バイオディーゼルは、メタノールと触媒を使用したエステル交換プロセスによって製造されます。バイオディーゼルには、高セタン価、酸化安定性、低排出など、いくつかの利点があります。ただし、バイオディーゼルの高粘度と沸騰温度は、ディーゼルエンジンの噴霧燃焼に影響を与える可能性があります。したがって、高燃料と低沸点燃料を混合することでバイオディーゼルの特性を改善するために、新しい燃料設計法が適用されます。 / Biodiesel is one of the promising alternative fuels in the future. Biodiesel is made from the trans-esterification process that uses methanol or alcohol and catalyst. The use of biodiesel in diesel engine has some advantages such as high cetane number, oxidation stability and can reduce some emissions. However, high viscosity, boiling temperatures and surface tension in biodiesel may affect the spray characteristics as compared to diesel oil. To overcome the unbenefited in biodiesel, therefore, the new fuel designed method that high-boiling point fuel is mixed to a low-boiling point fuel is applied in order to improve the properties in biodiesels. / 博士(工学) / Doctor of Philosophy in Engineering / 同志社大学 / Doshisha University

The continued global reliance on fossil fuels with impact on resource depletion, human health, atmospheric pollution and environmental degradation has necessitated a global drive to integrate renewable fuels such as biodiesels. Biodiesels are described as “fuels composed of fatty acid methyl or ethyl esters and obtained from vegetable oils or animal fats”. Their use in energy generation could diversify the world’s energy mix, reduce fossil fuel dependence, reduce emissions and energy cost to bring about other economic benefits, especially for developing economies and rural communities with lack of adequate access to modern energy. A techno-economic and environmental life cycle assessment is however required to ensure that these fuels are fit for use in engines and meet any regulatory standard and sustainability criteria. This thesis has evaluated the use of Jatropha- and microalgae-biodiesel for power generation in two industrial gas turbines with open and combined cycle configuration. This was achieved using a techno-economic and environmental life cycle impact assessment framework. Comparative fuel assessments have been carried out between biodiesels and fossil fuels. Furthermore, the concept of microbial fuel degradation was examined in gas turbines. The thesis have identified Jatropha biodiesel as a worthwhile substitute for conventional diesel fuel, because it has close performance and emission characteristics to conventional diesel fuel with added advantage of being renewable. The consequent displacement of conventional diesel fuel with Jatropha biodiesel has significant environmental benefits. For economic viability and sustainability of gas turbine operated power plants, energy producers require a minimum monetary amount to recover the added cost of operating 100% Jatropha biodiesel. Other integration mechanisms are also available for utilizing the fuel in engines without compromising on plant’s economic performance. In worst case scenarios, where there are no government incentives, local conditions such as high life cycle cost of electricity, open opportunities for distributed and independent power generation from renewable fuels like Jatropha-biodiesel. Furthermore, this thesis has identified salient energy conversion processes that occur in gas turbine fuels, especially with biodiesels and developed a bio-mathematical model, Bio-fAEG to simulate these processes in gas turbines. This platform is a first step in quantifiable assessment and could enable a better understanding of microbial initiated processes.

Fundação de Amparo a Pesquisa do Estado de Minas Gerais / Faced with the economic stimulus generated by agribusiness around the production of biofuels and environmental benefits, biodiesel production has been gaining market making it necessary quality control throughout its chain of production and distribution. In Brazil, such supervision is done by the National Agency of Petroleum, Natural Gas and Biofuels (ANP) establishing parameters based on international standards, eg, American Society for Testing and Materials (ASTM). It is found, in literature, great amount of studies aimed quality control in the production of biodiesel and blends with diesel. However, most of these techniques require large quantities of reagents, used are time consuming and ue expensive analytical instruments. Within this context, Spectroscopic techniques, especially in the infrared are presented as a rapid, direct, non-destructive, clean and efficient alternative, and can be applied in situ quality control of biodiesel in all stages of the production chain and supervision. The potential of these techniques become almost limitless when combined with the use of chemometric methods to extract relevant information from complex data making them simpler to be applied in routine laboratories. Given the situation described, the present work ims at the use of spectroscopy in the mid infrared, combined the technique of discriminant analysis classification by partial least squares (PLS-DA) for the development of analytical method for classifying samples according biodiesels with their energy relative to pure biodiesels (B100) and their blends with diesel content of 5% biodiesel (B5). , Classification models for compliance with the contents of B5 were also developed. The usage of Spectroscopy in the Middle Infrared allied to the method of discriminant analysis by Partial Least Squares (PLS-DA) was able to sort through nearly 100% efficiency the samples of interest of the models developed in this work. So your application becomes feasible for the monitoring and supervision of the quality of these types of fuels. / Frente aos estímulos econômicos gerados pelos agronegócios em torno da produção de biocombustíveis e benefícios ao meio ambiente, a produção de biodiesel vem ganhando mercado, fazendo-se necessário o controle de qualidade ao longo de toda sua cadeia de produção e distribuição. No Brasil, essa fiscalização é feita pela Agência Nacional de Petróleo, Gás Natural e Biocombustíveis (ANP) que estabelece parâmetros baseados em normas internacionais como, por exemplo, da American Society for Testing and Materials (ASTM). Na literatura, encontra-se grande quantidade de trabalhos que visam o controle de qualidade na produção de biodiesel e misturas com diesel. Porém, a maioria dessas técnicas demandam grandes quantidades de reagentes, são demoradas e utilizam instrumentos analíticos caros. Ao encontro desse contexto técnicas espectroscópicas, principalmente no infravermelho apresentam-se como uma alternativa rápida, direta, não destrutiva, limpa e eficiente, podendo ser aplicadas in situ no controle de qualidade do biodiesel em todas as etapas da cadeia produtiva e fiscalização. As potencialidades dessas técnicas tornam-se quase ilimitadas quando aliadas ao uso de métodos quimiométricos para extrair informações relevantes de dados complexos tornando-os mais simples de serem aplicados nas rotinas de laboratórios. Diante da situação apresentada, o presente trabalho visa à utilização de técnicas de espectroscopia no infravermelho médio, aliada a técnica de classificação por análise discriminante por mínimos quadrados parciais (PLS-DA) para o desenvolvimento de método analítico para classificação de amostras de biodieseis de acordo com sua matriz energética em relação aos biodieseis puros (B100) e de suas misturas em diesel com teor de 5% de biodiesel (B5). Foram desenvolvidos também, modelos de classificação para verificação da conformidade quanto ao teor de B5. O uso da Espectroscopia no Infravermelho Médio aliada ao método de Análise Discriminante por Quadrados Mínimos Parciais (PLS-DA) foi capaz de classificar com eficiência próxima a 100% as amostras de interesse dos modelos desenvolvidos nesse trabalho. Portanto sua aplicação torna-se viáveis para o monitoramento e fiscalização da qualidade destes tipos de combustíveis. / Mestre em Química

La gazéification de la biomasse par voie thermochimique constitue une ressource en énergie renouvelable ayant un grand potentiel de développement. Parmi les différentes techniques possibles, la voie cogénération Chaleur/bio-SNG (Substitute Natural Gaz) est proche de la maturité technologique. Un des verrous technologique de cette technologie est l’élimination des goudrons contenu dans le gaz issu du gazéifieur. Le présent travail de recherche constitue une contribution à la levée de ce verrou. La technique d’élimination des goudrons par lavage au moyen d’un solvant non miscible à l’eau ayant été sélectionnée pour un pilote de démonstration, le présent travail de recherche s’est principalement focalisé sur l’acquisition de données d’équilibre bi et triphasique des composés modèles des goudrons - eau – solvant de lavage. De telles données sont en effet indispensable pour la mise au point du modèle thermodynamique permettant la modélisation et l’optimisation du lavage. Les analyses des phases liquides en équilibre on été réalisées par CPG-FID ou CPG-SM. Dans certains cas les niveaux de concentration étaient particulièrement faibles. Les concentrations réciproque obtenues et les coefficients de partage qui s’en déduisent vérifie respectivement la corrélation empirique de Hands et la relation de Van’t Hoff. L’équilibre liquide-liquide-vapeur des binaires eau – solvant de lavage ont été étudiés par la méthode statique. Les concentrations des phases en équilibres ont été corrélées par les modèles NRTL et UNIQUAC au moyen du logiciel commercial ‘Simulis Thermodynamic’. Les paramètres d’interaction ainsi ajustés permettent une bonne restitution des données expérimentales. / Gasification of biomass is a promising thermochemical renewable energy resource. Among all biomass conversion processes, gasification by heat cogeneration / bio-SNG (Substitute Natural Gas) is the promising one. But still, one of the deadlocks to be raised is the reduction of the high level of tar present in the product gas. The objective of this work is to perform a data base which will be useful at the operation of tar removal from aqueous medium. The present work has mainly focused on the acquisition of bi and triphasic equilibrium data model molecules of tars - water - washing solvent. Such data are indeed essential for the development of the thermodynamic model for the modeling and the optimization of the washing process. Analyses of liquid phases in equilibrium have been performed by GC-FID or GC-MS. In some cases the concentration levels were particularly low (up to 10-10 mole fraction of anthracene in the aqueous phase). Reciprocal concentrations obtained and the partition coefficients which are deduced from the empirical correlation satisfy each of Hands and the Van't Hoff relationship. Liquid-liquid-vapor equilibrium of binary systems (water-extracting solvent) was studied with the static method. The concentrations of the phases in equilibrium were correlated by the NRTL and UNIQUAC models using the commercial software 'Thermodynamic Simulis'. The interaction parameters adjusted allow a good reproduction of experimental data.