L'objectif primordial de cette thèse est la recherche de modèles mathématiques qui sont à mieux de décrire le processus d'absorption gaz-liquide dans un contacteur membranaire à fibres creuses poreuses ou denses. La configuration géométrique de ces contacteurs combinée à leur compacité, et de leur faible consommation d'énergie leur permet de se substituer progressivement aux procédés conventionnels tels les colonnes à garnissage et autres tours d'absorption. Notre but est d'étudier la performance de ces processus novateurs par l'élaboration de modèles mathématiques de plus en plus rigoureux. Pour cela, nous avons étudié plusieurs cas de figures où l'hydrodynamique d'écoulement des fluides, la nature du soluté et/ou du solvant ont été changées. Dans un premier temps, il n'a été tenu compte que de l'hydrodynamique du compartiment côté fibre pour deux types de processus d'absorption avec et sans réaction chimique. Par la suite, l'hydrodynamique d'écoulement des fluides dans le côté fibre comme côté calandre a été prise en considération. Des modèles ont été développés pour l'absorption classique de gaz carbonique dans des solutions de monoéthanolamine (liquide d'absorption de référence) où l'écoulement du fluide côté calandre est assimilé à un écoulement piston dans un premier cas, obéissant au modèle dit de surface libre "modèle de Happel" dans un deuxième cas, et enfin caractérisé par des équations de moments de Navier-Stokes dans un troisième cas. La comparaison des résultats numériques de ces modèles a montré que ceux du troisième cas de figure sont les plus proches des résultats d"essais expérimentaux / The overarching objective of this thesis is the research of mathematical models which are better to describe the process of gas-liquid absorption in a membrane contactor with porous or dense hollow fibers. The geometric configuration of these contactors, combined with their low energy consumption and their compactness, allows them to gradually replace conventional processes such as packing towers and absorption columns. Our goal is to study the performance of these innovative processes by developing more rigorous mathematical models. In this scope, we studied several cases where the hydrodynamics of fluid flow, the nature of the solute or solvent have been changed. First, only the hydrodynamics of the fibre side compartment has been taken into account for two types of an absorption process with and without chemical reaction. Subsequently, the hydrodynamics of fluid flow in both the fiber side as shell side were taken into consideration. Models have been developed for classical carbon dioxide absorption in monoéthanolamine solutions (liquid absorption of reference) where the flow fluid in the shell were is assumed to obey a plug-flow in a first case, described by the surface free model known as "Happel model" in a second case, and finally characterized by the momentum Navier-Stokes equations in a third case. The comparison of the numerically simulated results collected from the three models showed that those of the third case matched very closely with the laboratory experimental results

La combustion en boucle chimique (CLC) est une nouvelle technologie prometteuse, qui implique la séparation inhérente du dioxyde de carbone (CO2) avec une perte minimale d'énergie. Un transporteur d'oxygène est utilisé pour le transfert de l'oxygène en continu du "réacteur air" vers le "réacteur fuel" où l'oxygène est apporté au combustible. Ainsi, le contact direct entre l'air et le combustible est évité. Le gaz résultant est riche en CO2 et n'est pas dilué avec de l'azote. Le transporteur d'oxygène réduit est ensuite transporté vers le "réacteur air" afin d'être ré-oxydé, formant ainsi une boucle chimique.Ce manuscrit présente des études conduites en utilisant une nouvelle configuration de CLC de 10 kWth construite pour étudier une large gamme de conditions opératoires. Cette unité met en oeuvre le concept des lits fluidisés interconnectés en utilisant des vannes-en-L pour contrôler le débit de solide et des siphons pour minimiser les fuites de gaz. L'hydrodynamique de la circulation de solide a été étudiée sur une maquette froide et un pilote chaud. Un modèle de la circulation du solide a ensuite été développé sur le principe du bilan de pression.L'hydrodynamique de la phase gaz dans le réacteur a été étudiée expérimentalement en utilisant la distribution des temps de séjour (DTS). Un modèle hydrodynamique a été développé sur le principe du lit fluidisé bouillonnant à deux phases. La combustion du méthane a été étudiée avec NiO/NiAl2O4 comme transporteur d'oxygène. De bonnes performances de combustion et de captage de CO2 ont été atteintes. Un modèle de réacteur a été finalement mis au point en utilisant le modèle hydrodynamique du lit fluidisé bouillonnant développé précédemment et en adaptant un schéma réactionnel à cette configuration / Chemical looping combustion (CLC) is a promising novel combustion technology involving inherent separation of carbon dioxide with minimum energy penalty. An oxygen carrier is used to continuously transfer oxygen from the air reactor to the fuel reactor where the oxygen is delivered to burn the fuel. Consequently, direct contact between the air and the fuel is prevented. The resulting flue gas is rich in CO2 without N2 dilution. The reduced oxygen carrier is then transported back to the air reactor for re-oxidation purposes, hence forming a chemical loop.This dissertation presents studies conducted on a novel 10 kWth CLC configuration built to investigate a wide range of conditions. The system employs concept of interconnected bubbling fluidized beds using L-valves to control solid flow rate and loop-seals to maximize gas tightness. Hydrodynamics of solid circulation was investigated with a cold flow prototype and a high temperature pilot plant in a wide temperature range. A solid circulation model was developed based on the experimental results using the pressure balance principle. Hydrodynamic of the gas phase in the reactors was investigated through RTD studies. A hydrodynamic model was then developed based on the two phase model of bubbling fluidized beds. Methane Combustion was experimentally studied in the pilot plant using NiO/NiAl2O4 oxygen carriers. Good combustion performances and CO2 capture efficiency were achieved. A reactor model was finally developed using the previously developed hydrodynamic model of bubbling fluidized bed and adapting a reaction scheme

Les procédés de captage de CO2 par absorption chimique engendrent une importante pénalité énergétique sur la production électrique des centrales à charbon, constituant un des principaux verrous technologiques au déploiement de la filière. L'objectif de cette thèse est de développer et valider une méthodologie à même d'évaluer précisément le potentiel d'un procédé de captage aux amines donné. La phénoménologie de l'absorption chimique a été étudiée en détail et représentée par des modèles à l'état de l'art. Le modèle e-UNIQUAC a été utilisé pour décrire les équilibres chimiques et de phases des solutions électrolytiques et les paramètres du modèle ont été régressés pour quatre solvants. Un modèle hors-équilibre a été utilisé pour représenter le transfert couplé de matière et de chaleur, accéléré par les réactions chimiques. Les modèles ont été validés avec succès sur des données expérimentales d'un pilote industriel et d'un pilote de laboratoire. L'influence des phénomènes sur les efficacités de séparation a été explicitée afin d'isoler les phénomènes les plus impactants. Une méthodologie a alors été proposée pour évaluer la pénalité énergétique, incluant les consommations thermiques et électriques, liée à l'installation d'un procédé de captage sur une centrale à charbon supercritique. Une méthode d'estimation du coût de l'électricité est proposée pour quantifier les dépenses opératoires et d'investissement d'un tel procédé. L'environnement de simulation et d'évaluation de procédés obtenu a ensuite été couplé à une méthode d'optimisation afin de déterminer les paramètres opératoires et les dimensions des équipements maximisant les performances énergétiques et économiques / CO2 capture processes by chemical absorption lead to a large energy penalty on efficiency of coal-fired power plants, establishing one of the main bottleneck to its industrial deployment. The objective of this thesis is the development and validation of a global methodology, allowing the precise evaluation of the potential of a given amine capture process. Characteristic phenomena of chemical absorption have been thoroughly studied and represented with state-of-the-art models. The e-UNIQUAC model has been used to describe vapor-liquid and chemical equilibria of electrolyte solutions and the model parameters have been identified for four solvents. A rate-based formulation has been adopted for the representation of chemically enhanced heat and mass transfer in columns. The absorption and stripping models have been successfully validated against experimental data from an industrial and a laboratory pilot plants. The influence of the numerous phenomena has been investigated in order to highlight the most limiting ones. A methodology has been proposed to evaluate the total energy penalty resulting from the implementation of a capture process on an advanced supercritical coal-fired power plant, including thermal and electric consumptions. Then, the simulation and process evaluation environments have been coupled with a non-linear optimization algorithm in order to find optimal operating and design parameters with respect to energetic and economic performances

Les travaux menés dans cette Thèse ont consisté à développer un pilote expérimental prouvant la faisabilité de la capture de CO2 par boucle chimique calcium en utilisant des chaudières du type Lit Fluidisé Circulant. Ceux-ci ont été conduits en deux phases: une phase expérimentale à l'échelle du laboratoire avec l'interprétation théorique des résultats et une phase expérimentale à l'échelle du pilote dans le but de valider le procédé. Les résultats expérimentaux à 1'échelle du laboratoire ont permis de montrer que le frittage de CaOest la cause de la décroissance du taux de carbonatation au cours des cycles successifs calcination/carbonatation. La vitesse de frittage étant accélérée par la présence de CO2 pendant la phase de calcination. Les analyses menées sur les échantillons calcinés ont révélé l'apparition d'une structure de micrograin à l'intérieur des grains initiaux de carbonate. Les micrograins de CaO non frittés sont le siège de la réaction de carbonatation.Un procédé de capture de CO2 par boucle chimique calcium a été conçu et réalisé. Il se compose de deux lits fluidisés circulants, un réacteur de carbonatation assurant la capture du CO2 et un réacteur de calcination permettant la régénération de la chaux. Ces deux lits fluidisés circulants sont couplés de façon à permettre un fonctionnement continu du procédé de capture de CO2. Malgré le faible rendement de capture obtenu à l'échelle de ce pilote (entre 18 à 23%), ces résultats apparaissent encourageants pour le développement de cette technologie, compte tenu du fait que beaucoup de facteurs limitant le rendement de capture disparaissent avec le changement d'échelle. / The works led in this Thesis consisted in developing an experimental pilot proving CO2 capture feasibility by calcium chemical looping using Circulating Fluidised Bed as boilers. These were undertaken in two step: At the laboratory scale with theoretical interpretation of the experimental results and at the pilot scale in the aim to validate the process.The experimental results on the scale of the laboratory allowed to show that the sintering of CaO bring about the decreasing of the carbonation rate during calcination/carbonation cycles. The sintering velocity are accelerated by CO2 during the calcinations step. The analysis of the calcined samples showed a micrograins structure inside the initial carbonate grains The not sintered CaO micrograins are the location of the carbonation reaction.A process of CO2 capture by calcium chemical looping was designed and built. It was made by two circulating fluidized beds, a carbonator where the CO2 capture were performed and the calcinator allowing the lime regeneration. These two circulating fluidized beds are coupled allowing a continuous CO2 capture.In spite of the low capture efficiency obtained on the scale of this pilot (from 18 to 23 %), these results seem encouraging for the development of this technology, considering the fact that many limiting factors of the capture efficiency disappear with the change of scale.

Offshore oil platforms are used for the exploitation and production of hydrocarbons and consist of a processing plant and a utility plant. The oil and gas industry operations are energy-intensive and, in the case of offshore platforms, the need to decrease energy consumption and reduce CO2 emissions has increased. In the oil and gas industry, the ISO 50001 standard promotes the implementation of energy management systems and proposes indicators based on energy. Interestingly, after several decades of knowledge of the concept of exergy, this has not been formally implemented in the programs and strategies of the oil and gas industry organizations. In this research, the implementation of the exergy method and the carbon capture and storage strategy for the assessment of the performance of a floating, production and storage offloading units FPSO is proposed. FPSO platforms and their processing and utility plants may have different configurations depending on, among others, the reservoir characteristics and production requirements. The possible configurations can therefore be numerous. In this sense, some operation scenarios based on different well-fluid compositions and operation modes are studied. The platform models are developed and simulated using the software Aspen HYSYS®. Results show that, on average, the reduction of 88.8% in CO2 emissions is penalized with a reduction in exergy efficiency of 1.7 points. Further, results allow a better understanding of exergy and environmental performance of the FPSO. / Plataformas de petróleo offshore são utilizadas para a exploração e produção de hidrocarbonetos e consistem em uma planta de processamento e uma planta de utilidade. As operações da indústria de petróleo e gás são de energia intensiva e, no caso de plataformas offshore, é necessário cada vez mais diminuir o consumo de energia e reduzir as emissões de CO2. Na indústria de petróleo e gás, a norma ISO 50001 promove a implementação de sistemas de gestão de energia e propõe indicadores baseados em energia. Entretanto, após várias décadas de conhecimento do conceito de exergia, este não foi formalmente implementado nos programas e estratégias das organizações da indústria de petróleo e gás. Neste trabalho, propõe-se a implementação da análise exergética e a estratégia de captura e armazenamento de carbono para a avaliação do desempenho de unidades flutuantes, de produção, de armazenamento e transferência FPSO. As plataformas FPSO e suas plantas de processamento e utilidade podem ter diferentes configurações dependendo, entre outras, das características do reservatório e dos requisitos de produção. As configurações possíveis podem, portanto, ser numerosas. Neste sentido, são estudados alguns cenários de operação baseados em diferentes composições dos fluidos do poço e em três modos de operação. Os modelos de plataforma são desenvolvidos e simulados usando o software Aspen HYSYS®. Os resultados mostram que, em média, a redução de 88,8% nas emissões de CO2 é penalizada com uma redução da eficiência exergética de 1,7 pontos. Além disso, os resultados permitem uma melhor compreensão da exergia e desempenho ambiental do FPSO.

A necessidade atual do mercado brasileiro para aumentar a oferta de gás incentiva a comunidade científica nacional no desafio de desenvolvimento de novas rotas tecnológicas, visando aumentar o aproveitamento do gás natural. Tal desafio é acompanhado por uma demanda mundial dos países signatários do Protocolo de Quioto (ratificado em 2005) para a redução das emissões de gases de efeito estufa. Apesar de o Brasil não apresentar nenhuma meta de redução, no primeiro período deste Protocolo (2008 a 2012), o setor do petróleo (atividade de E&P), através de suas companhias operadoras, que atuam no país, já estabeleceram metas corporativas para emissão evitada de gases de efeito estufa, em suas instalações de produção (maior predominância das unidades marítimas de produção). O presente trabalho aborda a análise técnica e econômica de um processo proposto de separação e captura de dióxido de carbono (CO2), através de estudo de caso (Primeira e Segunda Proposição) de simulação de processo, em uma instalação marítima de produção de petróleo, comparativamente a sua ausência (Caso Base). A Primeira Proposição considera a separação e a captura do CO2 oriundo tanto do gás natural produzido, quanto do gás de queima de uma turbina a gás. A Segunda Proposição considera a separação e a captura do CO2 oriundo somente do gás natural produzido. Até o momento, no Brasil, ainda não foram desenvolvidas tecnologias adequadas para a captura do CO2, em instalações marítimas de produção de petróleo. Adicionalmente a regulação atual (Portaria nº104/2002 da ANP) limita o potencial de utilização do CO2 que existe na composição do gás natural comercializado no país, pelo fato de não diferenciar em sua especificação técnica, os usos deste importante combustível. Os resultados obtidos nesta tese, com a utilização de simulador de processo de uso comercial mostraram emissões evitadas de CO2 para atmosfera de 55 % (caso Segunda Proposição que apresentou maior viabilidade econômica), em relação ao resultado obtido para o Caso Base. Este relevante resultado equivale a uma emissão evitada de aproximadamente 241 x 103 t/ano, para uma única unidade piloto proposta. De acordo com o estudo de análise econômica apresentado, a Segunda Proposição (VPL US$ 15,3 x 106) foi melhor do que a da Primeira Proposição (VPL: US$ 13,9 x 106) ambos usando o Caso Base como referência. Dentre os ganhos esperados com o uso desta nova tecnologia destacam-se: redução do consumo interno e das perdas de gás natural, emissão evitada de CO2 e hidrocarbonetos para a atmosfera, além do aumento das práticas de armazenamento de gás e CO2, em reservatórios geológicos depletados de petróleo. Estima-se que num cenário futuro, com a implantação deste novo processo proposto, em instalações marítimas de produção de petróleo, uma relevante contribuição de emissões evitadas de gases de efeito estufa possa ocorrer na área de E&P de petróleo no Brasil. / The current Brazilian market needs to increase the natural gas supply to incentive the national scientific community to the challenge of developing new technologies routes aiming increase the utilization of the produced natural gas. Such challenge is followed by a world demand from signatory countries of the Kyoto Agreement (ratified in 2005) to reduce the greenhouse gas emissions. In spite of, the Brazil does not have any reduction goal, in the first period (2008 to 2012) the oil sector (E&P activity), by their oil operators companies that works in our country, has already established corporative goals to avoided greenhouse gas emissions in their production facilities (bigger predominance of offshore production unities). The present work approaches the economic and technical evaluation of a carbon dioxide (CO2) separation and capture proposal process (First and Second Proposal Case) comparatively your absence (Base Case). The First Case consider the CO2 separation and capture both the produced gas and exhausted gases of one turbine driven by gas. The Second Case consider only the CO2 separation and capture from the produced gas. At the present, in Brazil, it has not been developed yet suitable technologies, for such use, and the CO2 is normally disposal to the atmosphere. Moreover, the present Regulation (104/2002 ANP Decree) limit the potential of CO2 use existing in the gas composition that is marketed in the country, due to not differentiate the uses of this important fuel. The results obtained of this thesis, by using a process simulator of commercially use showed CO2 avoided emissions of 55 % to the atmosphere (Second Proposal Case that shows the best economic evaluation) related to the result obtained from the Base Case. This relevant result is equivalent in mass flow, to the avoidance emission of roughly 241 x 103 tons per year, for a single pilot unity proposal. According the economic evaluation study, the Second Proposal Case (VPL:US$ 15,3 x 106) was better than the First Case (VPL: US$ 13,9 x 106), using the Case Base as reference. Within the benefits expected with the use of this new technology are the following: reduction both the internal gas consumption and natural gas losses (atmospheric disposal), emissions avoided of CO2 and hydrocarbons, beyond the increase of CO2 and gas storage practices in offshore depleted oil fields. It is estimated, in future scenery, with the implantation of this new proposal process in offshore production unities, relevant contribution of avoided greenhouse gases emissions can occur in oil E&P tasks in Brazil.

Líquidos iônicos imidazólios (LIIs) associados a ânions com caráter básico foram sintetizados, caracterizados e seu comportamento estudado em solução. Inicialmente a troca isotópica H/D preferencial no grupo C2-CH3 de sais de 1-nbutil-2,3-dimetilimidazólio (BMMI) foi avaliada. Ficou evidente que o contato entre os pares de íons e a atuação do ânion como uma base neutra influenciaram fortemente a deuteração. Após a análise dos resultados de RMN, cálculos de DFT (Teoria do Funcional de Densidade) e Difração de Raios X, um complexo entre uma molécula de água e alguns LI foi sugerido, modificando fortemente a estrutura organizacional e afetando também a troca isotópica nestes sais. Através do mecanismo reacional proposto, surgiu a possibilidade de deuteração de novos substratos contendo H ácidos, usando os LIIs como catalisadores. A reação de troca isotópica em alcinos e cetonas foi estudada e bons resultados foram obtidos. O efeito da variação de cátions e ânions na atividade catalítica foi analisado, assim como a variação dos substituintes dos substratos. Além disso, um estudo cinético foi realizado através de análises de RMN de 1H e o mecanismo reacional foi proposto. Por fim, a capacidade de formação de pares iônicos em soluções aquosas de LIIs foi avaliada na captura de CO2. Ótimos resultados foram obtidos e atribuídos à ocorrência de sorção física e química devido à ativação da água pelo LII. / Imidazolium based ionic liquids (ImIL) associated with basic anions were synthesized, characterized and studied. Initially the preferred H/D isotopic exchange to C2-CH3 group of 1-nbutyl-2,3-dimethylimidazolium salts (BMMI) was studied. In this context, it became evident that the ion-pairing formation and the anion action as a neutral base strongly influence the deuteration reaction. NMR analysis, theoretical calculation (Density Functional Theory) and X-ray Diffraction have been performed and a complex between a water molecule and the IL have been suggested, strongly modifying the IL structure and characteristics. The isotope exchange reaction in alkynes and ketones was studied using imidazolium based ionic liquids as catalysts and good results obtained. The effect of cation and anion variation on the catalyst activity were analyzed, also a variation of the substrate substituent’s. Also, a kinetic study was performed by 1H NMR analyzes and the reaction mechanism were proposed. Finally, the ability to form ion pair contact of ILs in aqueous solutions was evaluated for CO2 capture. Great results were obtained and this success can be attributed to the occurrence of physical and chemical sorption due to water activation by the IL.

A necessidade atual do mercado brasileiro para aumentar a oferta de gás incentiva a comunidade científica nacional no desafio de desenvolvimento de novas rotas tecnológicas, visando aumentar o aproveitamento do gás natural. Tal desafio é acompanhado por uma demanda mundial dos países signatários do Protocolo de Quioto (ratificado em 2005) para a redução das emissões de gases de efeito estufa. Apesar de o Brasil não apresentar nenhuma meta de redução, no primeiro período deste Protocolo (2008 a 2012), o setor do petróleo (atividade de E&P), através de suas companhias operadoras, que atuam no país, já estabeleceram metas corporativas para emissão evitada de gases de efeito estufa, em suas instalações de produção (maior predominância das unidades marítimas de produção). O presente trabalho aborda a análise técnica e econômica de um processo proposto de separação e captura de dióxido de carbono (CO2), através de estudo de caso (Primeira e Segunda Proposição) de simulação de processo, em uma instalação marítima de produção de petróleo, comparativamente a sua ausência (Caso Base). A Primeira Proposição considera a separação e a captura do CO2 oriundo tanto do gás natural produzido, quanto do gás de queima de uma turbina a gás. A Segunda Proposição considera a separação e a captura do CO2 oriundo somente do gás natural produzido. Até o momento, no Brasil, ainda não foram desenvolvidas tecnologias adequadas para a captura do CO2, em instalações marítimas de produção de petróleo. Adicionalmente a regulação atual (Portaria nº104/2002 da ANP) limita o potencial de utilização do CO2 que existe na composição do gás natural comercializado no país, pelo fato de não diferenciar em sua especificação técnica, os usos deste importante combustível. Os resultados obtidos nesta tese, com a utilização de simulador de processo de uso comercial mostraram emissões evitadas de CO2 para atmosfera de 55 % (caso Segunda Proposição que apresentou maior viabilidade econômica), em relação ao resultado obtido para o Caso Base. Este relevante resultado equivale a uma emissão evitada de aproximadamente 241 x 103 t/ano, para uma única unidade piloto proposta. De acordo com o estudo de análise econômica apresentado, a Segunda Proposição (VPL US$ 15,3 x 106) foi melhor do que a da Primeira Proposição (VPL: US$ 13,9 x 106) ambos usando o Caso Base como referência. Dentre os ganhos esperados com o uso desta nova tecnologia destacam-se: redução do consumo interno e das perdas de gás natural, emissão evitada de CO2 e hidrocarbonetos para a atmosfera, além do aumento das práticas de armazenamento de gás e CO2, em reservatórios geológicos depletados de petróleo. Estima-se que num cenário futuro, com a implantação deste novo processo proposto, em instalações marítimas de produção de petróleo, uma relevante contribuição de emissões evitadas de gases de efeito estufa possa ocorrer na área de E&P de petróleo no Brasil. / The current Brazilian market needs to increase the natural gas supply to incentive the national scientific community to the challenge of developing new technologies routes aiming increase the utilization of the produced natural gas. Such challenge is followed by a world demand from signatory countries of the Kyoto Agreement (ratified in 2005) to reduce the greenhouse gas emissions. In spite of, the Brazil does not have any reduction goal, in the first period (2008 to 2012) the oil sector (E&P activity), by their oil operators companies that works in our country, has already established corporative goals to avoided greenhouse gas emissions in their production facilities (bigger predominance of offshore production unities). The present work approaches the economic and technical evaluation of a carbon dioxide (CO2) separation and capture proposal process (First and Second Proposal Case) comparatively your absence (Base Case). The First Case consider the CO2 separation and capture both the produced gas and exhausted gases of one turbine driven by gas. The Second Case consider only the CO2 separation and capture from the produced gas. At the present, in Brazil, it has not been developed yet suitable technologies, for such use, and the CO2 is normally disposal to the atmosphere. Moreover, the present Regulation (104/2002 ANP Decree) limit the potential of CO2 use existing in the gas composition that is marketed in the country, due to not differentiate the uses of this important fuel. The results obtained of this thesis, by using a process simulator of commercially use showed CO2 avoided emissions of 55 % to the atmosphere (Second Proposal Case that shows the best economic evaluation) related to the result obtained from the Base Case. This relevant result is equivalent in mass flow, to the avoidance emission of roughly 241 x 103 tons per year, for a single pilot unity proposal. According the economic evaluation study, the Second Proposal Case (VPL:US$ 15,3 x 106) was better than the First Case (VPL: US$ 13,9 x 106), using the Case Base as reference. Within the benefits expected with the use of this new technology are the following: reduction both the internal gas consumption and natural gas losses (atmospheric disposal), emissions avoided of CO2 and hydrocarbons, beyond the increase of CO2 and gas storage practices in offshore depleted oil fields. It is estimated, in future scenery, with the implantation of this new proposal process in offshore production unities, relevant contribution of avoided greenhouse gases emissions can occur in oil E&P tasks in Brazil.

Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2018-10-10T14:17:08Z No. of bitstreams: 1 Dissertac?a?o mestrado_rafa p?s banca - final.pdf: 6925259 bytes, checksum: 04c8ab3a00fa276e3a89008c46ce0d72 (MD5) / Approved for entry into archive by Caroline Xavier (caroline.xavier@pucrs.br) on 2018-10-16T16:50:44Z (GMT) No. of bitstreams: 1 Dissertac?a?o mestrado_rafa p?s banca - final.pdf: 6925259 bytes, checksum: 04c8ab3a00fa276e3a89008c46ce0d72 (MD5) / Made available in DSpace on 2018-10-16T16:55:39Z (GMT). No. of bitstreams: 1 Dissertac?a?o mestrado_rafa p?s banca - final.pdf: 6925259 bytes, checksum: 04c8ab3a00fa276e3a89008c46ce0d72 (MD5) Previous issue date: 2018-03-05 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / Ionic liquids (ILs) grafting in inorganic solids sorbents is a promising alternative to replace the usual separation process of carbon dioxide from natural gas currently performed using amines. ILs presents unique properties such as, low environmental impact, non-corrosion and process efficiency. The ILs 1,3-bis(3-trimethoxysilylpropyl)imidazolium chloride and 1-methyl-3-(3-trimethoxysilylpropyl)imidazolium chloride were immobilized in MCM-41 and MCMRH silica. The MCMRH was synthesized from rice husk. ILs chemical immobilization was carried out by grafting method, where covalent bonds are formed between silane and hydroxyl groups present in the support. Syntheses were carried out in toluene under nitrogen atmosphere to prevent the hydrolysis and condensation of methoxy groups in the silane structure. CO2 sorption capacity and selectivity for CO2/CH4 were evaluated after synthesis. ILs in concentrations of 10 and 20% were tested. The samples characterization by XPS, NMR, FTIR and TGA confirmed the formation of the proposed IL structures. Sorption and selectivity results showed that the immobilization reduces the CO2sorption capacity, however the selectivity of the materials was higher in relation to the pristine silica. Supports immobilized with ILs 1-methyl-3- (3-trimethoxysilylpropyl) imidazole chloride presented better performance. The observed selectivity increase was 25% when 10% of IL was supported on MCMRH silica. / A imobiliza??o de l?quidos i?nicos ? LIs em suportes inorg?nicos ? uma alternativa ao uso de aminas no processo de separa??o e captura do di?xido de carbono contido no g?s natural, pois possui vantagens ligadas ao aumento de vida ?til de equipamentos, efici?ncia de processo e impacto ambiental. Os LIs cloreto de 1,3-bis(3-trimetoxisililpropil)imidazol e cloreto de 1-metil-3-(3-trimetoxisililpropil)imidazol foram imobilizados na s?lica comercial MCM-41 e na s?lica sintetizada a partir da casca de arroz nomeada neste trabalho como MCMRH. A imobiliza??o qu?mica dos LIs foi realizada atrav?s da forma??o de liga??es covalentes entre grupos silanos na estrutura do l?quido i?nico e grupos hidroxila presentes nos suportes. As s?nteses foram realizadas em tolueno sob condi??es inertes para controle da hidr?lise e condensa??o de grupos metoxi na estrutura dos silanos. Ap?s a sua s?ntese, os suportes imobilizados com LIs tiveram sua capacidade de sor??o de CO2 e seletividade em rela??o a CO2/CH4 avaliadas. LIs em concentra??es de 20 e 10% foram testadas. A caracteriza??o das amostras por XPS, RMN, FTIR e TGA confirmaram a forma??o das estruturas dos LIs propostos e os resultados de sor??o e seletividade mostraram que a imobiliza??o reduz a capacidade de sor??o em rela??o ao CO2, entretanto a seletividade dos materiais foram maiores em rela??o aos suportes antes da imobiliza??o. Os suportes imobilizados com o LIs cloreto de 1-metil-3-(3-trimetoxisililpropil)imidazol tiveram melhor desempenho em rela??o aos demais, o aumento de seletividade observado foi de 25% no melhor caso, onde 10% de LI foi suportado na s?lica MCMRH.

Ce travail porte sur l'étude de la capacité d'absorption du CO2 par différents types d'amines dissoutes en milieux aqueux et non aqueux. Ce dernier est constitué d'un mélange de chlorure de choline et d'éthylène glycol dans une proportion molaire respectivement de 1 pour 2. Ce solvant, communément appelé "Ethaline", appartient à la catégorie dite des « Solvants à Eutectique Profond » ainsi désignés car leur composition eutectique permet d'obtenir des mélanges généralement liquides à température ambiante. Pour ce faire un appareil d'équilibre liquide-vapeur avec analyse en ligne de la phase vapeur par GC a été réalisé et son fonctionnement validé. Les isothermes d'absorption du CO2 ainsi que la volatilité (composition de la phase vapeur) des mélanges étudiés, avec et sans CO2, ont été déterminées à différentes températures et pour différentes compositions en amines. Le domaine de pression exploré est particulièrement large : du Pascal à 800 kPa. L'étude a montré que la substitution de l'eau par "l'Ethaline" conduit à une capacité d'absorption du CO2 presque identique à celle de la MEA et DEA en solution aqueuse. Par contre dans le cas de la MDEA on observe une capacité d'absorption plus faible en milieu « Ethaline » qu'en milieu aqueux. Les isothermes d'absorption du CO2 des trois classes d'amines en milieu aqueux et non aqueux ont été corrélés par les modèles semi empiriques de (Gabrielsen et al., 2005) initialement établis par ces auteurs pour les solutions aqueuses (un modèle pour les amines primaires et secondaires conduisant à la formation de carbamates en présence de CO2, un modèle pour les amines tertiaires donnant des sels d'ammonium avec le CO2). Nous avons montré que ces deux modèles représentent avec succès les isothermes d'absorption en milieu non aqueux. Les constantes d'équilibre et les enthalpies de réaction qui s'en déduisent montrent que ces dernières sont plus faibles (en valeur absolue) pour la MEA et TMDEA en solution éthaline qu'en solution aqueuse. Dans le cas de la MDEA la nature du solvant n'a qu'une influence minime sur l'enthalpie de réaction. Les valeurs expérimentales des volatilités des amines dans les différents mélanges Amine- CO2 en milieu aqueux ont été corrélées par différents modèles semi-empiriques. Trois modèles thermodynamiques de coefficients d'activité ; le modèle de Wilson, NRTL et UNIQUAC ont été utilisés afin de restituer les données expérimentales de l'équilibre liquide-vapeur des systèmes aqueux d'amines (sans CO2). Une représentation satisfaisante des résultats expérimentaux par les trois modèles a été obtenue / This work focuses on the study of the absorption capacity of CO2 by different types of dissolved amines in aqueous and non-aqueous media. The latter consists of a mixture of choline chloride and ethylene glycol in a molar proportion of 1 to 2 respectively. This solvent, commonly called "Ethaline", belongs to the category called "Deep Eutectic Solvents" so designated because their eutectic composition makes it possible to obtain mixtures that are generally liquid at room temperature. With this aim, a liquid-vapor equilibrium apparatus with on-line analysis of the vapor phase by GC was performed and its operation validated. The CO2 absorption isotherms and the volatility (composition of the vapor phase) of the studied mixtures, with and without CO2, were determined at different temperatures and for different amine compositions. The explored pressure range is particularly large: from 1 Pa to 800 kPa. The study showed that the substitution of water by "Ethaline" leads to a CO2 absorption capacity almost identical to that of MEA and DEA in aqueous solution. On the other hand, in the case of MDEA, a lower absorption capacity is observed in Ethaline than in aqueous medium. In the hypothesis of a use of the DES+amine solvent for CO2 capture in post-combustion process, a decrease of the vapor pressure of the solvent (comparing to that of water+amine) has an advantage because of the low solvent loss due to vaporization in the absorber. The second advantage is most likely a lower effect of equipment corrosion, the third positive point is a lower enthalpy of absorption of MEA and MDEA in (1 ChCl : 2 EG) comparing to aqueous medium, resulting in a possible saving of energy in the regenerator of almost 40%. The disadvantage of the use of amines in "Ethaline" solution is the high viscosity of this solvent which decreases the kinetics of material transfer and reaction with CO2. The CO2 absorption isotherms and the experimental values of the amine volatilities in the different Amine-H2O-CO2 mixtures were well correlated by different semi-empirical models. Three thermodynamic models based on the activity coefficients; the Wilson model, NRTL and UNIQUAC were used to restitute experimental data for the liquid-vapor equilibrium of aqueous amine systems (without CO2). A satisfactory representation of the experimental results by the three models was obtained