A presente dissertação de mestrado consiste na realização de um estudo geológico acerca do potencial para exploração e produção de gás natural não convencional na Bacia do Paraná, regiões sul e sudeste do Brasil e norte do Uruguai. Com essa finalidade, foram analisadas as formações geológicas Irati e Ponta Grossa, situadas na porção sul da bacia e caracterizadas por seu potencial gerador de hidrocarbonetos. O estudo também inclui a avaliação da viabilidade do abastecimento da usina termoelétrica de Uruguaiana a partir desse recurso, considerando os aspectos geológicos, socioeconômicos e ambientais associados. O projeto visa incentivar o estudo à temática de recursos energéticos não convencionais, com destaque para o shale gas, principal fonte de gás natural não convencional explorada no mundo, além de ressaltar os benefícios na crescente implantação do gás natural na matriz energética brasileira, tanto em aspectos estratégicos quanto econômicos. O projeto propõe a elaboração de um modelo descritivo-comparativo baseado nos aspectos geológicos dos principais campos produtores de shale gas nos Estados Unidos, principal produtor mundial, por meio do qual é avaliado o potencial para ocorrência desse recurso nos folhelhos negros correspondentes às Formações Irati e Ponta Grossa, segundo parâmetros geoquímicos, petrofísicos e geológicos presentes em formações comprovadamente produtoras nos EUA: Marcellus, Barnett e Eagle Ford. O modelo descritivo tem finalidade de avaliar o potencial para exploração, produção e distribuição de gás natural não convencional nas regiões sul e sudeste do Brasil, as quais representam o maior mercado consumidor e demanda por energia no país. Com base na análise comparativa realizada, atribui-se às formações brasileiras potencial moderado a elevado para a geração de shale gas. Entretanto, a viabilidade no abastecimento da usina termoelétrica de Uruguaiana depende, além da geologia local, de fatores político-regulatórios ainda pouco consolidados no país para a incentivar a produção de recursos energéticos não convencionais. / The presented Masters Thesis consists on a geological study of the potential for exploration and production of unconventional natural gas in the Paraná Sedimentary Basin, southern and southeastern Brazil, and northern Uruguay. Therefore, the geological formations Irati and Ponta Grossa, located in the southern portion of the basin, were analyzed in terms of its hydrocarbon generating potential. The study also includes the viability evaluation of this occurrence as a supply for a thermal power plant in Uruguaiana, considering the geological socio-economic and environmental associated aspects. The project aims to promote studies on the topic of unconventional energy resources, especially shale gas, the main unconventional source of natural gas exploited in the world; in addition to emphasizing the advantages in increasing the implement of natural gas into the Brazilian energy matrix, both in strategic and economic aspects. The project proposes the development of a descriptive and comparative model based on geological aspects of the major shale gas producing fields in the United States, the world\'s leading producer; by which we are able to evaluate the potential for occurrence of this resource in the corresponding black shale formations Irati and Ponta Grossa according to geochemical, petrophysical and geological parameters present in these proven producing formations: Marcellus, Barnett and Eagle Ford. The descriptive model was elaborated in order to evaluate the potential for exploration, production and distribution of unconventional natural gas in the southern and southeastern regions of Brazil, which correspond to the largest consumer market and energy demand in the country. Based on a comparative analysis, the Brazilian geological formations are quantified with a moderate to high potential for generating shale gas. However, the viability of using this resource as supply for thermal electricity generation in Uruguaiana depends, in addition to the local geology, to political and regulatory aspects, which are still poorly consolidated among the country, in order to encourage the production of unconventional energy resources.

[pt] O desenvolvimento e exploração das formações shale gas a nível mundial é relativamente recente, tendo seu início nos Estados Unidos no final da década 1990. A partir dos resultados obtidos com a aplicação do procedimento de fraturamento hidráulico, como método de estimulação, o estudo e avaliação de outros prospectos shale gas em outras regiões do mundo foi estimulado. No entanto, a análise, estudo e caracterização deste tipo de reservatórios são dificultados uma vez que devem ser levados em conta múltiplos fatores relacionados a geologia, mineralogia, petrofísica, geoquímica, entre outros. O fraturamento hidráulico é um processo hidromecânico acoplado com alto grau de dificuldade especialmente em reservatórios shale gas, onde existe a presença de fraturas. Um estudo numérico é conduzido neste trabalho com o objetivo de investigar o comportamento hidromecânico de uma fratura natural durante a injeção de fluido. O software UDEC (Universal Distinct Element Code) baseado no método dos elementos discretos foi empregado no desenvolvimento da modelagem numérica. O UDEC tem a capacidade de modelar o comportamento hidromecânico de uma fratura incluindo os fenômenos de abertura/fechamento das fraturas, cisalhamento e dilatação sob condições de contato ou separação. Nesta investigação numérica foram criados modelos de reservatório com fraturas naturais aleatórias por meio de uma distribuição voronoi visando representar a complexidade da rede de fraturas naturais presentes nas formações shale gas. Os resultados do estudo numérico mostram que o comportamento hidromecânico do sistema é fortemente dependente da variação de parâmetros como tensões in situ, viscosidade do fluido de fraturamento e taxa de injeção de fluido. Portanto, estes resultados proporcionam um melhor entendimento dos mecanismos de fraturamento e resposta da pressão de um tratamento de fraturamento hidráulico em um reservatório de gás não-convencional naturalmente fraturado. / [en] The development and deployment of shale gas formations around the world are relatively recent, starting in the United Stated in the late 1990. From the results obtained with the application of hydraulic fracturing as a method of stimulation, the study and evaluation of other prospects of shale gas in others places in the world was encouraged. However, the analysis, study and characterization of this type of reservoirs are difficult, because it must be taken into account several factors such as geology, mineralogy, petrophysics, geochemistry among others. Hydraulic fracturing is a complicated hydro-mechanical coupled process, with high difficulty degree especially in shale gas reservoir, where natural fractures exist. A numerical study is conducted to investigate the hydromechanical behavior of a natural fracture during fluid injection. UDEC (Universal Distinct Element Code) software based on discrete elements method was employed to numerical modeling development. UDEC has the ability to model the hydro-mechanical behavior of a fracture including phenomena like fracture enlargement, closure, slippage, and dilation under contact or separation condition. In this numerical investigation, numerical reservoir models, with random natural fractures through a distribution voronoi were created aiming to represent the network complexity of natural fractures present in shale gas formations. The numerical study results show that the hydromechanical system behavior is strongly dependent on the parameters variation such as in situ stress, fluid fracturing viscosity and fluid injection rate. Therefore, these results provide a better understanding of fracturing mechanisms and pressure response of a hydraulic fracturing treatment in a non- conventional naturally fractured reservoir.

[pt] A Indústria de Gás Natural apresenta as características de uma indústria de rede. Assim, no caso de ocorrer uma falha em qualquer dos seus agentes ou modais logísticos, há impacto sobre toda a cadeia, com a possibilidade de torná-la inoperante. Esta indústria nasceu e cresceu de forma localizada, gerando mercados consumidores regionais. As regiões consumidoras de gás natural apresentam peculiaridades marcantes e diferentes em vários fatores, como: infraestruturas, volumes consumidos, produções, reservas provadas, formulações do preço e modais utilizados na exportação e importação. Com base nestas características pode-se inferir sobre a maturidade da Indústria de gás natural de cada região, bem como identificar desafios e oportunidade no atendimento do mercado consumidor. Esta dissertação analisa os fatores que determinam a regionalização do gás natural, as características regionais, os principais mercados mundiais e a estrutura da indústria no mercado brasileiro. Descreve as principais tecnologias atuais utilizadas no crescimento neste mercado gasífero, focando a revolução do Shale Gas no mercado norte-americano e a técnica do gasoduto virtual. Para esse fim, utilizou-se revisão narrativa da literatura internacional e nacional sobre a indústria e o mercado do gás natural, com ênfase em logística. / [en] The Natural Gas Industry has the characteristics of a network industry characteristic. Therefore, in the event of failure in any of the logistics agents or modals, there is impact over the entire chain, with the possibility of making it inoperative. This industry was born and raised in a localized way, generating regional consumers markets. Natural gas consuming regions have significant and different peculiarities in many factors, such as: infrastructures, consumed volumes, production, proven reserves, price formulations and modals used in exportation and importation. Based on these features, the maturity of Natural Gas Industry of each region can be inferred, as well as identifying challenges and opportunities in the consumer market service. This paper analyzes the factors which define the natural gas regionalization, regional characteristics, key global markets and industry structure in the Brazilian market. It outlines the main current technologies used in the growth of the gas Market, focused on the Shale Gas revolution in the North American market and in the virtual gas pipeline techniques. To this purpose, we used a narrative review of national and international literature on the natural gas industry and market with emphasis on logistics.

A presente dissertação de mestrado consiste na realização de um estudo geológico acerca do potencial para exploração e produção de gás natural não convencional na Bacia do Paraná, regiões sul e sudeste do Brasil e norte do Uruguai. Com essa finalidade, foram analisadas as formações geológicas Irati e Ponta Grossa, situadas na porção sul da bacia e caracterizadas por seu potencial gerador de hidrocarbonetos. O estudo também inclui a avaliação da viabilidade do abastecimento da usina termoelétrica de Uruguaiana a partir desse recurso, considerando os aspectos geológicos, socioeconômicos e ambientais associados. O projeto visa incentivar o estudo à temática de recursos energéticos não convencionais, com destaque para o shale gas, principal fonte de gás natural não convencional explorada no mundo, além de ressaltar os benefícios na crescente implantação do gás natural na matriz energética brasileira, tanto em aspectos estratégicos quanto econômicos. O projeto propõe a elaboração de um modelo descritivo-comparativo baseado nos aspectos geológicos dos principais campos produtores de shale gas nos Estados Unidos, principal produtor mundial, por meio do qual é avaliado o potencial para ocorrência desse recurso nos folhelhos negros correspondentes às Formações Irati e Ponta Grossa, segundo parâmetros geoquímicos, petrofísicos e geológicos presentes em formações comprovadamente produtoras nos EUA: Marcellus, Barnett e Eagle Ford. O modelo descritivo tem finalidade de avaliar o potencial para exploração, produção e distribuição de gás natural não convencional nas regiões sul e sudeste do Brasil, as quais representam o maior mercado consumidor e demanda por energia no país. Com base na análise comparativa realizada, atribui-se às formações brasileiras potencial moderado a elevado para a geração de shale gas. Entretanto, a viabilidade no abastecimento da usina termoelétrica de Uruguaiana depende, além da geologia local, de fatores político-regulatórios ainda pouco consolidados no país para a incentivar a produção de recursos energéticos não convencionais. / The presented Masters Thesis consists on a geological study of the potential for exploration and production of unconventional natural gas in the Paraná Sedimentary Basin, southern and southeastern Brazil, and northern Uruguay. Therefore, the geological formations Irati and Ponta Grossa, located in the southern portion of the basin, were analyzed in terms of its hydrocarbon generating potential. The study also includes the viability evaluation of this occurrence as a supply for a thermal power plant in Uruguaiana, considering the geological socio-economic and environmental associated aspects. The project aims to promote studies on the topic of unconventional energy resources, especially shale gas, the main unconventional source of natural gas exploited in the world; in addition to emphasizing the advantages in increasing the implement of natural gas into the Brazilian energy matrix, both in strategic and economic aspects. The project proposes the development of a descriptive and comparative model based on geological aspects of the major shale gas producing fields in the United States, the world\'s leading producer; by which we are able to evaluate the potential for occurrence of this resource in the corresponding black shale formations Irati and Ponta Grossa according to geochemical, petrophysical and geological parameters present in these proven producing formations: Marcellus, Barnett and Eagle Ford. The descriptive model was elaborated in order to evaluate the potential for exploration, production and distribution of unconventional natural gas in the southern and southeastern regions of Brazil, which correspond to the largest consumer market and energy demand in the country. Based on a comparative analysis, the Brazilian geological formations are quantified with a moderate to high potential for generating shale gas. However, the viability of using this resource as supply for thermal electricity generation in Uruguaiana depends, in addition to the local geology, to political and regulatory aspects, which are still poorly consolidated among the country, in order to encourage the production of unconventional energy resources.

[pt] Reservatórios de shale gas/shale oil possuem elevado grau de anisotropia devido à presença de fraturas naturais (NFs) e também da orientação dos estratos. Com isso as fraturas induzidas hidraulicamente (HFs) interagem com as NFs e geram uma rede de fraturas com morfologia complexa. A existência de NFs modifica o campo de tensões no folhelho e influencia diretamente o comportamento geomecânico das HFs durante a operação de fraturamento, gerando ramificações na fratura dominante e contribuindo para a formação da rede complexa de fraturas. A construção de uma rede de fraturas aumenta significativamente a condutividade da formação, pois conecta fraturas e poros que anteriormente encontravam-se isolados, incrementando assim o índice de produtividade dos poços e proporcionando maior viabilidade econômica nos projetos em reservatórios de shale gas/oil. Este trabalho apresenta uma análise de sensibilidade da influência do espaçamento entre fraturamentos na construção da rede de fraturas complexas gerada em shales, visando entender como este parâmetro modifica o volume de reservatório estimulado e a distribuição de propante na rede de fraturas, de maneira a evitar problemas nesta fase do projeto e assim, manter a sustentação da rede economicamente viável. A revisao de literatura contempla os principais trabalhos publicados sobre este tema e os modelos não-convencionais de fraturas (UFM) usados para a modelagem da rede de fraturas complexas. A análise de sensibilidade será realizada por meio do software MShale, que usa um método estocástico de rede de fraturas discretas (DFN) e resolve numericamente as equações de equilíbrio e da poroelasticidade para shales, em termos de tensões efetivas, além das equações de conservação de massa, momento linear e energia com dissipação viscosa para escoamento lento (creeping flow). Para a análise, os demais parâmetros que influenciam na contrução da rede serão mantidos constantes e somente o espaçamento entre fraturamentos sofrerá variação. / [en] Shale gas/shale oil reservoirs have a high degree of anisotropy due to the presence of natural fractures (NFs) and also the orientation of beddings. Thus, hydraulically induced fractures (HFs) interact with NFs and generate a network of fractures with complex morphology. The existence of NFs modifies the stress field in the shale and directly influences the geomechanical behavior of the HFs during the fracturing operation, generating branches in the dominant fracture and contributing to the complex network of fractures. The construction of a network of fractures significantly increases the conductivity of the formation, as it connects previously isolated fractures and pores, thus increasing the productivity index of the wells and providing greater economic viability in the shale gas/oil reservoir designs. This work presents a sensitivity analysis of the influence of fracturing spacing in the construction of the network of complex fractures generated in shales, aiming to understand how this parameter modifies the volume of stimulated reservoir and the distribution of propant in the network of fractures, in order to avoid problems in this step of the design and thus, maintain the economical viability of the network. The literature review includes the main published works on this subject and the non-conventional fracture models (UFM) used to model the network of complex fractures. Sensitivity analysis will be performed using the MShale software, which uses a stochastic of the discrete fracture network (DFN) method and numerically solves the equilibrium equations and poroelasticity for shales in terms of effective stresses, in addition to mass conservation equations, linear momentum and energy with viscous dissipation for creeping flow. For the analysis, the other parameters that influence the construction of the network will be kept constant and only the spacing between fracturings will suffer variation.

Given their potential applications for a number of engineering purposes, the geomechanics of shale reservoirs is becoming one of the most important issues in modern geomechanics. Borehole stability modeling, geophysics, shale oil and shale gas reservoirs, and underground storage of CO2 and nuclear waste are some of these potential applications to name a few. The growing interest in these reservoirs, as a source for hydrocarbons production, has resulted in an increasing demand for fundamental material property data. Laboratory analysis and constitutive models have shown that rock elastic and deformational properties are not single-value, well-defined parameters for a given rock. Finding suitable values for these parameters is of vital importance in many geomechanical applications. In this thesis an extensive experimental program to explore geomechanical properties of shale was developed. A series of triaxial tests were performed in order to evaluate the elasticity, yielding, and failure response of Marcellus shale specimens as a function of pressure, temperature, and bedding angle. Additional characterization includes mineralogy, porosity, and fabric. Rock samples used in this study came from three different locations and depths: one actual reservoir (~7,500 ft. deep), and two outcrops (~300 ft. and ~0 ft. deep).

<div>Currently, fossil resources dominate fuel and chemical production landscape. Besides concerns related to the ever-increasing greenhouse gas emission, fossil resources are also limited. In a petroleum-deprived future, sustainably available biomass can serve as a renewable carbon source. Due to its limited availability, however, this biomass resource must be utilized and converted effciently to minimize carbon losses to undesirable by-products. A modeling and optimization approach that can identify optimal process congurations for chemical and fuel production from biomass using stoichiometric and thermodynamic knowledge of the underlying biomass reaction system is proposed in this dissertation. Several case studies were performed with this approach, and the outcomes found agreement with reported experimental results. In particular, a case study on fast-hydropyrolysis vapor of cellulose led to the discovery of new reaction route and provided insights in comprehending the formation of experimentally observed molecules. The modeling and optimization approach consists of two main steps. The rst step is the generation of the search space and the second step is the identication of all optimal reaction routes.</div><div><br></div><div><div>For the rst step, literature review and automated reaction network generator are employed to identify all possible processes for biomass conversion. Through literature review, yield data on processes that generate biomass-derived molecules are collected. As these biomass-derived molecules often possess multiple functional groups, utilization of automated reaction network generator, which considers a set of biomass-derived molecules and reaction rules, enables generation of all possible reactions. In this work, an automated reaction network generator tool called Rule Input Network Generator is utilized. Using this generated search space, a mathematical optimization problem, which identies the optimal reaction network, is constructed. For the second step, the optimization problem identies all reaction routes with the minimum number of reactions for a given set of biomass and target products. This formulation constructs a process superstructure that contains processes that generate biomass-derived molecules and all possible reactions from biomass-derived molecules. In this optimization problem, the main constraint for the reaction is its thermodynamic favorability within a certain temperature range. Using optimization solver, optimal solutions for this problem are obtained.</div></div><div><br></div><div><div>Using this developed approach, a case study on upgrading fast-hydropyrolysis vapor of cellulose to higher molecular weight products was investigated. Levoglucosan and glycolaldehyde are major components from fast-hydropyrolysis of cellulose. This approach identied a reaction route that can upgrade these molecules to hydrocarbons with carbon number ranging from eight to 12 and this route has not been reported in the literature. The coupling of levoglucosan and glycolaldehyde requires a key intermediate, levoglucosenone, which is identied by this approach. Preliminary experimental results suggest that the proposed reactions are feasible and this serves as another validation for this approach. Other potential pathways to not only branched alkanes, but also substituted cycloalkanes and aromatics, were also identied. Molecules with those structures have been observed experimentally, and potential pathways to those molecules can provide insights for experimentalists as to how these products can form and which intermediates may lead to their formations. This approach has not only revealed unknown reaction routes, but also provided insights for experimentalists for analyzing complex systems.</div></div><div><br></div><div><div>Toward reduction of carbon losses toward char during fast pyrolysis, potential pathways toward char formation during fast pyrolysis were proposed. Investigating proposed char precursors identied using mass spectroscopy, several potential pathways toward the formation of these char precursors were obtained, which include initial insights to the potential driving force for the formation of these char precursors and, ultimately, char itself.</div></div><div><br></div><div><div>Going beyond fast pyrolysis, primary processes that have been developed in C3Bio along with several existing primary processes were considered in order to identify optimal biorenery congurations. This approach identied biorenery congurations with carbon effciencies from 60-64%. These congurations generate not only fuel type molecules, but also commodity chemicals that are being produced in a traditional renfiery. In addition, it is capable of providing these products at their current relative production rates in the United States. Other studies on biorefinery reported only 25-59% carbon effciency and generated mostly fuel-type molecules. Therefore, this approach not only indicates the appropriate reaction sequences, but also optimal utilization of carbon in biomass-derived molecules. This dissertation provides an initial roadmap toward sustainable production of fuels and chemicals from lignocellulosic biomass.</div></div><div><br></div><div><div>Considering that the transition to renewable energy is gradual and shale resource is an abundant fossil resource in the United States, opportunities to valorize shale gas condensate are explored. Recent shale gas boom has transformed the United States energy landscape. Most of the major shale basins are located in remote locations and historically non-gas producing regions. Therefore, many major shale basins regions are lacking the infrastructure to distribute the extracted gas into the rest of the US and particularly the Gulf Coast region. In this dissertation, shale gas catalytic upgrading processes were synthesized, designed, and simulated using Aspen Plus Simulation. Using Aspen Economic Analyzer, preliminary techno-economic analysis and evaluation of its economic potential were assessed at varying scales to assess its impact on the</div><div>United States chemical industry landscape.</div></div>

Dans cette thèse, nous avons développé 3 travaux principaux dans lesquels le phénomène d'adsorption joue un rôle prédominant.Selon le BP Statistical Review, le ratio réserves/production de la Colombie est proche de 12 et actuellement, toute la production de gaz naturel provient des réserves conventionnelles; para ailleurs, les réserves non conventionnelles de gaz techniquement récupérables sont 12 fois plus élevées que les conventionnelles. La plupart d’entre elles sont situées dans le Middle Magdalena Valley bassin (MMV). Dans ce contexte, nous avons mesuré la capacité d'adsorption du CH4 sur 5 échantillons obtenus de 3 forages exploratoires situés dans le MMV. Les mesures ont été réalisées à 50 et 75°C et pour pressures jusqu'à 3.5MPa. Les caractérisations géochimiques et structurales ont été réalisées à l'Université Autonome de Madrid. L'effet du carbone organique total (TOC), de la maturité thermique, de la teneur en argile et de la surface spécifique (SSA) sur la capacité d'adsorption du CH4 ont été étudiées. Les résultats montrent que la température a un effet négatif sur la capacité d'adsorption, et le TOC a un effet positif. Aucune corrélation n'a été observée entre la teneur en argile et la capacité d'adsorption normalisée en TOC par rapport au CH4, ce qui indique que les minéraux argileux ne contribuent pas significativement à l'adsorption du CH4 dans nos échantillons. De plus, il n'y a pas de tendance générale entre le TOC normalisé et la maturité thermique. Parmi les facteurs étudiés le TOC a la contribution majeure à la capacité d'adsorption. Une contribution similaire est trouvée pour la SSA, ce qui est cohérent, compte tenu de la corrélation positive entre le TOC et la SSA. Cet ensemble de données représente des informations significatives pour les estimations indirectes du gaz en place au cours des futures stratégies de récupération. Cette étude approfondit les projets en cours sur la compréhension de l'effet d'adsorption sur la production et l'évaluation du gaz de schiste de la Colombie. En plus, nous avons réalisé une étude sur l'adsorption sélective de CH4/CO2 sur un gaz de schiste, précédemment caractérisé. La capacité d'adsorption et l'enthalpie du CO2 et du CH4 à 50°C et pour pressions jusqu'à 3.2MPa ont été mesurées. De plus, les isothermes d'adsorption du mélange équimolaire CH4/CO2 ont été réalisées jusqu'à 2MPa à 50°C. Les résultats montrent que le CO2 est préférentiellement adsorbé par rapport au CH4, tant à l'état pur que dans le mélange équimolaire. La sélectivité estimée CO2/CH4 met en évidence une affinité significative du CO2 avec le kérogène de cet échantillon. Ces résultats sont d'un grand intérêt d'un point de vue industriel, car ils signifient que ce schiste pourrait être candidat à l'injection du CO2 comme méthode de récupération assistée et pour le stockage du CO2 quand il était épuisé.Enfin, sachant que les impacts environnementaux et sociétaux de la séparation et de la capture du CO2, nous avons exploré la séparation du CO2 d'un mélange équimolaire CH4/CO2 en utilisant des adsorbants de nanoparticules de silice (natives et fonctionnalisées avec des amines) développés à l'Université de Vigo. Nous avons mesurée la capacité d'adsorption et l'enthalpie du CO2 et du CH4 à 50°C et des pressions jusqu'à 3MPa et la capacité d'adsorption d'un mélange équimolaire CH4/CO2 à 50°C et jusqu'à 2MPa dans les deux séries de nanoparticules. Les résultats ont montré une adsorption préférentielle du CO2 sur le CH4, mais l'adsorption du CO2 est plus faible dans les particules natives que dans les particules fonctionnalisées. Cependant, les particules natives sont prometteuses pour la capture du CO2. La valeur de la sélectivité du CO2 par rapport au CH4 est presque identique pour les deux échantillons, cela signifie que le processus de fonctionnalisation n'a pas amélioré la performance des particules dans ce cas. Ces résultats obtenus sur la silice native ouvrent des perspectives et une ligne de travail. / In this dissertation we developed three main works in which adsorption phenomenon play a predominant role.According to the BP Statistical Review, Colombia’s reserves/production ratio is close to 12 and currently all the natural gas production comes from conventional reserves; meanwhile its unconventional technically recoverable gas reserves are about twelve times greater than conventional ones. Most of them are located in the Middle Magdalena Valley Sedimentary Basin (MMV). In this context we measured the methane adsorption capacity on five shale core samples obtained during exploratory drilling from three boreholes located in the MMV. The experiments were carried out at 50 and 75°C and for pressure ranging up to 3.5 MPa under dry conditions. The geochemical and structural characterizations were carried out in the Department of Geology of the Universidad Autonoma de Madrid. The effect of total organic carbon (TOC), thermal maturity, clay content and specific surface area (SSA) on methane adsorption capacity was studied. The results shows that the temperature has a negative effect on the adsorption capacity, while TOC has a positive effect, even if no linear regression was found between TOC and methane adsorption capacity. No correlation was observed between the clay content and the TOC-normalized adsorption capacity to methane, which indicates that clay minerals do not significantly contribute to methane adsorption in the case of our samples. In addition, there is not a general trend between TOC normalized and thermal maturity. Among the factors investigated in the present study, TOC has the major contribution to the adsorption uptake. A similar contribution is found for the SSA, which is consistent, considering the positive correlation between TOC and SSA. This set of data represents meaningful information for indirect estimations of the gas in place during the future recovery strategies. And maybe the most important, this study furthers the ongoing projects on the understanding of the adsorption effect on shale gas production and assessment.In addition to this work, we made a study on selective CH4/CO2 adsorption on a shale gas, which was previously characterized. The adsorption capacity and enthalpy of CO2 and CH4 pure at 50°C and for pressures up to 3.2 MPa were measured. Additionally, the equimolar mixture methane/carbon dioxide adsorption isotherms was performed up to 2 MPa at the same temperature. The results show that CO2 is preferentially adsorbed than methane, both in pure state as in the mixture. The estimated selectivity CO2/CH4 highlights a significant affinity of CO2 with the kerogen of this sample. These results are of great interest from an industrial point of view, because they mean that this shale could be a candidate for CO2 injection as recovery method; and for CO2 storage when it was depleted. Finally, having into account that separation and capture of CO2 have environmental connotations, we explored the separation of CO2 from an equimolar CH4/CO2 mixture using adsorbents of silica nanoparticles (natives and functionalized with amines) developed in the University of Vigo. We measured the adsorption capacity and enthalpy of CO2 and CH4 at 50°C and pressures up to 3MPa and the equimolar CH4/CO2 adsorption capacity at the same temperature and up to 2 MPa in both set of nanoparticles. The results showed that there is a preferential adsorption to CO2 over CH4 (in pure state and in the mixture), but CO2 adsorption is lower in native particles than in functionalized ones. However native particles are promising for CO2 capture. The value of selectivity of CO2 over CH4 is almost the same for both samples, it means that the functionalization process did not improve the performance of the particles in this case. This kind of works has a lot of perspective for the future.

The recent advent of shale gas in the U.S. has redefined the economics of ethylene manufacturing globally, causing a shift towards low-cost U.S. production due to natural gas feedstock, while reinforcing the industry's reliance on fossil fuels. At the same time, the global climate change crisis compels a transition to a low-carbon economy. These two influencing factors are complex, contested, and uncertain. This paper projects the United States' (U.S.) future ethylene supply in the context of two megatrends: the natural gas surge and global climate change. The analysis models the future U.S. supply of ethylene in 2050 based on plausible socio-economic scenarios in response to climate change mitigation and adaptation pathways as well as a range of natural gas feedstock prices. This Vector Error Correction Model explores the relationships between these variables. The results show that ethylene supply increased in nearly all modeled scenarios. A combination of lower population growth, lower consumption, and higher natural gas prices reduced ethylene supply by 2050. In most cases, forecasted CO2 emissions from ethylene production rose. This is the first study to project future ethylene supply to go beyond the price of feedstocks and include socio-economic variables relevant to climate change mitigation and adaptation.

Today everyone seems to agree that ultra-low permeability and shale reservoirs have become the potentials to transform North America's oil and gas industry to a new phase. Unfortunately, transient flow is of long duration (perhaps life of the well) in ultra-low permeability reservoirs, and traditional decline curve analysis (DCA) models can lead to significantly over-optimistic production forecasts without additional safeguards. Stretched Exponential decline model (SEDM) gives considerably more stabilized production forecast than traditional DCA models and in this work it is shown that it produces unchanging EUR forecasts after only two-three years of production data are available in selected reservoirs, notably the Barnett Shale. For an individual well, the SEDM model parameters, can be determined by the method of least squares in various ways, but the inherent nonlinear character of the least squares problem cannot be bypassed. To assure a unique solution to the parameter estimation problem, this work suggests a physics-based regularization approach, based on critical velocity concept. Applied to selected Barnett Shale gas wells, the suggested method leads to reliable and consistent EURs. To further understand the interaction of the different fracture properties on reservoir response and production decline curve behavior, a series of Discrete Fracture Network (DFN) simulations were performed. Results show that at least a 3-layer model is required to reproduce the decline behavior as captured in the published SEDM parameters for Barnett Shale. Further, DFN modeling implies a large number of parameters like fracture density and fracture length are in such a way that their effect can be compensated by the other one. The results of DFN modeling of several Barnett Shale horizontal wells, with numerous fracture stages, showed a very good agreement with the estimated SEDM model for the same wells. Estimation of P90 reserves that meet SEC criteria is required by law for all companies that raise capital in the United States. Estimation of P50 and P10 reserves that meet SPE/WPC/AAPG/SPEE Petroleum Resources Management System (PRMS) criteria is important for internal resource inventories for most companies. In this work a systematic methodology was developed to quantify the range of uncertainty in production forecast using SEDM. This methodology can be used as a probabilistic tool to quantify P90, P50, and P10 reserves and hence might provide one possible way to satisfy the various legal and technical-society-suggested criteria.