Este trabalho tem por objetivo avaliar a viabilidade técnica de processos de separação de gás carbônico em correntes de gases de combustão. Neste sentido, a separação por meio de membranas e por criogenia são avaliadas por meio de simulação de sistemas. As propostas envolvendo membranas avaliam arranjos de membranas em série, os quais são otimizados para condições de maior fluxo permeado e maior beneficio econômico. A corrente de alimentação é de 5 kmol/s e as respectivas frações molares de CO2 e N2 que compõem esta corrente são 0,15 e 0,85. Os resultados obtidos da otimização, para um arranjo de três membranas em série de polyimida de 9000 m² de área superficial, foram uma corrente de permeado de 443,1 mol/s de CO2 a 41,6%, correspondendo a aproximadamente 59% do CO2 da corrente de alimentação. Já com um arranjo de 6 membranas de 9000 m², onde a função objetivo é o maior lucro, foi selecionado o material kapton e a quantidade de CO2 separada é 161,12 mol/s, cuja concentração na mistura é de 79%, e a função objetivo tem um valor de 24.405,30 €/ano. Na outra parte do trabalho, propõe-se e avalia-se um ciclo para o aproveitamento da disponibilidade térmica na regasificação do gás natural líquido, para liquefação de CO2. Obtém-se como resultando em CO2 líquido com fração molar igual a 94%. Este processo consta de uma corrente proveniente da combustão completa de 1 mol/s de metano, contendo 1 mol/s de CO2 e 7,52 mol/s de N2. Esta corrente é comprimida e resfriada até atingir a pressão de 4000 kPa e 25 °C, posteriormente uma membrana enriquece a corrente de gases de combustão, que novamente é comprimida e resfriada até se obter a condensação e separação do CO2. Realiza-se o cálculo de equilíbrio líquido-vapor da mistura utilizando as equações de Peng-Robinson e a regra de mistura de Van der Waals no software VRTherm. A vazão molar do CO2 líquido obtida é de 0,3207 mol/s na concentração declarada. A intensidade energética do processo é de 1,135 kWh/kg de CO2 liquefeito. / The objective of this work is to evaluate the technical feasibility of carbon dioxide separation processes of flue gases streams. In this way, separation processes due membrane and cryogenics are evaluated by system simulation. The systems using membranes evaluates setup of those membranes in series, these setups are optimized for the largest permeate molar flow and the largest economic profit. The feed stream is a 5 kmol/s CO2 – N2 mixture, with molar fraction of 0.15 and 0.85 respectively. The result obtained from the optimization for a setup of three polyimide membranes of 9000 m² is a permeate stream of 443.1 mol/s with CO2 at 41.6%, corresponding to aproximadely 59% of the CO2 contained in the feed stream. When a setup of six 9000 m² membranes is analyzed using an objective function that results in the largest profit, kapton was selected as the material for the membranes. The quantity of CO2 captured is 161.12 mol/s, at 79% of concentration in the mixture, and the objective function has a value of 24,405.30 €/year. The second part of this work, proposes and evaluates a cycle that takes the thermal availability of the regasification of liquid natural gas in advantage for CO2 liquefaction. The product of the cycle is liquid CO2, with a molar fraction of 0.94. The process is fed with a stream that comes from the stoichiometric combustion of 1 mol/s of methane, that stream is composed by 1 mol/s of CO2 and 7.52 mol/s of N2. The stream is then compressed up to the pressure of 4000 kPa and cooled down to 25 °C. After that a membrane concentrates the CO2 in one stream, which is again compressed and cooled down until the condensation of CO2 is achieved. Calculations of liquid – vapor are performed with the Peng- Robinson’s equations and the Van der Waals mixture rule using the software VRTherm. The molar flow rate of liquid CO2 obtained is of 0.3207 mol/s in the concentration mentioned before. The energy intensity of the process is of 1.135 kWh/kg of liquid CO2.

Increasing CO2 emissions from the energy and industrial sectors are a worldwide concern due to the effects that these emissions have on the global climate. Carbon capture and storage has been identified as one of a portfolio of technologies that would mitigate the effects of global warming in the upcoming decades. Calcium looping is a second generation carbon capture technology aimed at reducing the CO2 emissions from the power and industrial sectors. This thesis assesses the improvement of the calcium looping cycle for CO2 capture through enhanced sorbent production and testing at lab-, bench- and pilot-scale, and a new operational mode with high oxygen concentrations in the calciner through experimental campaigns in Cranfield’s 25 kWth pilot unit. Novel biomass-templated sorbents were produced using the pelletisation technique and tested at different conditions in a thermogravimetric analyser (TGA) and a bench-scale plant comprising a bubbling fluidised bed (BFB) reactor. Moreover, the effects of sorbent poisoning by SO2, and the influence of steam were studied in order to explore the effects of real flue gas on this type of material. In addition to the chemical performance, the mechanical strength, i.e. resistance to fragmentation of these materials was tested. In additon, two different kinds of enhanced materials were produced and tested at pilot-scale. Namely, calcium aluminate pellets and HBr-doped limestone were used in experimental campaigns in Cranfield’s 25 kWth pilot plant comprising a CFB carbonator and a BFB calciner. The suitability of these materials for Ca looping was assessed and operation challenges were identified in order to provide a basis for synthetic sorbent testing at a larger scale. Lastly, a new operational mode was tested, which is aimed at reducing the heat provided to the calciner through high oxygen concentration combustion of a hydrocarbon (in this case natural gas) in the calciner. This approach reduces or even eliminates the recirculated CO2 stream in the calciner. In consequence, this results in a lower capital (reduced size of the calciner) and operational cost (less oxygen and less fuel use). Several pilot plant campaigns were performed using limestone as solid sorbent in order to prove this concept, which was successfully verified for concentrations of up to 100% vol oxygen in the inlet to the calciner.

La technologie de Captage et Stockage du CO2 (CSC) est considérée comme une des principales solutions pour limiter les rejets de gaz à effet de serre (CO2) et lutter contre le réchauffement climatique. L’étape de captage fait appel à un procédé de séparation des fumées de post combustion qui a pour fonction l’extraction sélective du CO2 des autres composés. Les principales performances visées sont un taux de capture et une pureté du CO2 supérieurs à 90%, ainsi qu’une consommation énergétique minimale afin de ne pas générer un niveau trop élevé d’émissions secondaires de CO2. La perméation gazeuse par membrane dense est une technologie de séparation potentiellement applicable au captage du CO2 en post combustion. Sur la base de différents types de matériaux et mécanisme de transport associés (processus physique ou chimique) une large plage de valeurs de perméabilité et de sélectivité peut être atteinte. Une des dernières familles de membrane ayant démontrée des performances de séparation pouvant être intéressantes pour le captage du CO2 sont les membranes à transport facilité dites ‘’réactives ‘’. Une analyse systématique des performances de séparation de modules membranaires basés sur des membranes physiques (polymères denses) et sur des membranes réactives (transport facilité) pour le traitement de fumées de post combustion a été réalisée. La simulation d’un procédé de captage complet, incluant un ou deux étages de séparation membranaire, une étape de séchage et une étape de compression a ensuite été effectuée. L’ensemble des résultats, en particulier la pénalité énergétique globale du système et l’estimation des surfaces membranaires nécessaires, permet de positionner la technologie de perméation gazeuse comparativement aux autres procédés de captage / CO2 Capture and Storage (CCS) is a promising solution to separate CO2 from flue gas, to reduce the CO2 emissions in the atmosphere, and hence to reduce global warming. In CCS, one important constraint is the high additional energy requirement of the different capture processes. That statement is partly explained by the low CO2 fraction in the inlet flue gas and the high output targets in terms of CO2 capture and purity (>90%).Gas permeation across dense membrane can be used in post combustion CO2 capture. Gas permeation in a dense membrane is ruled by a mass transfer mechanism and separation performance in a dense membrane are characterized by component’s effective permeability and selectivity. One of the newest and encouraging type of membrane in terms of separation performance is the facilitated transport membrane. Each particular type of membrane is defined by a specific mass transfer law. The most important difference to the mass transfer behavior in a dense membrane is related to the facilitated transport mechanism and the solution diffusion mechanism and its restrictions and limitations.Permeation flux modelling across a dense membrane is required to perform a post combustion CO2 capture process simulation. A CO2 gas permeation separation process is composed of a two-steps membrane process, one drying step and a compression unit. Simulation on the energy requirement and surface area of the different membrane modules in the global system are useful to determine the benefits of using dense membranes in a post combustion CO2 capture technology

L'objectif de ces travaux vise à évaluer les performances d'un contacteur membranaire à fibres creuses utilisé pour réaliser l'absorption chimique du CO2 dans une solution ammoniacale ainsi que la régénération de cette dernière. Les membranes utilisées sont composites, c'est-à-dire composées d'une fine couche dense recouverte sur un support microporeux, la couche dense permettant d'éviter le mouillage par pénétration de liquide dans la membrane. Pour réaliser ces études, une approche combinant expérimentation et modélisation a été adoptée. Lors de la réalisation de l'absorption chimique avec un contacteur membranaire, des chutes importantes d’efficacité de captage du CO2 au cours du temps ont été observées et confirment les résultats obtenus lors de travaux ultérieurs. Cette baisse des performances est attribuée à la précipitation de sels d’ammonium en phase gaz. Lors de l'utilisation d’un gaz saturé en vapeur d'eau, comme le seraient les fumées industrielles, les performances du procédé se sont révélées stables. Un modèle 1D multi-composant adiabatique du contacteur a été développé sur Aspen Custom Modeler® et validé à partir des résultats expérimentaux. Les simulations réalisées avec ce modèle ont confirmé le potentiel d'intensification volumique de la technologie, toutefois, la réduction des pertes de NH3, grâce à l'utilisation d’une couche dense sélective moins perméable à NH3 qu’au CO2, n’a pas été satisfaisante. Les phénomènes de condensation dans les contacteurs membranaires ont été étudiés par expérimentation et modélisation. Il a ainsi été montré que le mouillage par condensation de la membrane ne devrait pas survenir, par contre, la condensation dans le lumen des fibres creuses entraîne une augmentation importante de la perte de charge pouvant conduire à des coûts de compression des gaz à traiter plus élevés. Des expériences et des simulations sur la régénération de solutions ammoniacales chargées avec des contacteurs membranaires ont été effectuées et des disparités importantes ont été trouvées entre les flux de CO2 mesurés et simulés. Une réduction volumique de trois par rapport à la colonne à garnissage a pu être calculée laissant entrevoir un potentiel intéressant de la technologie pour l’étape de régénération. En collaboration avec les partenaires du projet C2B, dans lequel s’intègre cette thèse, des essais d’absorption de CO2 ont été réalisés sur site avec un contacteur de taille industrielle. Les résultats de ce pilote sont conformes aux résultats obtenus au laboratoire et encourageants quant au transfert de la technologie vers l’échelle industrielle / This work aims to evaluate the performances of hollow fiber membrane contactors used for the CO2 absorption in aqueous ammonia and the regeneration of the latter within the frame of post-combustion CO2 capture. Fibers are made of a thin dense layer coated on a microporous support, the dense layer prevent membrane wetting by liquid penetration. Both experiment and modelling were done. During absorption experiments, important decrease of the CO2 capture efficiency was observed due to ammonium salts precipitation in the gas-side corroborating results from previous works. Experiments with CO2/N2 mixture saturated with water vapor, as would be the case for flue gas, interestingly, showed stable performances of the process. A one-dimensional multi-component adiabatic transfer model for CO2 absorption in NH3 has been implemented in Aspen Custom Modeler® and validated with experimental results. The simulations performed with the model confirmed the volumetric intensification potential of the technology, however, the NH3 slip reduction expected, because of the use of a dense layer more permeable to CO2 than NH3, wasn’t satisfying. Water condensation phenomenon in membrane contactors were studied with both experiments and simulations. It was thus showed that membrane pore wetting by condensation should not happened but gas-side condensation led to an important increase of the pressure drop with the potential of increasing compression costs. Experiments and simulations of the desorption of CO2 from a loaded aqueous ammonia solution with a membrane contactor were performed and important disparities were found between CO2 flux measured and simulated. A volumetric reduction of the membrane contactor when compared to the packed column was calculated highlighting the potential of the technology for the stripping step. In collaboration with the partners of the C2B project, in which this thesis is integrated, CO2 absorption essays were carried out on site with an industrial scale membrane contactor. The results of this pilot are consistent with laboratory results and encourages the transfer of the technology to the industrial scale

Deux types de matériaux membranaires ont été développés pour la séparation du CO2. Les premiers associent un matériau polymère de référence (Pebax®) à de nouveaux additifs pseudopeptidiques bioconjugués. Ces bioconjugués pseudopeptide-polymère ont été obtenus par une stratégie de synthèse de type « grafting-to » à partir de pseudopeptides 1:1[α/α-Nα-Bn-hydrazino] dimère et tétramère fonctionnalisés par une fonction alcyne. La partie oligomérique poly(acrylate de diéthylène glycol) (PEDEGA) a été synthétisée de façon contrôlée par « Single Electron Transfer Living Radical Polymerization » (SET-LRP) à partir d’un amorceur azido fonctionnel permettant un couplage direct par chimie « click » CuAAC. L'influence de ces additifs sur les propriétés de sorption et de séparation du CO2 a été analysée en termes de relations propriétés-morphologie-structure. Ces additifs originaux ont permis d’augmenter les performances de séparation du CO2 de la membrane référence ; en améliorant de 46% la perméabilité au CO2, tout en maintenant de bonnes sélectivités αCO2/N2 = 44 et αCO2/CH4 = 13. Par ailleurs, deux familles de poly(uréthane-imide)s (PUIs) à architecture contrôlée ont été développées dans l'objectif d'obtenir des matériaux avec des proportions très élevées en unités oxyde d'éthylène tout en évitant leur cristallisation. Des PUIs multi-blocs linéaires ont été synthétisés par polycondensation avec différentes tailles de bloc souple polyéther Jeffamine, correspondant à des taux massiques de phase souple variant entre 40% et 70%. Afin d'augmenter encore la proportion de phase souple jusqu'à la valeur très élevée de 85%, des PUIs multi-blocs greffés ont ensuite obtenus par une stratégie de "grafting-to" à partir d'un précurseur PUI comportant des fonctions alcyne latérales et d'oligomères azido-PEDEGA de différentes masses molaires. L’évolution de leurs performances de séparation du CO2 a été corrélée à leur proportion de phase souple et morphologie et à leur capacité d’interaction avec le CO2. Au taux maximal de phase souple (85%), on obtient des performances élevées (PCO2 = 196 Barrer ; αCO2/N2 = 39 et αCO2/CH4 = 12). Ainsi, par rapport au PUI greffable précurseur, le greffage d'oligomères PEDEGA a permis de multiplier la perméabilité jusqu’à 17 fois en maintenant la valeur élevée de αCO2/N2 constante et avec une diminution de seulement 30% de αCO2/CH4. En permettant d'obtenir une proportion très élevée de phase souple non cristalline, la stratégie de greffage s'est donc révélée exceptionnellement efficace pour améliorer les performances des copolymères multi-blocs PUI pour la capture du CO2. / In this PhD thesis, two types of membrane materials were developed for CO2 separation. The first ones associate a reference polymer material (Pebax®) with new pseudopeptidic bioconjugates additives. These pseudopeptide-polymer bioconjugates were obtained by a "grafting-to" synthetical pathway from alkyne-functionalized 1:1[α/α-Nα-Bn-hydrazino] dimer and tetramer pseudopeptides. Poly(diethylene glycol acrylate) (PEDEGA) oligomeric part was synthesized under controlled conditions using Single Electron Transfer Living Radical Polymerization (SET-LRP) from an azido-functionalized initiator allowing direct coupling via CuAAC "click" chemistry. The influence of these additives on CO2 sorption and separation properties was analyzed in terms of properties-morphology-structure relationships. These original additives allowed to enhance CO2 separation performances of the reference membrane, increasing CO2 permeability by 46%, and maintaining good selectivities αCO2/N2 = 44 et αCO2/CH4 = 13. In another work, two families of poly(urethane-imide)s (PUIs) with controlled architecture were developed for obtaining membrane materials with high content in ethylene-oxide units while avoiding their crystallization. Linear multi-blocks PUIs were first synthesized by polycondensation with different sizes of Jeffamine polyether soft block, corresponding to soft block contents varying from 40 to 70%wt. To further increase the soft phase content until a very high level (85%wt), grafted multi-blocks PUIs were obtained by a "grafting-to" strategy from an alkyne-functionalized precursor PUI and azido-PEDEGA oligomers with different molar weights. The evolution of their CO2 separation performances were correlated to their soft phase content, morphology and CO2 sorption ability. For the maximum soft phase content (85%wt), high performances were obtained for CO2 separation (PCO2 = 196 Barrer ; αCO2/N2 = 39 et αCO2/CH4 = 12). Compared to the precursor PUI, the grafting strategy allowed to increase CO2 permeability 17-fold. At the same time, the good selectivity αCO2/N2 was maintained with a slight decrease (-30%) of the selectivity αCO2/CH4. By allowing very high non-crystalline soft phase contents, the grafting strategy was exceptionally efficient in improving multi-block copolymer performances for CO2 capture

Este trabalho tem por objetivo avaliar a viabilidade técnica de processos de separação de gás carbônico em correntes de gases de combustão. Neste sentido, a separação por meio de membranas e por criogenia são avaliadas por meio de simulação de sistemas. As propostas envolvendo membranas avaliam arranjos de membranas em série, os quais são otimizados para condições de maior fluxo permeado e maior beneficio econômico. A corrente de alimentação é de 5 kmol/s e as respectivas frações molares de CO2 e N2 que compõem esta corrente são 0,15 e 0,85. Os resultados obtidos da otimização, para um arranjo de três membranas em série de polyimida de 9000 m² de área superficial, foram uma corrente de permeado de 443,1 mol/s de CO2 a 41,6%, correspondendo a aproximadamente 59% do CO2 da corrente de alimentação. Já com um arranjo de 6 membranas de 9000 m², onde a função objetivo é o maior lucro, foi selecionado o material kapton e a quantidade de CO2 separada é 161,12 mol/s, cuja concentração na mistura é de 79%, e a função objetivo tem um valor de 24.405,30 €/ano. Na outra parte do trabalho, propõe-se e avalia-se um ciclo para o aproveitamento da disponibilidade térmica na regasificação do gás natural líquido, para liquefação de CO2. Obtém-se como resultando em CO2 líquido com fração molar igual a 94%. Este processo consta de uma corrente proveniente da combustão completa de 1 mol/s de metano, contendo 1 mol/s de CO2 e 7,52 mol/s de N2. Esta corrente é comprimida e resfriada até atingir a pressão de 4000 kPa e 25 °C, posteriormente uma membrana enriquece a corrente de gases de combustão, que novamente é comprimida e resfriada até se obter a condensação e separação do CO2. Realiza-se o cálculo de equilíbrio líquido-vapor da mistura utilizando as equações de Peng-Robinson e a regra de mistura de Van der Waals no software VRTherm. A vazão molar do CO2 líquido obtida é de 0,3207 mol/s na concentração declarada. A intensidade energética do processo é de 1,135 kWh/kg de CO2 liquefeito. / The objective of this work is to evaluate the technical feasibility of carbon dioxide separation processes of flue gases streams. In this way, separation processes due membrane and cryogenics are evaluated by system simulation. The systems using membranes evaluates setup of those membranes in series, these setups are optimized for the largest permeate molar flow and the largest economic profit. The feed stream is a 5 kmol/s CO2 – N2 mixture, with molar fraction of 0.15 and 0.85 respectively. The result obtained from the optimization for a setup of three polyimide membranes of 9000 m² is a permeate stream of 443.1 mol/s with CO2 at 41.6%, corresponding to aproximadely 59% of the CO2 contained in the feed stream. When a setup of six 9000 m² membranes is analyzed using an objective function that results in the largest profit, kapton was selected as the material for the membranes. The quantity of CO2 captured is 161.12 mol/s, at 79% of concentration in the mixture, and the objective function has a value of 24,405.30 €/year. The second part of this work, proposes and evaluates a cycle that takes the thermal availability of the regasification of liquid natural gas in advantage for CO2 liquefaction. The product of the cycle is liquid CO2, with a molar fraction of 0.94. The process is fed with a stream that comes from the stoichiometric combustion of 1 mol/s of methane, that stream is composed by 1 mol/s of CO2 and 7.52 mol/s of N2. The stream is then compressed up to the pressure of 4000 kPa and cooled down to 25 °C. After that a membrane concentrates the CO2 in one stream, which is again compressed and cooled down until the condensation of CO2 is achieved. Calculations of liquid – vapor are performed with the Peng- Robinson’s equations and the Van der Waals mixture rule using the software VRTherm. The molar flow rate of liquid CO2 obtained is of 0.3207 mol/s in the concentration mentioned before. The energy intensity of the process is of 1.135 kWh/kg of liquid CO2.

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Agradecemos a compreensão. on 2016-04-07T20:05:13Z (GMT) / Submitted by KELY REGINA MAXIMO VIEIRA null (kely_eng@hotmail.com) on 2016-04-07T20:34:23Z No. of bitstreams: 1 Dissertação Kely UNESP FEG.pdf: 6196946 bytes, checksum: bf09868facff4fd8869dde5f2fcde047 (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2016-04-08T16:21:52Z (GMT) No. of bitstreams: 1 vieira_krm_me_guara.pdf: 6196946 bytes, checksum: bf09868facff4fd8869dde5f2fcde047 (MD5) / Made available in DSpace on 2016-04-08T16:21:52Z (GMT). No. of bitstreams: 1 vieira_krm_me_guara.pdf: 6196946 bytes, checksum: bf09868facff4fd8869dde5f2fcde047 (MD5) Previous issue date: 2016-03-08 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Nesta dissertação, investiga-se a reação de dissolução ácida de rochas silicatos brasileiras visando a aplicação em um processo de captura e sequestro de carbono denominado por Carbonatação Mineral. Na carbonatação mineral pela rota indireta utiliza-se ácidos, bases ou sais de amônia para a extração do magnésio, principalmente, presente na rocha silicato a fim de a formar carbonatos estáveis. Destaca-se que a etapa de dissolução ácida é uma fase limitante para o processo de carbonatação mineral, principalmente por apresentar baixa taxa de reação. O objetivo deste trabalho é utilizar o ácido clorídrico (HCl) e dois serpentinitos oriundos do estado de Goiás e Minas Gerais para avaliar o processo de dissolução ácida. Os serpentinitos foram preparados, selecionados e caracterizados para determinar a composição elementar. Aplicou-se o planejamento experimental e arranjo L9 de Taguchi na avaliação dos fatores que influenciam o processo de dissolução, tais como, temperatura do processo, concentração do HCl, tamanho médio das partículas da matéria prima e excesso de ácido. Os 9 ensaios previstos na matriz de planejamento para cada serpentinito foram executados de forma aleatória e em duplicata. Os produtos finais, resíduo sólido retido no papel filtro e solução contendo os elementos de interesse, foram analisados obtendo-se a composição elementar das soluções. Considerando-se os testes previstos na matriz de planejamento, a condição de melhor ajuste para extração de Mg foi utilizando-se a granulometria média de 69 µm, temperatura de 70°C, HCl 2 M com quatro vezes a quantidade estequiométrica. Nas soluções foram obtidas as concentrações de 29 % e 76 % de Mg para as amostras de serpentinito de Minas Gerais e de Goiás, respectivamente. Foram também avaliadas as melhores condições para extração de Fe e Ca e menor extração de Si, uma vez que o Si diminui a conversão no processo. Na análise estatística verificou-se que para a amostra de Minas Gerais todos os fatores apresentaram significância. No caso da a amostra de Goiás a temperatura no nível alto (70°C) apresentou maior significância. / In this dissertation, acid dissolution reaction of Brazilian silicate rocks was investigated aiming the implementation in a Carbon Capture and Storage process named Mineral Carbonation. In the mineral carbonation by indirect route, acids, bases or salts of ammonia are used for magnesium extraction, mainly, present in the silicate rock in order to form stable carbonates. It is noteworthy that the acid dissolution step is a limiting step in the process of mineral carbonation, mainly because of its low reaction rate. The objective of this study was to use hydrochloric acid (HCl) and two serpentinites from Goiás and Minas Gerais states to evaluate the acid dissolution process. The serpentinites were prepared, selected, and characterized to determine the elemental composition. The L9 experimental design and Taguchi arrangement were applied to evaluate the factors that influence in the dissolution process, such as process temperature, HCl concentration, average particle size of material and acid excess. The nine tests prescribed in planning matrix for each serpentinite were performed at random and in duplicate. The end products, solid residue retained on the filter paper and the solution containing the elements of interest were analyzed obtaining the elemental composition of the solutions. Considering the prevised tests on planning matrix, the best adjust condition for Mg extraction was using the average particle size of 69 µm temperature of 70°C, 2 M HCl with four times the stoichiometric amount. In the solutions, the concentrations obtained were 29 % and 76 % Mg for samples of serpentinite from Minas Gerais and Goiás, respectively. The best conditions for the extraction of Fe and Ca and lower extraction of Si were evaluated, since Si decreases the conversion in the process. In the statistical analysis was found that in Minas Gerais sample all factors were significant. In the case of Goiás sample, the temperature at the high level (70°C) showed greater significance.

Selective Exhaust Gas Recirculation (S-EGR) consists of selectively transferring CO2 from the exhaust gas stream of a gas-fired power plant into the air stream entering the gas turbine compressor. Unlike in “non-selective” Exhaust Gas Recirculation (EGR) technology, recirculation of, principally, nitrogen does not occur, and the gas turbine still operates with a large excess of air. Two configurations are proposed: one with the CO2 transfer system operating in parallel to the post-combustion carbon capture (PCC) unit; the other with the CO2 transfer system operating downstream of, and in series to, the PCC unit. S-EGR allows for higher CO2 concentrations in the flue gas of approximately 13-14 vol%, compared to 6.6 vol% with EGR at 35% recirculation ratio. The oxygen levels in the combustor are approximately 19 vol%, well above the minimum limit of 16 vol% with 35% EGR reported in literature. At these operating conditions, process model simulations show that the current class of gas turbine engines can operate without a significant deviation in the compressor and the turbine performance from the design conditions. Compressor inlet temperature and CO2 concentration in the working fluid are critical parameters in the assessment of the effect on the gas turbine net power output and efficiency. A higher turbine exhaust temperature allows the generation of additional steam which results in a marginal increase in the combined cycle net power output of 5% and 2% in the investigated configurations with S-EGR in parallel and S-EGR in series, respectively. With aqueous monoethanolamine scrubbing technology, S-EGR leads to operation and cost benefits. S-EGR in parallel operating at 70% recirculation, 97% selective CO2 transfer efficiency and 96% PCC efficiency results in a reduction of 46% in packing volume and 5% in specific reboiler duty, compared to air-based combustion CCGT with PCC, and of 10% in packing volume and 2% in specific reboiler duty, compared to 35% EGR. S-EGR in series operating at 95% selective CO2 transfer efficiency and 32% PCC efficiency results in a reduction of 64% in packing volume and 7% in specific reboiler duty, compared to air-based, and of 40% in packing volume and 4% in specific reboiler duty, compared to 35% EGR. An analysis of key performance indicators for selective CO2 transfer proposes physical adsorption in rotary wheel systems as an alternative to selective CO2 membrane systems. A conceptual design assessment with two commercially available adsorbent materials, activated carbon and Zeolite X13, shows that it is possible to regenerate the adsorbent with air at near ambient temperature and pressure. Yet, a significant step change in adsorbent materials is necessary to design rotary adsorption systems with dimensions comparable to the largest rotary gas/gas heat exchanger used in coal-fired power plants, i.e. approximately 24 m diameter and 2 m height. An optimisation study provides guidelines on the equilibrium parameters for the development of materials. Finally, a technical feasibility study of configuration options with rotary gas/gas heat exchangers shows that cooling water demand around the post-combustion CO2 capture system can be drastically reduced using dry cooling systems where gas/gas heat exchangers use ambient air as the cooling fluid. Hybrid cooling configurations reduce cooling and process water demand in the direct contact cooler of a wet cooling system by 67% and 35% respectively, and dry cooling configurations eliminate the use of process and cooling water and achieve adequate gas temperature entering the absorber.

Submitted by ALCINÉA GUIMARÃES DE CASTRO (neia.gcastro@ig.com.br) on 2017-07-06T14:47:04Z No. of bitstreams: 1 Tese Alcinéa Final 1.pdf: 4587551 bytes, checksum: a7dc82329f88aa34f25ffc873a918ab7 (MD5) / Approved for entry into archive by LUIZA DE MENEZES ROMANETTO (luizamenezes@reitoria.unesp.br) on 2017-07-07T16:20:03Z (GMT) No. of bitstreams: 1 castro_ag_dr_guara.pdf: 4587551 bytes, checksum: a7dc82329f88aa34f25ffc873a918ab7 (MD5) / Made available in DSpace on 2017-07-07T16:20:03Z (GMT). No. of bitstreams: 1 castro_ag_dr_guara.pdf: 4587551 bytes, checksum: a7dc82329f88aa34f25ffc873a918ab7 (MD5) Previous issue date: 2017-06-26 / São inúmeros os serviços econômicos, sociais e ambientais atribuídos às florestas, sendo a fixação do carbono atmosférico o mais recente, pois contribui para a redução de gases do efeito estufa (GEE) e do aquecimento global, através do processo de fotossíntese na absorção do dióxido de carbono (CO2) pelas árvores. Buscando a redução dos GEE e a absorção do CO2, as centrais geradoras hidrelétricas (CGHs) e as pequenas centrais hidrelétricas (PCHs) são consideradas, por muitos estudiosos, como uma forma mais limpa de obtenção de energia, ainda que existam algumas discussões sobre os impactos ambientais gerados pelas mesmas. Assim, este estudo visa propor a mitigação da emissão do CO2, por meio da restauração ecológica, devido à instalação de uma central geradora hidrelétrica, com base na análise do potencial dos remanescentes florestais como sumidouros de carbono. Desta forma, utilizou-se mapas georreferenciados com dados físicos ambientais (hidrologia, classe de solo, uso da terra, drenagem, área de preservação permanente e maciços florestais nativos) que possibilitaram delimitar os remanescentes florestais existentes na bacia hidrográfica do Rio do Chapéu, localizada no município de São Luís do Paraitinga, SP, Brasil. Paralelamente, levantou-se os dados dendrométricos (altura da árvore e diâmetro à altura do peito) de 658 indivíduos arbóreos, distribuídos em 119 espécies de um fragmento florestal de 10.000 m2, que foram aplicados em equações alométricas, resultando uma estimativa de 62,25 t C ha-1 fixados pelas árvores e uma emissão de 9.232,92 t CO2 ha-1 devido à área de floresta inundada (reservatório) com a implantação de uma CGH hipotética na bacia hidrográfica. Esses dados evidenciaram que os componentes arbóreos contribuem para a fixação do carbono e que há necessidade da compensação ambiental, por meio da restauração ecológica, em 323,8 hectares de áreas de preservação permanente localizadas na bacia hidrográfica de contribuição. Considerando que atualmente não existem modelos para se estimar as GEE antes da construção do reservatório e que no Brasil a maior parte da energia elétrica gerada advém de usinas hidrelétricas, esta pesquisa poderá contribuir com o processo de licenciamento ambiental e na tomada de decisão quanto à implantação de centrais hidrelétricas, obtendo parâmetros e formas seguras de compensação ambiental, aos efeitos negativos gerados pelas emissões de GEE, em especial o CO2. / There are numerous economic, social and environmental services to forests, among which atmospheric carbon sequestration is the most recent, which contributes to reducing greenhouse gas (GHG) emissions and global warming through photosynthesis, i.e. carbon dioxide (CO2) absorption by trees. With the aim of reducing greenhouse gas emissions and absorbing CO2, small hydropower stations (SHS) and small hydropower plants (SHPs) are considered as a cleaner way to generate energy in literature, although there is some discussion regarding their environmental impacts. Thus, the present study aims to mitigate CO2 emissions from building a hydropower station through ecological restoration based on analyzing the potential of utilizing remnant forests as carbon sinks. Therefore, georeferenced maps have been used with environmental physical data (hydrology, soil type, land use, drainage, permanent preservation areas and native forest) that allowed defining the existing remnant forests along the Chapéu River watershed, which is located in São Luís do Paraitinga, SP, Brazil. In addition, dendrometric data (height and diameter at breast height) has been collected on 658 individual trees classified into 119 species in a forest area of 10,000 m2. Data used in an allometric equation resulted in an estimate of 62.25 C ha-1 t sequestrated by trees and CO2 emission of 9232.92 t ha-1 due to the flooded forest area (dam) if a SHS were constructed in the watershed. These data evidenced that trees contribute to carbon sequestration, and that there must be an environmental compensation through ecological restoration of 323.8 hectares of permanent environmental reserve areas located in the contributing watersheds. This research is going to assist in environmental licensing and decision-making processes regarding the implementation of hydropower stations due to obtaining parameters and safe forms of environmental compensation for the negative impacts generated by greenhouse gas emissions, especially CO2, given that there are currently no GHG estimation models before the dam implementation and most of the electricity supply is generated by hydropower plants in Brazil.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The increasing CO2 concentration in the atmosphere after Industrial Revolution mainly due to the increasing consumption of fossil fuels is considered the major role in global warming and greenhouse effect. Thereafter, alternatives have been sought to decrease this gas emission. CO2 capture is an appropriate option to achieve that reduction. It consists of separation of CO2 from flue gas and storage in a safe place. An economical way to separate it is through cycles of carbonation - calcination reactions, based on the carbonation reaction of CaO to capture CO2 and the subsequent calcination of CaCO3 to regenerate the sorbent. However, it has been found that the conversion of CaO to CaCO3 in the carbonation step decreases with increasing cycles because of the sintering phenomena. Hence, it is reasonable include a step of hydration of calcium oxide to keep the reactivity along many cycles. In this work, it was aimed to evaluate the use of a high limestone content waste from Vale Fertilizantes produced in apatite process to produce lime and capture CO2 over five calcination/hydration/carbonation reaction cycles. Firstly, it was studied the characteristics of the waste and it was determined its mean diameter, crystalline phases, specific surface area and the temperature which it starts calcining. Then, it was set a Central Composite Planning with the variables calcination temperature and time and it was used a thermogravimetric analysis to monitor the capture capacity of CO2 and the ASTM-C-110-76 to evaluate lime reactivity. The results indicate that, to all cycles, as calcination time and temperature increase the reactivity also increases until reach the best region, and then begins to decrease due to sintering. Furthermore, for the first cycle, those samples conducted at higher calcination temperatures showed better ability to capture, but over the cycles the ability to capture for all conditions tends to the same value. Therefore, it appears that temperature and time calcination do influence on CO2 uptake in initial cycles, but a large number of cycles, the effect becomes insignificant. Furthermore, the reactivity and the capture capacity showed similar behavior and were strongly influenced by the calcination temperature and time at the first cycle and become more independent of these conditions as cycle number increases. The maximum capacity declines over the cycles and drops from about 0,42 at the first cycle to about 0,23 at the fifth cycle and it is due to sintering phenomena which becomes more noticeable. / O aumento da concentração de CO2 na atmosfera após a Revolução Industrial, devido principalmente à queima de combustíveis fósseis, é apontado como um possível responsável pela intensificação do efeito estufa e consequente aumento da temperatura da Terra. Diante disto, tem-se buscado alternativas para diminuir as emissões deste gás. A captura de CO2 é uma técnica satisfatória para alcançar esta diminuição e consiste em separar o CO2 do gás efluente e armazená-lo em local seguro. Uma forma econômica de separá-lo é através de ciclos de reações calcinação-carbonatação, porém com o passar dos ciclos o óxido de cálcio produzido torna-se menos reativo devido à sinterização. Desta forma, é interessante incluir uma etapa intermediária de hidratação do óxido a fim de evitar o fechamento dos poros e manter a capacidade de captura ao longo de um número maior de ciclos. Diante disso, este trabalho visou aproveitar um resíduo em pó rico em calcário, produzido no processamento da apatita da Vale Fertilizantes, para produção de cal e captura de CO2 ao longo de cinco ciclos de reações calcinação-hidratação-carbonatação. Inicialmente, caracterizou-se o resíduo determinando o diâmetro médio de Sauter, as fases cristalinas, a área superficial específica e a faixa de temperatura em que ocorre a decomposição. Posteriormente, elaborou-se um Planejamento Composto Central com as variáveis temperatura e tempo de calcinação e foram utilizadas a análise termogravimétrica para monitorar a capacidade de captura de CO2 e a Norma ASTM-C-110-76 para avaliar a reatividade da cal. Os resultados indicam que, para todos os ciclos, conforme o tempo e a temperatura aumentam, a reatividade também aumenta até atingir um valor máximo e então começa a diminuir, devido à sinterização. Observou-se ainda que para o primeiro ciclo de reações, os experimentos conduzidos a temperaturas mais altas de calcinação proporcionaram maior reatividade e capacidade de captura. Porém, ao longo dos ciclos a diferença entre os resultados alcançados pelas amostras submetidas a diferentes condições de calcinação se torna cada vez menor, e as reatividades e capacidades de captura das amostras tendem para um mesmo valor, independente da temperatura e do tempo de calcinação. Desta forma, a reatividade e a capacidade de captura apresentaram comportamento análogos, sendo fortemente influenciadas pela temperatura e tempo de residência da calcinação no primeiro ciclo e se tornando cada vez mais independentes dessas condições. Observa-se ainda que a máxima capacidade de captura de CO2 diminui com o passar dos ciclos, passando de cerca de 0,42 no primeiro ciclo para cerca de 0,23 no quinto, indicando que a sinterização se torna mais acentuada. / Mestre em Engenharia Química