O aproveitamento da energia luminosa por bactérias que produzem hidrogenases poderia aumentar a eficiência do processo de produção de biohidrogênio. Neste trabalho, foi realizada a clonagem do gene que codifica a proteorrodopsina (PR) do isolado metagenômico SAR86 num plasmídeo de expressão para bactérias Gram-negativas. PR é uma proteína ligada ao cromóforo retinal, que, sob iluminação, promove o efluxo de prótons através da membrana celular. O excesso de prótons na face externa da membrana pode servir como substrato para a hidrogenase, resultando em maior eficiência na produção de hidrogênio (2H+ + 2e→ H2). O plasmídeo contendo o gene da PR foi utilizado na transformação genética das bactérias Cupriavidus necator e Escherichia coli, que produzem diversas hidrogenases. Enquanto a PR não se mostrou funcional em C. necator, na linhagem recombinante de E. coli, cultivada em presença de luz e retinal, foi obtido um aumento de até 2,17 vezes na produção de H2 em relação ao cultivo no escuro, desde que a linhagem estivesse produzindo a hidrogenase endógena HYD-4. / The utilization of light energy by hydrogenase producing bacteria could increase the efficiency of the biohydrogen production process. In the present work, the gene coding for proteorhodopsin (PR) of the SAR86 metagenomic lineage was cloned in an expression plasmid for Gram-negative bacteria. PR is an apoprotein linked to the chromophore retinal, which, upon illumination, promotes proton efflux across the cell membrane. The excess of protons on the plasma membrane surface may serve as a substrate for hydrogenases, resulting in a higher efficiency of hydrogen production (2H+ + 2e→ H2). The plasmid containing the PR gene was used to transform the Gram-negative bacteria Cupriavidus necator and Escherichia coli which produce several hydrogenases. Whereas PR did not display functionality in C. necator, in the recombinant E. coli cells, grown under illumination in the presence of retinal, an enhancement up to 2.17 fold in H2 production was found, relative to cells grown under darkness, provided that the cells were expressing the endogenous HYD-4 hydrogenase.

O etanol (álcool etílico) tem sido cada vez mais estudado e testado como combustível alternativo para substituição do uso de alguns derivados de petróleo em motores de combustão interna. O presente trabalho procura abordar o emprego do etanol na forma vaporizada em motores do ciclo Otto, objetivando a obtenção de melhores níveis de rendimento térmico total. Deste modo, um motor para teste de octanagem (motor CFR) foi equipado com um vaporizador de álcool instalado no coletor de escapamento, e após uma série de ensaios, várias análises puderam ser feitas. Essas considerações procuraram se ater a aspectos como rendimento térmico, relação ar/combustível, ângulo de avanço da centelha, temperatura de escape, assim como potência e eficiência volumétrica, levando em conta, sempre, a sua influência no funcionamento geral do motor. Ficou constatado que o motor movido a etanol vaporizado apresenta rendimento consideravelmente maior, menor consumo de combustível e funcionamento mais suave que aqueles verificados quando o mesmo motor e alimentado com álcool líquido. / The ethanol (ethyl alcohol) has been studied more and more as alternative fuel to replace some petroleum derivatives for internal combustion engines. The attached study examines the application of vaporized ethanol for Otto cycle engines, searching for better levels of total thermal efficiency. Therefore, an engine for test of octane number (CFR motor) was equipped with an alcohol vaporizer installed inside the escape pipe, and after many experiences, several analysis were made. The various analysis included aspects as thermal efficiency, air/fuel ratio, advance ignition, escape temperature, power and volumetric efficiency, always considering their influence on the operation of the engine. It was confirmed that the engine moved by vaporized ethanol presents higher thermal efficiency, smaller fuel consumption and smoother working than in case of alimentation by liquid alcohol.

O álcool etílico ou etanol vem se tornando, neste novo século, uma importante referência para estudos e aplicações que procuram um combustível alternativo ao uso de derivados de petróleo em motores de combustão interna. Neste trabalho, o uso do etanol vaporizado pelos gases de escape em motores do ciclo Otto busca a obtenção de melhores níveis de rendimento térmico e emissões de poluentes. Assim sendo, um motor de 1.0 litro foi montado em laboratório com um trocador de calor instalado ao lado do coletor de escapamento, e uma série de testes foram feitos, possibilitando uma cuidadosa análise quanto a rendimento térmico, relação ar/álcool, ângulo de avanço da centelha, temperatura de escape e gases de emissão, entre outros aspectos. Conclui-se que o motor a álcool vaporizado, em certos regimes de funcionamento, apresenta rendimento maior e emissões menores que aqueles verificados no motor a álcool líquido. / The ethyl alcohol or ethanol is becoming, in this new century, an important reference for studies and applications that search for an alternative fuel to be used in internal combustion engines, replacing oil derivatives. In this study, an Otto cycle engine is fueled with ethanol vaporized by the exhaust gases, aiming for better levels of thermal efficiency and exhaust emissions. Therefore, a 1.0 liter engine with a heat exchanger connected to the exhaust manifold was prepared in a test bench, and several tests were made, which allowed a criterious analysis about air/alcohol ratio, spark ignition time, exhaust temperature and exhaust emissions, and others. It was concluded that the engine fueled with vaporized alcohol presents, in some operation points, higher thermal efficiency and less emissions compared to the case of engine fueled with liquid alcohol.

Submitted by William Justo Figueiro (williamjf) on 2015-07-10T22:43:09Z No. of bitstreams: 1 42b.pdf: 11938841 bytes, checksum: 548f5c4ae8b13931af52bc417ff2da4f (MD5) / Made available in DSpace on 2015-07-10T22:43:09Z (GMT). No. of bitstreams: 1 42b.pdf: 11938841 bytes, checksum: 548f5c4ae8b13931af52bc417ff2da4f (MD5) Previous issue date: 2012 / Nenhuma / O objetivo desta dissertação de mestrado é estudar um projeto de coprocessamento de resíduos, e desenvolver um meio de torná-lo sustentável economicamente, à luz das teorias sobre logística reversa. Este projeto traz consigo resultados que vão além da área financeira, ao utilizar, da melhor forma, as cadeias logísticas já existentes na região, reduzindo, assim, o seu impacto na natureza. Uma vez que este projeto foi identificado ainda na sua fase de desenvolvimento, o método de pesquisa utilizado foi a pesquisa-ação. Neste tipo de método, usam-se as teorias existentes para planejar as intervenções de campo, ao mesmo tempo que se aproveitam os resultados para gerar avanços teóricos. Os objetivos específicos deste trabalho buscam estudar, primeiramente, as empresas fornecedoras de resíduos, analisando as suas localizações, bem como os tipos de produtos disponibilizados. A partir daí, ver o melhor lugar para instalar a planta produtora de mistura (blend), levando em consideração as restrições ambientais, os custos envolvidos e a oferta de modais de transporte, e por fim, analisar as empresas cimenteiras consumidoras de tal mistura. Os resultados mais importantes estão relacionados à mudança de localização da planta de coprocessamento, ao processo logístico de coleta dos resíduos bem como do produto final e o desenvolvimento de uma embalagem para o seu transporte. As implicações finais são ambientais, financeiras e estratégicas. Este projeto viabiliza o uso de uma parte significativa de resíduos que antes teriam como destino, na melhor das opções, os aterros sanitários da região, e agora passam ser uteis como combustíveis em uma nova cadeia de produção. Já os resultados econômicos atingiram as duas principais empresas estudas. Para a primeira, houve uma redução de 27% no custo logístico dos produtos produzidos. Já para a segunda, 8% no custo de combustível utilizado em fornos. Por fim, as estratégicas garantem, para a unidade de blendagem, um diferencial perante possíveis novos entrantes no mercado. Para garantir tudo isso, esta pesquisa passa pelos conceitos de logística e logística reversa, fazendo um apanhado sobre a produção de cimento e relatando os combustíveis utilizados nestas plantas, com as suas futuras opções de substituição, uma vez que este é um tipo de indústria altamente demandante de energia e calor. Finalmente, o caso analisado é a primeira planta de coprocessamento do Rio Grande do Sul que fará uso de diversos tipos de resíduos na confecção de um combustível alternativo para fornos de clinquer. / This dissertation aims to study a waste co-processing, and develop a way to make it economically sustainable within the logistic and reverse logistics theory. This brings together results that go beyond the financial area, when the logistics chains in the region are used at best in order to reduce the impact on the environment. Once this research project has already been identified in its development phase, the method of research is action-research. In this type of method, they use existing theories to plan interventions in the field, while the results take advantage to generate theorist advancements. The specific aims of this paper target the study, firstly, of the waste suppliers, analyzing their locations as well as the kinds of available products. From this point of view, we can see the best place to install the production blend plant, taking into consideration the environmental restrictions, the costs and the offering of different types of transport, and finally it analyzes the cement consumer companies of such blend. The most important results are related to the changing of the co-processing plant location, the logistic process of waste collection as well as the final product and the development of a kind of suitable wrapping for its transport. The final consequences are environmental, financial and strategic. This project enables the use of a significant portion of waste that would previously have as destination, at best, the region's landfills, and are now being useful as fuels in a new production chain. Since the economic results achieved two major companies studied. For the first, there was a 27% reduction in logistics costs of products produced. As for the second, 8% of the cost of fuel. Finally, the strategic guarantee, for the blending unit, a differential to possible new entrants in the market. So, this study analyses the concepts on logistics and reverse-logistics, making an overview on the cement production and the different kinds of fuel used in these plants, with its future replacement options - once this is a type of industry that demands high amounts of energy and heating. Finally, the case study talks about the first co-processing plant in Rio Grande do Sul, which is going to use several sorts of waste in the manufacturing of an alternative kind of fuel for clinker kilns.

Dans le cadre de cette thèse, je m'intéresse à la gestion des combustibles fossiles (pétrole, gaz naturel, charbon) en présence d'interactions stratégiques entre diffé­rents types d'agents. Dans un premier temps, j'étudie sous quelles conditions deux firmes asymétriques, exploitant une ressource non renouvelable, peuvent s'entendre autour d'un accord de coopération et ainsi former un cartel. J'analyse en parti­culier l'ensemble des accords possibles ainsi que la possibilité que ceux-ci soient acceptés par toutes les parties prenantes. Dans un second temps, je m'intéresse plus spécifiquement à l'incitation des pays membres du cartel de l'Opep à sures­timer ou sous-estimer leurs réserves de pétrole depuis l'instauration du système des quotas de production en 1982. Enfin, je caractérise la politique optimale d'un gouvernement en faveur du développement des technologies backstop au travers de subventions en R&D afin d'assurer la transition énergétique depuis des énergies fossiles polluantes à des énergies renouvelables non polluantes. Mais, je fais cette analyse dans le contexte où la production est contrôlée par une firme indépendante et lorsque le gouvernement ne peut pas implémenter une taxe sur les émissions. Un point commun de ces trois chapitres est la présence d'agents ayant des intérêts divergents. D'un point de vue méthodologique, j'utilise la théorie des jeux et, en particulier, les jeux différentiels dans les deux premiers chapitres. / This dissertation provides an analysis of the management of fossil fuels (oil, gas, coal) in the presence of strategic interactions between different types of agents. First, I study under which conditions two asymmetric firms, extracting a nonre­newable resource, may agree upon a cooperative agreement and, thus, merge into a cartel. I analyse, in particular, the set of feasible agreements and the possibility that every players accept one of them. Second, I focus more specifically on the incentives for the Opec members to over-report or under-report their oil reserves since the set of production quotas in 1982. Third, I characterize the optimal policy of a government in favor of the developing of backstop technologies through R&D subsidies in order to ensure the ecological transition from polluting fossil fuels to non-polluting renewable energies. However, I conduct this analysis in the context where the supply is controlled by an independent firm and when the government cannot implement a Pigovian tax on emissions. A common theme of these dif­ferent chapters is the presence of agents whose interests are contradictory. From a methodological point of view, I use game theory and, in particular, differential games in the two first chapters.

Dans le contexte actuel de développement de nouvelles sources d'énergie non fossiles tout en minimisant l'impact environnemental, la production de carburants solaires par la valorisation des émissions anthropiques de CO2 apparaît comme une solution à fort potentiel. Le principal défi dans les processus artificiels photo-induits concerne le caractère bidimensionnel des systèmes utilisés, en raison de la faible profondeur de pénétration des photons. Ce travail de thèse se concentre sur le développement de mousses solides alvéolaires, issues de la chimie intégrative, présentant une porosité hiérarchiquement organisée. A travers l’imprégnation de précurseurs de TiO2, des photocatalyseurs autosupportés ont été synthétisés et ont montré une augmentation de la pénétration des photons d’un ordre de grandeur. D’autre part, ces solides limitent les réactions inverses par un effet de dilution, tout en assurant une sélectivité élevée envers la génération d'alcanes. Un modèle cinétique, basé sur un formalisme mixte de Langmuir-Hinshelwood et Eley-Rideal, est proposé pour décrire le comportement des matériaux. / In the current context of developing novel non-fossil energy sources while minimizing the environmental impact, solar-driven-fuel-production by exploiting anthropogenic CO2 emissions appears to be a solution with great potential. The main challenge in artificial photo-induced processes concerns the two-dimensional character of the systems used, due to the low photon penetration depth. This thesis work focuses on the development of alveolar solid foams, derived from integrative chemistry and bearing a hierarchically organized porosity. By TiO2 precursor impregnation, self-standing photocatalysts were synthesized and provided a photon penetration increase by an order of magnitude. Moreover, these solids limit back-reactions by a dilution effect, while ensuring high selectivity towards alkane generations. A kinetic model, based on a mixed formalism of Langmuir-Hinshelwood and Eley-Rideal, is proposed to describe material behavior.

É cada vez maior a busca por fontes de energia alternativas com vistas à substituição dos derivados do Petróleo, em especial após a crise da década de 70. A indústria automotiva segue a mesma tendência, buscando alternativas viáveis frente à incerteza do tempo e quantidade que ainda resta de estoque de combustíveis fósseis líquidos. Além do Álcool como meio de substituição ao Diesel e a Gasolina, a utilização de GNV - Gás Natural Veicular - está entre as tecnologias atualmente consideradas viáveis e eficientes. Segundo a ANP - Agência Nacional do Petróleo, Gás Natural e Biocombustíveis (2006), o Brasil possui reservas comprovadas de 306,4 x 109 m3 de Gás Natural, quantidade estimada para abastecer o mercado nacional, no cenário mais pessimista, pelos próximos cinqüenta anos. A associação desses fatores resulta na busca do consumidor brasileiro pela redução dos gastos cada vez maiores com combustível e no aumento da demanda por veículos movidos a Gás Natural. Apesar da notória demanda de mercado, atualmente existem no Brasil poucas opções de veículos leves com Sistemas de Conversão originalmente instalados pelas montadoras e com manutenção da garantia de fábrica. A falta de opções de oferta abre espaço para o grande aumento do número de oficinas de conversão, freqüentemente ignorando aspectos técnicos e de legislação de conversão, na intenção de apenas obterem lucros com o aumento de demanda. Mais do que pretensiosas conclusões definitivas, o presente trabalho tem como objetivo oferecer uma pequena contribuição à indústria e à sociedade, através da análise da viabilidade técnica, econômica, ambiental e mercadológica da instalação original de fábrica de Sistema de Conversão para uso de Gás Natural em veículos leves movidos a Gasolina e / ou Álcool, frente ao atual mercado de veículos convertidos e ao aumento da demanda por fontes de energia alternativa. / The search for alternative energy sources aiming the substitution of derivate Oil products is each time higher, especially after the 70s Petroleum crisis. The automotive industry follows this trend too, looking for possible alternatives in face of the uncertainness of time and quantity available stocks of liquid fossil fuels. Besides the Ethanol as a way of Gasohol and Diesel substitution, the CNG - Compressed Natural Gas - use is nowadays considered one of the most possible and efficient technologies. According to the ANP - National Petroleum, Natural Gas and Biofuel Agency (2006), Brazil owns 306,4 x 109 m3 of Compressed Natural Gas proved reserves, which are considered enough to supply the national market, in the worst case, for the next fifty years. The conjunction of these issues results in the Brazilian customers search for the each higher fuel expenses reduction and the raise of Compressed Natural Gas impelled vehicles demand. Despite the notorious market demand, there are nowadays on Brazil only a few options of light vehicles with Conversion System originally installed by automotive assemblers and warrantys maintenance. This lack of supply options creates a large field to the raise in the quantity of conversion workshops, frequently ignoring the technical aspects and the conversion legislation only with intent of achieving profit with the demand raise. More than pretentious definitive conclusions, the present work aims to offer a small contribution to the industry and society through the technical, economical, environmental and merchandizing practicability analysis of original assemblers installation of Conversion System to the use of Compressed Natural Gas in Gasohol and / or Ethanol impelled light vehicles, in face of the actual converted vehicles market and the demand raise for alternative energy sources.

La température et la pression partielle d’oxygène (PO2) constituent les paramètres majeurs contrôlantles évolutions thermochimiques en réacteur des combustibles nucléaires de type oxyde, et notammentla spéciation des produits de fission potentiellement corrosifs (Cs, I, Te). Pour limiter les risques derupture de la gaine en Zr par corrosion, une solution innovante consiste à imposer au combustible defonctionner dans un domaine de PO2 où les espèces chimiques des gaz de fission sont inoffensives, pardopage in-situ avec un tampon oxydo-réducteur solide. Le niobium, avec ses couples redoxNbO2/NbO et Nb2O5/NbO2, a été identifié comme le candidat le plus prometteur. Un procédé defabrication d’un combustible dopé niobium répondant à cet objectif et conforme aux spécificationsd’usage (densité, microstructure) a été optimisé. L’étude expérimentale du système UO2-NbOx a révélél’existence à 810°C d’une phase liquide entre UO2 et NbO2, non identifiée à ce jour. La caractérisationdes phases solides et en solution du niobium nous a conduit à proposer un modèle thermodynamiquede solubilité du dopant dans UO2 à 1700°C. Une étude approfondie de la spéciation du niobiumprécipité a permis d’identifier la présence simultanée dans le matériau des phases majeures NbO2 etNbO, ainsi que Nb en moindre teneur. La coexistence du niobium sous deux degrés d’oxydationdifférents constitue un élément-clé de démonstration d’un possible effet tampon in-situ, dont l’impactest observé sur certaines propriétés du combustible dépendantes de la PO2, la densification notamment.Les résultats confirment le potentiel prometteur des combustibles tamponnés en PO2 au regard de sesperformances en réacteur. / Temperature and oxygen partial pressure (PO2) of nuclear oxide fuels are the main parametersgoverning both their thermochemical evolution in reactor and the speciation of volatile fissionproducts such as Cs, I or Te. An innovative way to limit the risk of cladding rupture by corrosionunder irradiation consists in buffering the oxygen partial pressure of the fuel under operation in a PO2domain where the fission gas are harmless towards Zr clad, by using solid redox buffers as additives.Niobium, with its NbO2/NbO and Nb2O5/NbO2 redox couples has been found to be a promisingcandidate to this end. A manufacturing process of a buffered UO2 fuel, doped with niobium has beenoptimized, in order to fulfill usual specifications (density, microstructure). The experimental study ofthe UO2-NbOx system has shown the existence of a liquid phase between UO2 and NbOx at 810°C,which was not reported in the literature. The characterization of Nb containing phases present in UO2both in solid solution and as precipitates has lead us to propose a solubility thermodynamic model ofniobium in UO2 at 1700°C. An extensive study of the niobium precipitates shows the co-existence inthe fuel of NbO2 and NbO as major phases, together with small amounts of metallic Nb. The coexistenceof niobium under two oxidation states inside the fuel is a key element of demonstration of apossible in-situ buffering effect, which is likely to impact some properties of the material that aredependent upon PO2, such as densification. These results confirm the promising potential of oxygenbuffered fuels as regard to their performance in reactor.

Mobile source emissions are a major contributor to global and local air pollution. Governments and regulatory agencies have been increasing the stringency of regulations in the transportation sector for the last ten years to help curb transportation sector air pollution. The need for regulations has been emphasized by scientific research on the impacts from ambient pollution, especially research on the effect of particulate matter on human health. The particulate emissions from diesel vehicles, diesel particulate matter (DPM) is considered a known or probable carcinogen in various countries and increased exposure to DPM is linked to increased cardiovascular health problems in humans. The toxicity of vehicle emissions and diesel particulate emissions in particular, in conjunction with an increased awareness of potential petroleum fuel shortages, international conflict over petroleum fuel sources and climate change science, have all contributed to the increase of biodiesel use as an additive to or replacement for petroleum fuel. The goal of this research is to determine how this increased use of biodiesel in the particular emission testing setup impacts urban air quality. To determine if biodiesel use contributes to a health or climate benefit, both the size range and general composition were investigated using a comprehensive comparison of the particulate component of the emissions in real time. The emissions from various biodiesel and diesel mixtures from a common diesel passenger vehicle were measured with a cavity ring-down transmissometer (CRDT) coupled with a condensation particle counter, a SMPS, a nephelometer, NOx, CO, CO2, and O3 measurements. From these data, key emission factors for several biodiesel and diesel fuel mixtures were developed. This approach reduces sampling artifacts and allows for the determination of optical properties, particle number concentration, and size distributions, along with several important gas phase species' concentrations. Findings indicate that biodiesel additions to diesel fuel do not necessarily have an air quality benefit for particulate emissions in this emission testing scenario. The often cited linear decrease in particulate emissions with increasing biodiesel content was not observed. Mixtures with half diesel and half biodiesel tended to have the highest particulate emissions in all size ranges. Mixtures with more than 50% biodiesel had slightly lower calculated mass for light absorbing carbon, but this reduction in mass is most likely a result of a shift in the size of the emission particles to a smaller size range, not a reduction in the total number of particles. Evaluation of the extensive optical properties from this experimental set-up indicates that biodiesel additions to diesel fuel has an impact on emission particle extinction in both visible and near-IR wavelengths. The B99 mixture had the smallest emission factor for extinction at 532 nm and at 1064 nm. For the extinction at 532 nm, the trend was not linear and the emission factor peaked at the B50 mixture. Results from intensive properties indicate that emissions from B5 and B25 mixtures have Ångström exponents close to 1, typical for black carbon emissions. The mixtures with a larger fraction of biodiesel have Ångström exponent values closer to 2, indicating more absorbing organic matter and/or smaller particle size in the emissions. Additional experimental testing should be completed to determine the application of these results and emission factors to other diesel vehicles or types of diesel and biodiesel fuel mixtures.

<p>The aim of this report is to give a picture of how attitudes and behaviours of owners of environment cars look like and how they can be influenced. The alignment lies on environmental cars which run on biogas and ethanol which both are renewable fuels. The starting point is to sort out if it is environmental thinking that controls the choice and use of an environmental car. The feeling is that there are many other factors that can be more controlling, for example the price and the quality of the car. The result of the questionnaire survey which is the foundation of the report shows however that those who buy an environmental car do it mostly because of environmental reasons. Also the daily choice of fuel is mainly environmentally influenced; it however shows that there is dissatisfaction with the high fuel consumption, the short reach and above all the high price of ethanol. It also shows that the source of information which had the biggest impact on the choice to buy an environmental car is the mass media and that the most influencing policy instruments is the price, partly the cheaper on renewable fuel and the more costly fossil fuel. In general the environmental car owners are also positively inclined to using policy instruments of various kinds in order to increase the proportion of environmental cars on our roads. The conclusion becomes thus that the original feeling is incorrect and that environment cars have not at all lost credibility, not anyway on the level that has been investigated in this report.</p> / <p>Syftet med den här rapporten är att gen en bild av hur attityder och beteenden hos ägare av miljöbilar ser ut samt hur de kan påverkas. Inriktningen ligger på miljöbilar drivna med biogas och etanol vilka båda är förnyelsebara bränslen. Utgångspunkten är att reda ut om det är miljötänkandet som styr val och användning av en miljöbil. Känslan är att det finns många andra faktorer som kan vara mer styrande, exempelvis pris och kvalitet på bilen. Resultatet av den enkätundersökning som ligger till grund för rapporten visar dock att de som köper en miljöbil gör det till största delen på grund av miljömässiga orsaker. Även det dagliga valet av bränsle påverkas mestadels av miljömässiga orsaker, det visar sig dock att det finns ett missnöje med den höga bränsleförbrukningen, den korta räckvidden och framförallt det höga priset på etanol. Det visar sig också att den källa till information som haft den största påverkan vid valet att köpa en miljöbil är media samt att det mest påverkande styrmedlet är priset, dels det billigare på förnyelsebara bränslen samt det dyrare på fossila bränslen. Generellt är miljöbilägarna också positivt inställda till att använda styrmedel av olika slag för att öka andelen miljöbilar på vägarna. Slutsatsen blir således att den ursprungliga känslan är felaktig och att miljöbilar inte alls tappat i trovärdighet, i alle fall inte på det plan som granskas i denna rapport.</p>