Uma das desvantagens dos bio-óleos precursores do biodiesel é a alta carga de compostos oxigenados que diminuem seu poder de combustão, reduzindo sua eficiência e inviabilizando seu uso em larga escala. Nesse contexto, o processo de hidrodesoxigenação (HDO) é relevante, dado que elimina esses compostos através de uma reação catalítica e, portanto, aumenta o poder calorífico do combustível. Neste trabalho, estudou-se a HDO do guaiacol (2-metoxifenol) como composto modelo dos bio-óleos derivados da biomassa e avaliou-se o desempenho de catalisadores de Ni e Mo no processo. Estudou-se a performance de um catalisador suportado em SBA-15 - um material mesoporoso de sílica de alta área superficial - em comparação a de um catalisador tradicional suportado em gama-alumina. Para tal, utilizou-se um sistema contínuo em fase gasosa e reator de leito fixo. Utilizaram-se técnicas de caracterização de catalisadores, como adsorção de N2, MEV, MET, DRX, TPR-H2, FTIR, TPO-O2, Raman e TGA. Através das análises DRX e MET, comprovou-se que se formaram partículas de NiO e MoO3 de menor tamanho e mais dispersas no caso do catalisador de SBA-15, devido à menor interação com o suporte e maior área superficial, o que resultou em um grau de redução de 91,6 % deste catalisador, em comparação a 73,4 % do outro, analisados por TPR-H2. Os testes catalíticos mostraram que o catalisador de NiMo/SBA-15 supera o de alumina em termos de conversão no intervalo de 200 a 300 °C, com ciclohexeno e ciclohexano como principais produtos, em face à maior seletividade a catecol e fenol no NiMo/?-Al2O3. A 300 °C, o catalisador suportado em sílica alcançou taxas de 66,5 % para a HDO e 35,3 % HDA (hidrodesaromatização), enquanto o de alumina obteve somente 30,8 e 2,7 %, respectivamente. Finalmente, comprovou-se que o SBA-15 teve uma taxa de desativação por coque de 1,14 mgcoque gcat-1 h-1, 31 % menor que a taxa do catalisador de alumina, cujos depósitos foram de carbono grafítico bem estruturado e irreversível. Em vista dos resultados obtidos, esta dissertação apresenta as rotas e mecanismos de reação do guaiacol nos catalisadores estudados, conhecimento que é relevante para o desenvolvimento e aprimoramento de futuros catalisadores da HDO. / A key disadvantage of the bio-oils precursors of biodiesel is the high load of oxygenated compounds that reduce their heat of combustion, dropping their efficiency and making them unfeasible on a large scale. In light of that, the hydrodeoxygenation process (HDO) is relevant, since it eliminates these compounds through a catalytic reaction, thus increasing the calorific value of the fuel. In this work, the HDO of guaiacol (2-methoxyphenol) as a model compound of the bio-oils derived from biomass was studied and the performance of Ni-Mo catalysts was evaluated. A catalyst supported on SBA-15 - a high surface area mesoporous silica material - was compared to a traditional gamma-alumina-supported catalyst. For this purpose, a continuous gas phase setup with fixed bed reactor was employed. The catalysts properties were identified by N2 adsorption, SEM, TEM, XRD, H2-TPR, FTIR, O2-TPO, Raman and TGA techniques. Through XRD and TEM, it was verified that smaller and more dispersed NiO and MoO3 particles were formed in the case of the SBA-15 catalyst, due to the lower interaction with the support and the greater surface area, which resulted in a degree of reduction of 91.6% for this catalyst, as opposed to 73.4% for the other one, both analyzed by H2-TPR. The catalytic tests showed that the NiMo/SBA-15 outperforms the alumina catalyst in terms of conversion in the range of 200 to 300 °C, with cyclohexene and cyclohexane as main products, in contrast with major selectivity to catechol and phenol on NiMo/?-Al2O3. At 300 °C, the silica-supported catalyst achieved rates of 66.5% for HDO and 35.3% for HDA (hydrodearomatization), whereas alumina reached only 30.8 and 2.7%, respectively. Finally, it was shown that the SBA-15 catalyst had a coke deactivation rate of 1.14 mgcoke gcat-1 h-1, 31% lower than the alumina catalyst, whose coke deposits consisted of well-structured irreversible graphitic carbon. In view of the results, this dissertation proposes the routes and reaction mechanisms of guaiacol on the studied catalysts, knowledge that is pertinent for the development and improvement of future HDO catalysts.

Uma das desvantagens dos bio-óleos precursores do biodiesel é a alta carga de compostos oxigenados que diminuem seu poder de combustão, reduzindo sua eficiência e inviabilizando seu uso em larga escala. Nesse contexto, o processo de hidrodesoxigenação (HDO) é relevante, dado que elimina esses compostos através de uma reação catalítica e, portanto, aumenta o poder calorífico do combustível. Neste trabalho, estudou-se a HDO do guaiacol (2-metoxifenol) como composto modelo dos bio-óleos derivados da biomassa e avaliou-se o desempenho de catalisadores de Ni e Mo no processo. Estudou-se a performance de um catalisador suportado em SBA-15 - um material mesoporoso de sílica de alta área superficial - em comparação a de um catalisador tradicional suportado em gama-alumina. Para tal, utilizou-se um sistema contínuo em fase gasosa e reator de leito fixo. Utilizaram-se técnicas de caracterização de catalisadores, como adsorção de N2, MEV, MET, DRX, TPR-H2, FTIR, TPO-O2, Raman e TGA. Através das análises DRX e MET, comprovou-se que se formaram partículas de NiO e MoO3 de menor tamanho e mais dispersas no caso do catalisador de SBA-15, devido à menor interação com o suporte e maior área superficial, o que resultou em um grau de redução de 91,6 % deste catalisador, em comparação a 73,4 % do outro, analisados por TPR-H2. Os testes catalíticos mostraram que o catalisador de NiMo/SBA-15 supera o de alumina em termos de conversão no intervalo de 200 a 300 °C, com ciclohexeno e ciclohexano como principais produtos, em face à maior seletividade a catecol e fenol no NiMo/?-Al2O3. A 300 °C, o catalisador suportado em sílica alcançou taxas de 66,5 % para a HDO e 35,3 % HDA (hidrodesaromatização), enquanto o de alumina obteve somente 30,8 e 2,7 %, respectivamente. Finalmente, comprovou-se que o SBA-15 teve uma taxa de desativação por coque de 1,14 mgcoque gcat-1 h-1, 31 % menor que a taxa do catalisador de alumina, cujos depósitos foram de carbono grafítico bem estruturado e irreversível. Em vista dos resultados obtidos, esta dissertação apresenta as rotas e mecanismos de reação do guaiacol nos catalisadores estudados, conhecimento que é relevante para o desenvolvimento e aprimoramento de futuros catalisadores da HDO. / A key disadvantage of the bio-oils precursors of biodiesel is the high load of oxygenated compounds that reduce their heat of combustion, dropping their efficiency and making them unfeasible on a large scale. In light of that, the hydrodeoxygenation process (HDO) is relevant, since it eliminates these compounds through a catalytic reaction, thus increasing the calorific value of the fuel. In this work, the HDO of guaiacol (2-methoxyphenol) as a model compound of the bio-oils derived from biomass was studied and the performance of Ni-Mo catalysts was evaluated. A catalyst supported on SBA-15 - a high surface area mesoporous silica material - was compared to a traditional gamma-alumina-supported catalyst. For this purpose, a continuous gas phase setup with fixed bed reactor was employed. The catalysts properties were identified by N2 adsorption, SEM, TEM, XRD, H2-TPR, FTIR, O2-TPO, Raman and TGA techniques. Through XRD and TEM, it was verified that smaller and more dispersed NiO and MoO3 particles were formed in the case of the SBA-15 catalyst, due to the lower interaction with the support and the greater surface area, which resulted in a degree of reduction of 91.6% for this catalyst, as opposed to 73.4% for the other one, both analyzed by H2-TPR. The catalytic tests showed that the NiMo/SBA-15 outperforms the alumina catalyst in terms of conversion in the range of 200 to 300 °C, with cyclohexene and cyclohexane as main products, in contrast with major selectivity to catechol and phenol on NiMo/?-Al2O3. At 300 °C, the silica-supported catalyst achieved rates of 66.5% for HDO and 35.3% for HDA (hydrodearomatization), whereas alumina reached only 30.8 and 2.7%, respectively. Finally, it was shown that the SBA-15 catalyst had a coke deactivation rate of 1.14 mgcoke gcat-1 h-1, 31% lower than the alumina catalyst, whose coke deposits consisted of well-structured irreversible graphitic carbon. In view of the results, this dissertation proposes the routes and reaction mechanisms of guaiacol on the studied catalysts, knowledge that is pertinent for the development and improvement of future HDO catalysts.

The objective of this project is to investigate hydrodeoxygenation (HDO), a crucial step in the treatment of bio-oil, on transition metal phosphide catalysts. The study focuses on reactions of simple oxygenated compounds present in bio-oil -- ethanol and 2-methyltetrahydrofuran (2-MTHF). The findings from this project provide fundamental knowledge towards the hydrodeoxygenation of more complex bio-oil compounds. Ultimately, the knowledge contributes to the design of optimum catalysts for upgrading bio-oil. A series of transition metal phosphides was prepared and tested; however, the focus was on Ni2P/SiO2. Characterization techniques such as X-ray diffraction (XRD), temperature-programmed reduction and desorption (TPR and TPD), X-ray photoelectron spectroscopy (XPS), and chemisorption were used. In situ Fourier transform infrared (FTIR) spectroscopy was employed to monitor the surface of Ni2P during various experiments such as: CO and pyridine adsorption and transient state of ethanol and 2-MTHF reactions. The use of these techniques allowed for a better understanding of the role of the catalyst during deoxygenation. / Ph. D.

La vapeur d’eau est le principal gaz à effet de serre de l’atmosphère et implique un processus de rétroaction climatique positif qui se traduit par une augmentation importante de l’humidité dans la troposphère dans les prochaines décennies. La vapeur d’eau joue également un rôle primordial dans le système climatique, notamment via le transport d’énergie de l’équateur vers les pôles. Malgré ceci, la compréhension des mécanismes qui contrôlent la distribution de la vapeur d’eau sur le globe reste insuffisante, ce qui se répercute sur les prédictions de l’évolution de notre climat. Depuis quelques années, les observations de la composition isotopique de la vapeur d’eau se sont révélées être particulièrement utiles pour aider à mieux comprendre les processus hydrologiques car les différents isotopologues de la vapeur d’eau (H216O, H218O, HDO) se comportent différemment selon les processus en jeu.<p>Dans cette perspective, les mesures de radiances du système terre-atmosphère dans l’infrarouge thermique par l’Interféromètre Atmosphérique de Sondage Infrarouge (IASI) à bord de la plateforme météorologique MetOp, peuvent fournir des observations du rapport isotopique δD (rapport HDO/H216O), à l’échelle globale et à haute résolution spatio-temporelle, pour autant que la restitution du rapport puisse être obtenue avec une précision suffisante.<p>Dans ce travail, nous présentons une méthodologie robuste et précise pour la restitution du profil de δD à partir des spectres IASI. Basée sur la méthode d’estimation optimale, elle consiste à appliquer des contraintes d’inversion adaptées afin d’obtenir des profils de δD fiables. Nous décrivons le choix de celles-ci et nous montrons que la méthode mise en place permet de fournir des profils de δD qui présentent un maximum de sensibilité dans la troposphère libre. L’adéquation de la méthode mise en place est ensuite évaluée grâce à une étude d’inter-comparaison avec des mesures dérivées de l’instrument spatial TES (Tropospheric Emission Spectrometer sur AURA) et FTIR localisés au sol. L’exactitude des profils IASI a aussi pu être déterminée grâce à des comparaisons avec des mesures in situ. <p>Dans une autre partie du travail, nous nous attachons à préciser les applications liées à l’utilisation des nouvelles mesures dans le domaine des géosciences. Nous documentons ainsi les capacités du sondeur IASI à fournir des mesures de δD à une résolution spatio-temporelle inégalée et décrivons les diverses distributions obtenues. Nous montrons et analysons notamment les premières cartes globales à haute résolution de δD dans la troposphère. Les mesures de δD et de l’humidité sont analysées conjointement à l’aide de modèles simples et permettent de démontrer la plus-value mesures de δD depuis les satellites. Parmi les résultats les plus significatifs, citons la mise en évidence de la signature isotopique des différentes sources de la vapeur d’eau (évaporation continentale/océanique), et celle de l’empreinte des différents processus hydrologiques qui contrôlent l’humidification de l’atmosphère (convection, mélange de masse d’air, ré-évaporation des gouttes de pluie). <p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

The work deals with the measurement and management in power. Provides an introduction to the problems of remote meter reading, management, and describes the current situation in the field of modern technologies Smart metering and Smart grids. It also analyzed the issue of collection of networks and data collection from a large number of meters over a wide area. For the purpose of data transmission are described GPRS, PLC, DSL, ... Further, there are given options to streamline communication. This area is used hierarchical aggregation. Using k-means algorithm is a program designed to calculate the number of concentrators and their location in the group of meters. The finished program is written in Java. It has a graphical interface and shows how the calculation is conducted. To verify the results of the optimization program is given simulation model in OPNET Modeler tool. Audited results are described in the conclusion and can deduce that using the optimization program is to streamline communications.

It is necessary to judge the influences of producers on the electric compounds while creating electrical energy or during the regulation of those existing. These analyses are sorted out by so called studies of connectivity. These calculations analyze the degree of connection of the producer and the standby unit during a break-down. The results of this report are several recommendations for creating such unit and succeeding steps leading to secure the stability and safety of the electric compound operation. The aim of this thesis is to discuss about software for PC solutions for static and dynamic network model, to draft power outlet into a network of generating high voltage, to complete a study of connectivity with respect to all the distortion factor, as increased voltage, inrush current at startup, flicker, harmonic currents, interference ripple, contribution to short-circuit current, reactive power control options, and demands for compensation.