Dimensionally Ordered Macro-porous (3DOM) Fe based Fischer-Tropsch catalyst was developed using a facile in-situ Nitrate Oxidation-PMMA templating technique in Chapter III. Several techniques (including SEM, BET, TPR, HRTEM, XRD, XPS, and DRIFTS) were combined to characterize the morphology, textural properties and microstructures of 3DOM Fe catalysts at different stages. The effects of bio-syngas composition on carbonaceous species formation, iron phase transformation and catalytic performance were investigated and correlated. A novel hybrid bio-refinery process co-converting biomass and natural gas into liquid fuels via FTS with a CO2 recycle loop was developed, modeled and simulated by using Aspen Plus in Chapter IV. The Aspen Plus model utilized experimental data from the 3DOM Fe catalyst. Economic analysis was performed on different scenarios based on the simulation results to determine profitability of the process. Results indicated that 102.65 t/h gasoline and 22.93 t/h diesel can be produced with the co-processing of 100.00 t/h biomass and 112.3 t/h natural gas using 307.78 t/h of recycled CO2 in the process simulation. The carbon conversion rate was estimated to be 81.23% for the hybrid process. Economic analysis revealed that the process can be profitable when using at least 10.00 t/h biomass and 11.23 t/h natural gas.

[pt] Neste trabalho foram sintetizadas amostras bimetálicas de cobalto e ferro suportadas em sílicas mesoporosas do tipo SBA-15 e HMS. A preparação das mesmas ocorreu pelo método de impregnação incipiente do ponto úmido com soluções aquosas de nitratos de Co e Fe para obtenção de amostras com 25% p/p total de metal. Para estudos de efeitos comparativos das diversas propriedades, amostras monometálicas de Co ou Fe foram também preparadas com o mesmo teor metálico. Para investigar o efeito de diferentes direcionadores de estrutura, duas séries da sílica mesoporosa HMS foram preparadas utilizando dois tipos de direcionadores: dodecilamina (DDA) e tetradecilamina (TDA). As amostras foram caracterizadas por medidas de fisissorção de N(2), análise de difração de Raios-X (DRX), redução com temperatura programada (RTP), microscopia eletrônica de transmissão (TEM), quimissorção de H(2) e espectroscopia fotoeletrônica de raios-X (XPS). A quantidade de metal incorporado foi estimada por espectroscopia de absorção atômica (EAA). Os suportes foram também caracterizados por análise diferencial termogravimétrica (ATG/ATD). As curvas ATG evidenciaram que os direcionadores de estrutura foram, em grande parte, removidos até 700 K. As propriedades de textura mostraram que após a introdução metálica no suporte SBA-15, a área específica, o volume de poros e o diâmetro de poro decresceram em menor extensão para a amostra bimetálica em relação às monometálicas. As análises de DRX detectaram a formação das fases de Co(3)O(4) e CoFe(2)O(4) para todas as amostras bimetálicas; sendo que para a amostra de Co-Fe/HMS (TDA), a fase a-Fe(2)O(3) foi também indicada. A presença do suporte HMS (TDA) resultou na formação de fases cristalitas de maiores dimensões. Os valores das espessuras de parede para os suportes do tipo HMS foram maiores em relação aos encontrados na literatura, sugerindo a formação de materiais mais estáveis. Os perfis de RTP foram similares entre as amostras monometálicas e bimetálicas, entretanto, maiores temperaturas de redução do óxido de cobalto na amostra bimetálica foi indicada em relação às amostras monometálicas de cobalto, no suporte HMS (TDA). Uma interação metal-suporte mais forte foi evidenciada para a amostra Co-Fe/SBA-15. As medidas de quimissorção de H(2) indicaram valores das dispersões metálicas maiores para as amostras bimetálicas em comparação as monometálicas de ferro e menores em relação às monometálicas de cobalto. A partir das micrografias obtidas por MET, foi observada uma menor formação (percentual) de aglomerados para a amostra de Co-Fe/SBA-15 em relação à de Co-Fe/HMS (DDA). O espectro Co2p resultante da análise de XPS, para a amostra bimetálica de Co-Fe/HMS (DDA) indicou a presença de Co(3)O(4). O catalisador de Co-Fe/HMS (DDA) apresentou maiores seletividades para C(5+) e álcoois em relação ao catalisador Fe/HMS (DDA) na síntese de Fischer-Tropsch. O parâmetro de probabilidade de crescimento da cadeia (a) foi maior para o catalisador bimetálico Co-Fe/HMS (DDA) em comparação ao catalisador Co-Fe/SBA-15. Ambos os catalisadores bimetálicos exibiram uma seletividade (%) maior para a fração de leves, C2-C4. / [en] In this work, cobalt and iron bimetallic samples supported on SBA-15 or HMS mesoporous sílicas were prepared by incipient wetness impregnation. Cobalt nitrate and iron salts were used to obtain samples containing 25 wt% total of metal content. Also, a series of supported monometallic cobalt or iron samples were synthesized, with the same metal loading, and compared to bimetallic ones. In order, to investigate the effect of different templates, a series of HMS sílicas have been prepared using two types of structure direction: dodecylamine (DDA) and tetradecylamine (TDA). The samples were cheracterized by N(2)-physisorption, X-ray diffraction (XRD), temperature programmed reduction (TPR), transmission electron microscopy (TEM), H(2) chemisorption and X-ray photoelectron spectroscopy (XPS) analysis. The amount of incorporated metal was estimated by atomic absorption spectroscopy (AAS). The supports were, also, characterized by thermogravimetric (TGA), as well as differential thermal (DTA) analyses. The TGA/DTA curves showed that the templates were mainly removed until 700 K. The textural properties revealed that after metal introduction to SBA-15 support, specific area, pore volume and pore diameter decreased in a lesser extension for the bimetallic sample compared to monometallic ones. XRD measurements detected the formation of Co(3)O(4) and CoFe(2)O(4) phases for all bimetallic samples. For Co-Fe/HMS (TDA) sample, the a-Fe(2)O(3) phase formation and a higher Co(3)O(4)/CoFe(2)O(4) crystallite sizes were also observed. The wall thickness valour for HMS supports was higher than previously reported values, suggesting more stable materials. The TPR profiles indicated similar behavior between bimetallic and monometallic samples. In case of cobalt oxide on bimetallic sample, higher reduction temperatures were indicated compared to monometallic ones for HMS (TDA) support. A higher interaction metal-support was showed for Co-Fe/SBA- 15. According to hydrogen chemisorption, the bimetallic samples dispersions were higher than iron monometallic and lower than cobalt monometallic samples. From TEM microphotografs, it was observed a lesser fraction of agglomerates to Co-Fe/SBA-15 than Co-Fe/HMS (DDA) sample. XPS spectrum of Co2p region indicated the presence of Co(3)O(4) for the bimetallic sample, Co-Fe/HMS (DDA). The Fe-Co/HMS (DDA) bimetallic catalyst showed higher C(5+) and alcohols selectivities than Fe/HMS (DDA) on the Fischer-Tropsch reaction. Also, the bimetallic cobalt and iron based catalyst supported on HMS (DDA) recorded a higher value for the chain growth parameter (a) than Co-Fe/SBA-15. Both bimetallic catalysts exhibited highter selectivities (%) for lighter fractions, C2-C4.

Ce travail met en évidence le potentiel que la technologie des plasmas présente dans l’élaboration, en une seule étape, des catalyseurs de la synthèse Fischer-Tropsch (SFT), alors que les méthodes habituelles ou conventionnelles comme l’imprégnation et la précipitation sont des voies de production multi-étapes du matériau catalytique. Les nouveaux catalyseurs ont été mis en œuvre à partir d’espèces monométalliques ayant comme support le carbone (Fe/C, Co/C) pour développer des bimétalliques (Co-Fe), des ternaires (Mo-Co-Fe, Ni-Co-Fe) qui ont été ensuite formulés avec la présence de promoteurs (Au/Ni-Co-Fe). Du fait que la préparation par plasma thermique de ces catalyseurs nanométriques supportés par le carbone soit relativement récente, cela permet d’envisager des perspectives d’applications avec des retombées industrielles, car les hautes températures caractéristiques des plasmas permettent de générer des carbures de fer (Fe3C, Fe5C2) très importants dans le processus catalytique de SFT. Des efforts de quantification de toutes les phases de carbures ont été effectués à l’aide de la diffraction des rayons X (DRX), tandis que l’analyse quantitative à l’aide du Rietveld (AQR) n’a été que partiellement concluante à cause de la taille nanométrique des matériaux étudiés qui est en dessous des limites de détection instrumental. Avec des aires spécifiques de BET comprises entre 35 et 93 m2.g-1, les catalyseurs sont typiques de matériaux poreux et présentent ainsi un avantage pour la SFT car les transformations réactionnelles ne sont pas limitées par les phénomènes de transfert de masse. La microscopie électronique à transmission (MET) et la microscopie électronique à balayage (MEB) couplées avec la Spectroscopie à rayons X à dispersion d'énergie (EDX) et la cartographie des rayons X (cartographie X) ont montré une grande dispersion des particules métalliques dans la matrice de carbone, indiquant ainsi l’absence d’agglomération sur les échantillons frais et post réactionnels. Les caractérisations par la spectroscopie Raman et la Spectroscopie photoélectronique par rayon X (XPS) ont mis en évidence un support de catalyseur essentiellement graphitique. Les analyses par la spectroscopie d’absorption des rayons X (SAX), par la spectroscopie de structure près du front d’absorption des rayons X (XANES) ont confirmé que le catalyseur Co/C obtenu par plasma contenait des carbures (Co3C) qui n’ont pu être révélés par XPS. Le test catalytique initial a été effectué en réacteur à lit fixe à 503 K (230°C), sous une pression de 3 MPa avec une vitesse volumique spatiale (VVH) de 6 000 〖cm〗^3 〖.h〗^(-1).g^(-1), pour une durée de 24 heures. Par la suite, les tests ont été performés dans un réacteur triphasique agité continu (3-φ-CSTSR) opérant de façon isotherme pendant 24 heures à des températures de 493–533 K (220–260°C), sous 2 MPa et à VVH = 3 600 〖 cm〗^3 〖.h〗^(-1).g^(-1). Tous les catalyseurs étudiés ont été actifs pour la SFT, produisant des fractions de gasoline (essence) et de diesel mais avec des sélectivités qui dépendaient de la proportion de métal présent dans le catalyseur et des conditions réactionnelles. À 493 K, le catalyseur le plus actif a été Co/C, obtenu par plasma, avec 40% de conversion qui contraste avec les 32% du meilleur catalyseur commercial Fe/C. Ces performances ont été comparées avec celles d’autres catalyseurs synthétisés par plasma Fe/C (25% de conversion) et 80%Co-20%Fe/C (10%), tandis que 50%Co-50%Fe/C, 30%Co-70%Fe/C n’ont montré aucune activité. Le catalyseur Co/C a été aussi le plus sélectif pour la formation de gasoline; mais à 533 K il a généré des quantités excessives de CH4 (46%) et CO2 (19%); ce qui a conduit à l’idée de synthétiser des bimétalliques Co-Fe/C qui ont permis d’abaisser la sélectivité en CH4 ou CO2 en dessous de 10%, pour une conversion de CO dépassant 40%. De même, les catalyseurs contenant du Ni (Ni-Co-Fe/C) ont été plus actifs avec des conversions de CO dépassant 50% avec des sélectivités en gasoline (38%) plus élevées qu’en diesel (20%). Ce catalyseur bimétallique a aussi favorisé la formation importante de CH4 (23%) et de CO2 (14%) beaucoup plus que dans le cas du solide Co-Fe/C. Globalement, le catalyseur bimétallique Co-Fe et sa variante acidifiée (exemple Mo-Co-Fe) ont été plus sélectifs en diesel (~ 55%). L’influence du prétraitement a été examinée et, selon la composition des catalyseurs, ceux qui ont été initialement réduits par CO avaient montré une amélioration de la sélectivité en diesel (50–67%); ces performances se sont avérées meilleures par rapport à celles des solides initialement réduits par H2 (45–55%). En outre, les catalyseurs aux concentrations élevées en cobalt, ainsi que ceux prétraités sous hydrogène ont généré plus d’eau que ceux prétraités ou réduits par CO. La présence d’atomes d’or comme promoteur dans le catalyseur Ni-Co-Fe/C (Au/Ni-Co-Fe/C) a non seulement ralenti l’activité de Ni-Co-Fe/C, mais aussi a diminué sa capacité à former l’eau, bien que n’ayant eu aucun impact significatif sur la sélectivité en composés hydrocarbonés. / Abstract : This work reveals the potential plasma technology presents in producing highly active catalysts for Fischer-Tropsch synthesis (FTS), while simultaneously contracting catalyst production into a single step, which is a certain departure from the traditional multi-step methods such as impregnation or precipitation. Novel catalysts proposed were carbon-based, developed from single metal (Fe/C, Co/C) to bimetallic (Co-Fe), ternary (Mo-Co-Fe, Ni-Co-Fe) and then the promoted Au/Ni-Co-Fe formulations. Since the preparation of nanometric carbon-supported catalysts by plasma is a relatively new phenomenon, it offers the Fischer-Tropsch catalysis prospects of future commercial applications, because of the high temperatures that are achieved in plasma create Fe carbides (Fe3C, Fe5C2), which are assumed to account for Fe-based FTS catalysis. An attempt to fully quantify the carbide phases in the samples by X-ray diffraction (XRD) and Rietveld Quantitative Analysis (RQA) was only partially successful due to the nanometric nature of the materials existing below the instrument’s detection limits. With BET specific surface areas of 35–93 m2.g-1, the catalysts were found to be non-porous, a characteristic that is advantageous because Fischer-Tropsch reaction would operate away from mass transfer limitations. Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) coupled with Energy Dispersive X-ray Spectroscopy (EDX) and X-ray mapping indicated high dispersion of the metal moieties in the carbon matrix, with no signs of nanoparticle agglomeration both in the fresh and used samples. Raman and X-ray Photoelectron Spectroscopy (XPS) characterized the support as highly graphitic, mixed with amorphous carbon arising from substantial defects in the graphite. Evidence from X-ray Absorption Spectroscopy (XAS) using X-ray Absorption Near Edge Structure (XANES) analysis confirmed that plasma synthesized Co/C catalyst contained some carbides (Co3C), which went undetected by XPS. Initial catalyst testing was performed in the fixed-bed reactor at 503 K (230C), 3 MPa pressure, and gas hourly space velocity (GHSV) of 6 000 〖cm〗^3 〖.h〗^(-1).g^(-1) of catalyst for 24 h. Elaborate tests were further executed in a 3-phase continuously stirred-tank slurry reactor (3-φ-CSTSR) isothermally operated between 493–533 K (220–260°C) at 2 MPa pressure, and GHSV = 3 600 〖cm〗^3 〖.h〗^(-1).g^(-1) of catalyst, for 24 h. It was observed that all catalysts were active for FTS, producing both gasoline and diesel fractions, but selectivity depended on the amount of metal in the catalyst or the reaction conditions. The most active catalyst at 493 K was the plasma-synthesized Co/C that showed 40% CO conversion, which was benchmarked against the commercial Fe/C at 32%. This performance was compared to the plasma-synthesized Fe/C (25% CO conversion) and 80%Co-20%Fe/C (10% CO conversion), while both the 50%Co-50%Fe/C and 30%Co-70%Fe/C were inactive. The plasma-synthesized Co/C was also more selective towards the gasoline fraction, but at 533 K it generated excessive CH4 (46%) and CO2 (19%) prompting the development of the Co-Fe/C bimetallics, which exhibited less than 10% selectivity towards CH4 or CO2 at over 40% CO conversion. Similarly, Ni-containing catalysts (Ni-Co-Fe/C) were relatively more active than the bimetallics, exhibiting over 50% CO conversion with higher selectivity towards the gasoline fraction (38%) than towards diesel (20%). The Ni-Co-Fe/C catalysts also produced excessive CH4 (23%) and CO2 (14%), than the Co-Fe/C bimetallics. Overall, the Co-Fe bimetallics and the acidified Co-Fe catalyst (i.e. Mo-Co-Fe/C) were more selective towards diesel formation (~55%). When the effect of pre-treatment medium was investigated, depending on catalyst composition, the CO-reduced catalysts showed enhanced selectivity for diesel fraction (50–67%) than catalysts reduced in H2 (45–55%). In addition, it was observed that catalysts containing high concentration of Co as well as those reduced in H2 generated more H2O than those reduced in CO, and the presence of Au (that is, in Ni-Co-Fe/C) not only depressed the Ni-Co-Fe/C catalyst activity, but it also lowered its capacity to form H2O, although it had no significant impact on the catalyst’s hydrocarbon selectivity.

Há uma demanda global pelo abastecimento de combustíveis veiculares menos poluentes, tanto por questões energéticas quanto sócio-ambientais. Uma potencial alternativa, que traduz a possibilidade de um biocombustível sem as limitações da Primeira Geração, é a rota tecnológica conhecida como Biomass-to-Liquids (BTL) que, através da gaseificação e da síntese Fischer-Tropsch, possibilita a obtenção de biocombustíveis líquidos, como o óleo diesel sintético, provenientes da biomassa moderna, nesse estudo, a biomassa lignocelulósica. Para a produção em escala comercial de um biocombustível da Segunda Geração, um complexo planejamento e altos investimentos são demandados dado seu pioneirismo e ausência de histórico de mercado ou modelos precisos. Uma metodologia desenvolvida em 2006 pelo pesquisador Harold Boerrigter propõe o dimensionamento ideal de uma planta BTL a partir de uma planta Gas-to-Liquids (GTL); são aqui propostas correções e atualizações para esta metodologia, sugerindo-se uma curva capaz de apontar a influência da economia de escala em plantas BTL e uma fórmula para o cálculo estimado do Total Capital Investment (TCI) destas plantas até o momento o Brasil não dispõe de nenhuma planta que opere pela rota BTL. Segue-se com considerações sobre a oferta de resíduos florestais no território brasileiro e a constatação de que a mesma seria insuficiente como matéria-prima para sustentar grandes plantas BTL, fazendo-se necessário o emprego de culturas planejadas na forma de florestas energéticas. Uma vez feita tal análise, apresenta-se o histórico, desde sua concepção até o seu fechamento, da primeira planta a operar pela rota BTL e a produzir o designer fuel batizado de SunDiesel®: construída na Alemanha, a CHOREN Industritechnik contribui com sua experiência de anos e também com a tecnologia de gaseificação Carbo-V® para as pesquisas com os biocombustíveis sintéticos. Seu exemplo pode sinalizar um alerta com relação ao dispêndio de esforços em projetos desta natureza dadas as incertezas econômicas que circundam as fronteiras tecnológicas dos combustíveis da Segunda Geração. / There is a global demand for the supply of less polluting vehicular fuels as much by energy issues as socio-environmental. A potential alternative meaning the possibility of a biofuel without the limitations from the First Generation is the technological route known as Biomass-to-Liquids (BTL) which via gasification and the Fischer-Tropsch synthesis turns possible to obtain liquid biofuels such synthetic diesel oil from modern biomass, in this study, the lignocellulosic biomass. For commercial-scale production of a Second Generation biofuel, a complex planning and high investments are required given its pioneering and absence of market history or precise models. A methodology developed in 2006 by researcher Harold Boerrigter proposes the ideal sizing for a BTL plant assuming a Gas-to-Liquids (GTL) plant; here are proposed corrections and updates for this methodology, suggesting a curve able to point the influence of economy of scale in BTL plants and a formula for the calculation of an estimated Total Capital Investment (TCI) of these plants by the present time Brazil has no plant operating by BTL route. The research follows up with issues regarding forest residues provision in the Brazilian territory and conlcuding that the same would be insufficient as a raw material to sustain large BTL plants, making necessary the use of planned crops in the form of energy forests. Once made such analysis, it is presented the history since its beginning until its closing for the first plant to operate by the BTL route and to produce the designer fuel called SunDiesel®: built in Germany, the CHOREN Industritechnik contributes with its experience of years and also with the gasification technology Carbo-V® for researches with synthetic biofuels. Such example may indicates an alert regarding the expenditure of efforts on projects of this nature, given the economic uncertainties that surround the Second Generation fuels technological frontiers.

[pt] A síntese de Fischer-Tropsch converte o gás de síntese (H2 + CO), em uma variedade complexa de hidrocarbonetos na presença de um catalisador (principalmente Co/Al2O3). Neste trabalho foram estudados catalisadores de Co e o Fe (1 e 5% em massa), incorporados aos suportes: zeólitas KL, HL 0,1M e HL 1,0 M, além da peneira molecular mesoporosa MCM- 41, pelo método de impregnação úmida incipiente, para a reação de Fischer- Tropsch. As amostras preparadas foram analisadas pelas técnicas de: Espectometria de Emissão Atômica de Plasma Acoplado Induzido, Adsorção Física de N2 pelo método BET, Difração de Raios-X, Redução com Temperatura Programada, Microscopia Eletrônica de Transmissão (MET), Quimissorção de Hidrogênio e Espectroscopia no Infravermelho de piridina adsorvida. Além disso, as amostras foram avaliadas em um reator de leito fixo na reação de Fischer-Tropsch. Para as amostras de ferro, com mesmo teor e suportes diferentes, pode-se observar que a amostra suportada na MCM-41 apresentou um grau de redução menor. Entre as amostras de ferro suportadas na KL, a 5% Fe/KL apresentou maior grau de redução e foi observado por microscopia eletrônica de transmissão (MET) que as partículas de ferro apresentaram diâmetro em torno de 6 nm. Para as amostras de cobalto foi observado que a temperatura de redução da amostra suportada na MCM-41 foi mais alta. A amostra 5% Co/KL apresentou um maior grau de redução. Foi possível observar por MET que as partículas de cobalto apresentaram diâmetro variando entre 8 e 20 nm. Verificou-se que o catalisador com maior teor de ferro proporcionou uma maior conversão de CO, tendo sido a distribuição de produtos deslocada para as frações mais leves. Comparando os catalisadores de ferro suportados na zeólita KL e na MCM-41 pode-se concluir que as conversões são da mesma ordem de grandeza. Foi observado que o ferro foi mais ativo que o cobalto em termos de conversão do CO, sendo que o cobalto promoveu a formação de uma maior quantidade de produtos na faixa de diesel, assim como uma menor quantidade de leves. / [en] The Fischer- Tropsch synthesis converts the synthesis gas (H2 + CO), in a complex variety of hydrocarbons, using a catalyst (Co/Al2O3 normally) were introduced to the used supports by the wetness incipient impregnation. The samples were analyzed by several techniques such as: plasma- emission spectrometry (ICP- EAS), N2 physical adsorption by BET method, X-ray diffraction (XRD), temperature programmed reduction (TPR), transmission electronic microscopy (TEM), hydrogen chemisorption and Infrared Spectroscopy of adsorbed pyridine. The catalysts were evaluated using a fixed bed reactor in the Fischer-Tropsch synthesis. For the iron samples, with the same metal content and different supports, it was observed that the MCM-41 sample presented the lowest reduction level. Among the iron samples supported in KL zeolite, the 5% Fe/KL sample presented the largest reduction level. It was observed by transmission electronic microscopy that the iron particles diameter measured around 6 nm. For the cobalt samples, it was observed that the reduction temperature of the MCM-41 supported was the highest one. The 5% Co/KL sample presented the largest reduction level. It was observed by TEM that the cobalt particles presented diameters in the range from 8 to 20 nm. It was verified that the catalyst with the largest iron percentage promoved the highest CO conversion. The products distribuition was shifted to light fractions. It was observed similar conversions to iron catalysts supported in the KL zeolite and in the MCM- 41 mesoporous molecular sieve. The iron catalysts were more active than the cobalt ones in the CO conversion, but tha cobalt catalysts promoted a higher content of diesel fraction and lesser light fractions.

Há uma demanda global pelo abastecimento de combustíveis veiculares menos poluentes, tanto por questões energéticas quanto sócio-ambientais. Uma potencial alternativa, que traduz a possibilidade de um biocombustível sem as limitações da Primeira Geração, é a rota tecnológica conhecida como Biomass-to-Liquids (BTL) que, através da gaseificação e da síntese Fischer-Tropsch, possibilita a obtenção de biocombustíveis líquidos, como o óleo diesel sintético, provenientes da biomassa moderna, nesse estudo, a biomassa lignocelulósica. Para a produção em escala comercial de um biocombustível da Segunda Geração, um complexo planejamento e altos investimentos são demandados dado seu pioneirismo e ausência de histórico de mercado ou modelos precisos. Uma metodologia desenvolvida em 2006 pelo pesquisador Harold Boerrigter propõe o dimensionamento ideal de uma planta BTL a partir de uma planta Gas-to-Liquids (GTL); são aqui propostas correções e atualizações para esta metodologia, sugerindo-se uma curva capaz de apontar a influência da economia de escala em plantas BTL e uma fórmula para o cálculo estimado do Total Capital Investment (TCI) destas plantas até o momento o Brasil não dispõe de nenhuma planta que opere pela rota BTL. Segue-se com considerações sobre a oferta de resíduos florestais no território brasileiro e a constatação de que a mesma seria insuficiente como matéria-prima para sustentar grandes plantas BTL, fazendo-se necessário o emprego de culturas planejadas na forma de florestas energéticas. Uma vez feita tal análise, apresenta-se o histórico, desde sua concepção até o seu fechamento, da primeira planta a operar pela rota BTL e a produzir o designer fuel batizado de SunDiesel®: construída na Alemanha, a CHOREN Industritechnik contribui com sua experiência de anos e também com a tecnologia de gaseificação Carbo-V® para as pesquisas com os biocombustíveis sintéticos. Seu exemplo pode sinalizar um alerta com relação ao dispêndio de esforços em projetos desta natureza dadas as incertezas econômicas que circundam as fronteiras tecnológicas dos combustíveis da Segunda Geração. / There is a global demand for the supply of less polluting vehicular fuels as much by energy issues as socio-environmental. A potential alternative meaning the possibility of a biofuel without the limitations from the First Generation is the technological route known as Biomass-to-Liquids (BTL) which via gasification and the Fischer-Tropsch synthesis turns possible to obtain liquid biofuels such synthetic diesel oil from modern biomass, in this study, the lignocellulosic biomass. For commercial-scale production of a Second Generation biofuel, a complex planning and high investments are required given its pioneering and absence of market history or precise models. A methodology developed in 2006 by researcher Harold Boerrigter proposes the ideal sizing for a BTL plant assuming a Gas-to-Liquids (GTL) plant; here are proposed corrections and updates for this methodology, suggesting a curve able to point the influence of economy of scale in BTL plants and a formula for the calculation of an estimated Total Capital Investment (TCI) of these plants by the present time Brazil has no plant operating by BTL route. The research follows up with issues regarding forest residues provision in the Brazilian territory and conlcuding that the same would be insufficient as a raw material to sustain large BTL plants, making necessary the use of planned crops in the form of energy forests. Once made such analysis, it is presented the history since its beginning until its closing for the first plant to operate by the BTL route and to produce the designer fuel called SunDiesel®: built in Germany, the CHOREN Industritechnik contributes with its experience of years and also with the gasification technology Carbo-V® for researches with synthetic biofuels. Such example may indicates an alert regarding the expenditure of efforts on projects of this nature, given the economic uncertainties that surround the Second Generation fuels technological frontiers.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Diante das atuais exigÃncias ambientais e uma possÃvel instabilidade no mercado internacional de petrÃleo, o processo de SÃntese de Fischer-Tropsch (SFT) representa uma nova trajetÃria tecnolÃgica na busca de combustÃveis alternativos limpos. A SFT Ã uma reaÃÃo de polimerizaÃÃo, na qual o gÃs de sÃntese (H2 + CO) reage na presenÃa de um catalisador produzindo uma mistura de hidrocarbonetos. A fim de se estudar o efeito das condiÃÃes operacionais (temperatura e pressÃo) e do teor de lÃtio como promotor em catalisadores de ferro para a (SFT) foram sintetizados trÃs catalisadores suportados em sÃlica. A composiÃÃo desses catalisadores em base molar seguiu o padrÃo: 100Fe/5Cu/24K/240SiO2, variando apenas a concentraÃÃo de lÃtio, em 06Li, 12Li e 24Li. Os catalisadores foram caracterizados atravÃs das tÃcnicas de fluorescÃncia de raios-X, difraÃÃo de raios-X, anÃlise termogravimÃtrica, anÃlise textural e reduÃÃo a temperatura programada. Foi realizado um planejamento experimental fatorial para cada catalisador e as variÃveis respostas selecionadas foram o nÃmero mÃdio de carbono (Nm), a dispersÃo e a curtose da distribuiÃÃo dos produtos. A pressÃo variou de 240 a 270ÂC e a pressÃo de 20 a 30 atm. As reaÃÃes foram conduzidas em um reator de leito de lama de alta pressÃo e os produtos gerados foram analisados por cromatografia gasosa e identificados atravÃs de padrÃes internos e quantificados a partir de balanÃos molares e programa computacional de estimativa de Ãrea dos picos. A distribuiÃÃo de hidrocarbonetos resultantes da reaÃÃo da SÃntese de Fischer-Tropsch apresentou comportamento de uma distribuiÃÃo normal para fraÃÃo diesel e graxa, semelhante ao comportamento de uma Gaussiana para todos os catalisadores nas condiÃÃes estudadas. Os produtos lÃquidos obtidos nas corridas experimentais da SFT sÃo constituÃdos principalmente de n-parafinas. Os resultados de todos os experimentos para os trÃs tipos de catalisador apresentaram quantidades significativas de n-parafinas na faixa de 20 a 36 Ãtomos de carbono. A anÃlise estatÃstica da perturbaÃÃo das variÃveis independentes do processo (temperatura, pressÃo e concentraÃÃo de lÃtio no catalisador) sobre o nÃmero mÃdio de carbonos mostra que apenas a concentraÃÃo de lÃtio no catalisador tem um efeito significativo para um intervalo de confianÃa de 90%. A concentraÃÃo de lÃtio apresenta influÃncia negativa, indicando que sua utilizaÃÃo desfavorece a produÃÃo de hidrocarbonetos de maior peso molecular. / New environmental regulations and a possible instability in the international oil market have led to a renewal interest in the Fischer-Tropsch Synthesis (FTS), which is an alternative to produce more environmental friendly fuels. The FTS is a polymerization reaction, in which syngas (H2 + CO) reacts in the presence of catalyst to produce hydrocarbons. Three iron-based catalysts supported in silica and promoted with lithium were synthesized and the effects of lithium content and operating conditions (temperature and pressure) were studied. The composition of the catalysts was based on 100Fe/5Cu/24K/240SiO2 (molar basis) with varying lithium concentration 06Li, 12Li e 24Li. The catalysts were characterized by X-ray fluorescence, X-ray diffraction, thermogravimetric analysis, textural analysis and temperature programming reduction. An experimental planning was carried out for each catalyst, varying the temperature from 240 to 270 ÂC and the pressure from 20 to 30 atm. The answer variables were the average carbon number (Nm), dispersion and curtosis of the product distribution. The reactions were carried out in a slurry bed reactor and the products were analyzed by gas chromatography. The products were identified by means of internal standards and quantified by mass balance. The product distribution of the FTS presented a normal distribution in the diesel and wax region. The distribution was similar to a Gaussian curve for all catalysts. The liquid products consisted mainly of n-parafins. The results for all catalysts presented significant quantities of n-parafins in the range of 20 to 36 carbons. The perturbation analysis of the independent variables (temperature, pressure and lithium content) showed that only the lithium content has a significant effect over the average carbon number, at a 90% confidence level. The lithium content presented a negative effect over the average carbon number.

La chimie de surface de petites nanoparticules métalliques ( ~ 1 nm), principalement de ruthénium ou d'alliages de ruthénium, a été étudiée par une approche théorique au niveau DFT. Cela est appuyé par le développement d'outils d'analyse de propriétés structurales, électroniques et thermodynamiques de ces nanoparticules. Une première partie est consacrée à l'étude des propriétés structurales de nanoparticules métalliques. La variété de morphologie des nanoparticules ainsi que la nécessité de pouvoir générer des modèles appropriés sont mises en évidence. En particulier, l'affinement de la génération de modèles structuraux théoriques est rendu possible via l'implémentation de méthodes de modélisation de nanoparticules génériques couplées à l'utilisation de la méthode de Monte Carlo inversé permettant se rapprocher au plus près de la réalité expérimentale. L'application à ces nanoparticules de descripteurs électroniques ou morphologiques, tels que le d-band center ou le nombre de coordination généralisé, est par la suite proposée en relation avec leur capacités d'adsorption, et plus généralement dans le cadre du principe de Sabatier. Un descripteur électronique de la liaison chimique (COHP) est appliqué aux différentes nanoparticules, pour mettre en évidence les différences entre structures aussi bien que la nature des interactions au sein du cœur métallique, ainsi qu'entre ce cœur et les espèces de surface. Enfin, l'adsorption d'espèces à la surface de ces modèles est étudiée. L'adsorption d'un seul ligand à la surface d'une nanoparticule modèle est utilisée comme sonde de détermination de sites d'adsorption préférentiels, puis des taux d'adsorption plus élevés sont considérés dans le but d'étudier l'influence de celui-ci sur l'adsorption de ligands surnuméraires, ainsi que pour rendre compte de l'influence des ligands de surface sur la morphologie du cœur métallique. Pour cela, les propriétés thermodynamiques des systèmes adsorbés ont été modélisées par prise en compte de l'influence de la pression et de la température sur la stabilité relative des diverses structures via une modélisation de thermodynamique ab initio. Enfin, cette même approche à été utilisée pour étudier la co-adsorption de ligands H2 et CO à la surface de nanoparticules de ruthénium et de rhénium dans le cas particulier de la synthèse de Fischer-Tropsch, permettant notamment de proposer un intermédiaire thermodynamiquement favorable pour cette réaction. Une étude préliminaire de cette réaction, d'un fort intérêt chimique et sociétal, conclut ce manuscrit. L'utilisation combinée des approches structurale, électronique et thermodynamique permet alors d'avoir un point de vue élargi sur certains aspects de la chimie de ces nanoparticules de ruthénium. / Surface chemistry of small metallic nanoparticles ( ~ 1 nm), mainly ruthenium or ruthenium alloys, has been studied at the DFT level via a theoretical approach. This study is supported by the development of analytical tools, that allow to investigate structural, electronic and thermodynamical properties of those nanoparticles. A first part is dedicated to the structural properties of metallic nanoparticles. Morphological diversity is highlighted as well as the necessity of being able to desing reliable models. The refinement of structural models is made possible via the combined use of generic nanoparticles structure design and of the reverse Monte Carlo method in order to fit experiments. Electronic or morphologic descriptors such as d-band center or generalized coordination number are applied to those nanoparticles, in relationship with their adsorption possibilities and, to a larger extent, with the Sabatier principle. An electronic descriptor of the chemical bond (COHP) is applied to the considered nanoparticles in order to show differences between structures, as well as the interactions within the metallic core and between the core and surface species. Finally, adsorption of surface species is studied. A single ligand probe is used to spot favorable adsorption sites, then higher coverages are considered so as to test its influence on the adsorption of extra ligands, and to investigate the effect of surface ligands on the metallic core morphology. To do this, thermodynamical properties of adsorbed systems have been modeled by taking into account the effect of pressure and temperature on the nanoparticles relative stabilities via ab initio thermodynamics. The same approache was eventually applied to H2/CO coadsorbed at ruthenium and rhenium nanoparticles surface, in the context of the Fischer-Tropsch synthesis, allowing to propose a thermodynamically favorable intermediate for this reaction. Preliminary study of this reaction, of high chemical and societal interest, conclude this manuscript. The combined use of structural, electronic and thermodynamical approaches widens the overview on some aspects of ruthenium nanoparticles chemistry

Lower C2–C4 olefins are important commodity chemicals usually produced by steam cracking of naphtha or fluid catalytic cracking of vacuum gas oil. The Fischer–Tropsch synthesis of lower olefins (FTO) with iron-based catalysts uses synthesis gas as an alternative feedstock. Nanostructured carbon materials are widely applied as supports for the iron nanoparticles due to their weak interaction with the metal species, facilitating the formation of catalytically active iron carbide. Numerous synthetic approaches towards carbon-supported FTO catalysts with various structures and properties have been published in recent years but structure-performance relationships remain poorly understood. We apply ordered mesoporous carbon (CMK-3) as a support material with well-defined pore structure to investigate the relationships between calcination/activation conditions and catalytic properties. After loading of iron and sodium/sulfur as the promoters, the structures and properties of the FTO catalysts are varied by using different calcination (300–1000 °C) and activation (350 or 450 °C) temperatures followed by FTO testing at 1 bar, 350 °C, H2/CO = 1. Carbothermal reduction of iron oxides by the support material occurs at calcination temperatures of 800 or 1000 °C, leading to a higher ratio of catalytically active iron(carbide) species but the catalytic activity remains low due to particle growth and blocking of the catalytically active sites with dense graphite layers. For the samples calcined at 300 and 500 °C, the formation of non-blocked iron carbide can be enhanced by activation at higher temperatures, leading to higher catalytic activity. Olefin selectivities of ∼60%C in the formed hydrocarbons with methane of ∼10%C are achieved for all catalysts under FTO conditions at low CO conversion. The influence of the calcination temperature is further investigated under industrially relevant FTO conditions. Promoted CMK-3-supported catalysts obtained at low calcination temperatures of 300–500 °C show stable operation for 140 h of time on stream at 10 bar, 340 °C, H2/CO = 2.