14 resultados para alternative fuel


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International Biodeterioration & Biodegradation 64(2010)388 e 396

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Dissertation presented to obtain a PhD degree in Biochemistry at the Instituto de Tecnologia Química e Biológica, Universidade Nova de Lisboa

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Dissertation presented to obtain the Ph.D. degree in Chemistry (Physical Chemistry) at the Instituto de Tecnologia Química e Biológica da Universidade Nova de Lisboa

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Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquimica

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Based on a report for the seminar Industrial Networks, at Goethe Universität Frankfurt am Main Dozent: Prof. Dr. Blättel-Mink, Prof. Dr. António Moniz SS 2011

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Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Mestrado Integrado em Engenharia Química e Bioquímica

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Dissertation presented to obtain the Ph.D degree in Sustainable Chemistry

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Dissertation presented to confer Master Degree in Chemical and Biochemical Engineering

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A Work Project, presented as part of the requirements for the Award of a Masters Degree in Economics from the NOVA – School of Business and Economics

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Carbon dioxide valorization, will not only help to relieve the greenhouse effect but might also allow us to transform it in value-added chemicals that will help overcoming the energy crisis. To accomplish this goal, more research that focus on sequestering CO2 and endeavors through a carbon-neutral or carbon-negative strategy is needed in order to handle with the dwindling fossil fuel supplies and their environmental impact. Formate dehydrogenases are a promising means of turning CO2 into a biofuel that will allow for a reduction of greenhouse gas emissions and for a significant change to the economic paramount. The main objective of this work was to assess whether a NAD+-independent molybdenum-containing formate dehydrogenase is able to catalyze the reduction of CO2 to formate. To achieve this, a molybdenum-containing formate dehydrogenase was isolated from the sulfate reducing bacteria Desulfovibrio desulfuricans ATCC 27774. Growth conditions were found that allowed for a greater cellular mass recovery and formate dehydrogenase expression. After growth trials, kinetic assays for formate oxidation and CO2 reduction were performed and kinetic parameters determined. For the formate oxidation reaction, a KM of 49 μM and a turnover constant of 146 s-1 were determined. These kinetic parameters are in agreement with those determined by Mota, et al. (2011). Finally, we found that this molybdenum-containing enzyme was able to catalyze the reduction of CO2 to formate with a turnover constant of 4.6 s-1 and a KM of 13 μM. For the first time a NAD+-independent molybdenum-containing formate dehydrogenase was found to catalyze CO2 reduction, allowing its use as a biocatalyst in energetically efficient CO2 fixation processes that can be directed towards bioremediation or as an alternative and renewable energy source. Characterizing these enzymes may lead to the development of more efficient synthetic catalysts, make them readily available and more suited for practical applications.

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This work studies fuel retail firms’ strategic behavior in a two-dimensional product differentiation framework. Following the mandatory provision of “low-cost” fuel we consider that capacity constraints force firms to eliminate of one the previously offered qualities. Firms play a two-stage game choosing fuel qualities from three possibilities (low-cost, medium quality and high quality fuel) and then prices having exogenous opposite locations. In the highest level of consumers’ heterogeneity, a subgame perfect Nash equilibrium exists in which firms both choose minimum quality differentiation. Consumers’ are worse off if no differentiation occurs in medium and high qualities. The effect over prices from the mandatory “low-cost” fuel law is ambiguous.

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The work presented in this thesis explores novel routes for the processing of bio-based polymers, developing a sustainable approach based on the use of alternative solvents such as supercritical carbon dioxide (scCO2), ionic liquids (ILs) and deep eutectic solvents (DES). The feasibility to produce polymeric foams via supercritical fluid (SCF) foaming, combined with these solvents was assessed, in order to replace conventional foaming techniques that use toxic and harmful solvents. A polymer processing methodology is presented, based on SCF foaming and using scCO2 as a foaming agent. The SCF foaming of different starch based polymeric blends was performed, namely starch/poly(lactic acid) (SPLA) and starch/poly(ε-caprolactone) (SPCL). The foaming process is based on the fact that CO2 molecules can dissolve in the polymer, changing their mechanical properties and after suitable depressurization, are able to create a foamed (porous) material. In these polymer blends, CO2 presents limited solubility and in order to enhance the foaming effect, two different imidazolium based ILs (IBILs) were combined with this process, by doping the blends with IL. The use of ILs proved useful and improved the foaming effect in these starch-based polymer blends. Infrared spectroscopy (FTIR-ATR) proved the existence of interactions between the polymer blend SPLA and ILs, which in turn diminish the forces that hold the polymeric structure. This is directly related with the ability of ILs to dissolve more CO2. This is also clear from the sorption experiments results, where the obtained apparent sorption coefficients in presence of IL are higher compared to the ones of the blend SPLA without IL. The doping of SPCL with ILs was also performed. The foaming of the blend was achieved and resulted in porous materials with conductivity values close to the ones of pure ILs. This can open doors to applications as self-supported conductive materials. A different type of solvents were also used in the previously presented processing method. If different applications of the bio-based polymers are envisaged, replacing ILs must be considered, especially due to the poor sustainability of some ILs and the fact that there is not a well-established toxicity profile. In this work natural DES – NADES – were the solvents of choice. They present some advantages relatively to ILs since they are easy to produce, cheaper, biodegradable and often biocompatible, mainly due to the fact that they are composed of primary metabolites such as sugars, carboxylic acids and amino-acids. NADES were prepared and their physicochemical properties were assessed, namely the thermal behavior, conductivity, density, viscosity and polarity. With this study, it became clear that these properties can vary with the composition of NADES, as well as with their initial water content. The use of NADES in the SCF foaming of SPCL, acting as foaming agent, was also performed and proved successful. The SPCL structure obtained after SCF foaming presented enhanced characteristics (such as porosity) when compared with the ones obtained using ILs as foaming enhancers. DES constituted by therapeutic compounds (THEDES) were also prepared. The combination of choline chloride-mandelic acid, and menthol-ibuprofen, resulted in THEDES with thermal behavior very distinct from the one of their components. The foaming of SPCL with THEDES was successful, and the impregnation of THEDES in SPCL matrices via SCF foaming was successful, and a controlled release system was obtained in the case of menthol-ibuprofen THEDES.

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The present Master dissertation is a project whose main objective is to identify value creation opportunities through fuel switching in the Portuguese industry, services, agriculture and fishing sectors. Fuel switching opportunities are characterized by type of fuel transition, type of technology transition, economy subsectors prone to have fuel switching and value created through fuel shift. Results suggest tomato concentrate, dairy, beer manufacturing and sugar refining subsectors is where prevalence of fuel oil steam boilers is high, for such cases conversion to natural gas steam boilers should result in operations having a ratio of NPV over CAPEX larger than ten and a payback period just under one year. Results further suggest food, beverages, textile, chemicals and wood subsectors currently operate between ten and twenty cogeneration Diesel engines that can be either modified to operate with natural gas or replaced by new natural gas cogeneration systems. Financial modeling indicates that both options have great value creation potential. The current analysis aims to be used by natural gas suppliers and energy project promoters to identify new potential deals as well as by heavy energy consumers to mitigate their energy related costs.