The Arizona Oil and Gas Commission in conjunction with the Arizona Geological Survey have collected a large amount of data for the oil and gas wells in the State of Arizona. The data covers over 1,000 wells that were drilled from the 1940s to present. This data includes copies of permits, location information, scanned copies of well logs and digitized versions of the well logs in .las file format. These files have been difficult to distribute efficiently because of an unfriendly web user interface. The purpose of this project is to give the Arizona Geological Survey a way to distribute the oil and gas well data through an effective web application. The web application will leverage existing web services at the Arizona Geological Survey. To create this map I used the Esri JavaScript API. In this application the users can select multiple wells by clicking and dragging over the well heads they want. This will then display the metadata in a grid along with hyperlinks to the available files for those wells. This data will be primarily used by companies involved with carbon sequestration or others seeking information for geological exploration.

Numerical simulation has been used, as common practice, to estimate the CO2 storage capacity of depleted reservoirs. However, this method is time consuming, expensive and requires detailed input data. This investigation proposes an analytical method to estimate the ultimate CO2 storage in depleted oil and gas reservoirs by implementing a volume constrained thermodynamic equation of state (EOS) using the reservoir?s average pressure and fluid composition. This method was implemented in an algorithm which allows fast and accurate estimations of final storage, which can be used to select target storage reservoirs, and design the injection scheme and surface facilities. Impurities such as nitrogen and carbon monoxide, usually contained in power plant flue gases, are considered in the injection stream and can be handled correctly in the proposed algorithm by using their thermodynamic properties into the EOS. Results from analytical method presented excellent agreement with those from reservoir simulation. Ultimate CO2 storage capacity was predicted with an average difference of 1.3%, molar basis, between analytical and numerical methods; average oil, gas, and water saturations were also matched. Additionally, the analytical algorithm performed several orders of magnitude faster than numerical simulation, with an average of 5 seconds per run.

Green chemistry principles served as a guide for three industrially-relevant projects. In the first project, silylamines were applied as reversible ionic liquids for carbon dioxide capture from post-combustion flue gas streams. The effect of silylamine structure was thoroughly researched to develop a comprehensive library of silylamines and an accompanying set of structure-property relationships. The proposed solvent systems have the potential to present significant energy savings, as design has focused on their use in a non-aqueous, solvent-free environment. The second project also dealt extensively with carbon dioxide capture, as a reversible, in-situ protecting group for amines. Three strategies for the reversible protection of amines using carbon dioxide were developed and evaluated. Further, a chemoselective reaction was performed using carbon dioxide to protect a reactive amine and consequentially direct reactivity elsewhere within the same molecule. The carbon dioxide-protection technology developed has significant impact in multi-step industrial syntheses, as reversible, in-situ protection with carbon dioxide could eliminate the need for separate protection and deprotection unit operations. Lastly, a study was performed on the thermal degradation and stabilization of PVC in the presence of both plasticizers and thermal stabilizers. The study combined both model compound experiments as well as work with bulk PVC blends to gain a holistic understanding of the processes that take place during the degradation and stabilization of PVC. A bio-based plasticizer was investigated as a replacement for petroleum-based phthalate plasticizers. Additionally, two novel thermal stabilizers for PVC were presented and evaluated.

The detrimental effects of rising CO₂ levels on the global climate have made carbon abatement technologies one of the most widely researched areas of recent times. In this thesis, we first present a techno-economic analysis of a novel approach to directly capture CO₂ from air (Air Capture) using highly selective adsorbents. Our process modeling calculations suggest that the monetary cost of Air Capture can be reduced significantly by identifying adsorbents that have high capacities and optimum heats of adsorption. The search for the best performing material is not limited to Air Capture, but is generally applicable for any adsorption-based separation. Recently, a new class of nanoporous materials, Metal-Organic Frameworks (MOFs), have been widely studied using both experimental and computational techniques. In this thesis, we use a combined quantum chemistry and classical simulations approach to predict macroscopic properties of MOFs. Specifically, we describe a systematic procedure for developing classical force fields that accurately represent hydrocarbon interactions with the MIL-series of MOFs using Density Functional Theory (DFT) calculations. We show that this force field development technique is easily extended for screening a large number of complex open metal site MOFs for various olefin/paraffin separations. Finally, we demonstrate the capability of DFT for predicting MOF topologies by studying the effect of ligand functionalization during CuBTC synthesis. This thesis highlights the versatility and opportunities of using multiscale modeling approach that combines process modeling, classical simulations and quantum chemistry calculations to study nanoporous materials for adsorptive separations.

Submitted by TIARA MORAES GUIMARÃES null (tiaraguimaraes@yahoo.com.br) on 2016-04-12T20:05:10Z No. of bitstreams: 1 VERSÃO FINAL - DISSERTAÇÃO.pdf: 2061074 bytes, checksum: cd312ff121220dcddbf2d2a217e78cfd (MD5) / Approved for entry into archive by Ana Paula Grisoto (grisotoana@reitoria.unesp.br) on 2016-04-15T13:36:41Z (GMT) No. of bitstreams: 1 guimaraes_tm_me_bot.pdf: 2061074 bytes, checksum: cd312ff121220dcddbf2d2a217e78cfd (MD5) / Made available in DSpace on 2016-04-15T13:36:41Z (GMT). No. of bitstreams: 1 guimaraes_tm_me_bot.pdf: 2061074 bytes, checksum: cd312ff121220dcddbf2d2a217e78cfd (MD5) Previous issue date: 2016-02-19 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A calagem destaca-se entre as práticas agrícolas mais eficientes em resolver os problemas relacionados à acidez do solo, entretanto resulta em emissões de gases de efeito estufa (GEE), principalmente CO2. É possível que o aumento no desenvolvimento radicular no perfil do solo e da biomassa aérea, decorrente da aplicação de corretivos de acidez, como o calcário, e de condicionadores, como o gesso agrícola, promova maior retorno de C ao solo na forma de resíduos, o que pode favorecer a fixação do CO2 da atmosfera no solo. Desta forma objetivou-se avaliar a emissão de gases de efeito estufa, bem como possíveis alterações no estoque de carbono do solo, em função da correção da acidez do solo utilizando calcário e gesso em sistema semeadura direta (SSD), além da emissão de carbono equivalente por unidade de massa de grãos produzida pelo feijoeiro. O presente trabalho é parte de um experimento de longa duração, instalado em 2002/03, na Fazenda Experimental Lageado, pertencente à Faculdade de Ciências Agronômicas da UNESP, em Botucatu (SP). Após a colheita do trigo em julho de 2014 semeou-se em outubro do mesmo ano milheto para produção de palha, e posteriormente a dessecação da área foi realizada a semeadura da cultura do feijão, no início de dezembro de 2014. O delineamento experimental foi em blocos casualizados no esquema de parcelas subdivididas, com 4 repetições. As parcelas foram constituídas por quatro doses de calcário (0, 1000, 2000 e 4000 kg ha-1) e as subparcelas por duas doses de gesso agrícola (0 e 2100 kg ha-1). Foram realizadas as seguintes avaliações: carbono orgânico total e nitrogênio total do solo, estoque de C e N do solo, C e N da biomassa microbiana do solo e teor de C e N na matéria seca. Foram determinados os fluxos de CO2; CH4 e N2O por meio de câmaras estáticas, nos períodos 1; 3; 5; 8; 15; 30 dias após a semeadura do milheto e 1; 3; 5; 8; 15; 21; 30; 60; 90 dias após a semeadura do feijão, totalizando 15 períodos de amostragens. Observou-se que as maiores emissões de CO2 estão relacionadas com o teor de CBMS, que é um indicativo de imobilização/mineralização de C pelos microrganismos. Sendo assim quanto maior o teor de CBMS, maior a imobilização de nutrientes no solo, maior a taxa de respiração e consequentemente maior emissão de CO2. A aplicação de gesso agrícola aumenta a oxidação de CH4 no solo, favorecendo assim a mitigação de GEE. A emissão de N2O está relacionada com a maior acidificação do solo e com o teor de água no solo. / Liming stands out among the most efficient agricultural practices in solving the soil acidity-related problems, however results in emissions of greenhouse gases (GHGs), particularly CO2. It is possible that the increase in root development in the soil profile and biomass, resulting from the application of soil correctives such as limestone and conditioners such as agricultural gypsum, promote greater return of C to the soil in the form of waste, which can promote the fixation of CO2 from the atmosphere into the soil. Thus aimed to evaluate the emission of greenhouse gases, and possible changes in the stock of soil carbon, depending on soil acidity correction using lime and phosphogypsum in no-tillage, in addition to carbon emissions equivalent per unit mass of grain produced by bean plants. This work is part of a long-term experiment, installed in 2002/03, at Lageado Experimental Farm, belonging to the College of Agricultural Sciences - UNESP in Botucatu (SP). After the wheat harvest in July 2014 the millet was sown in October of that year to produce straw, and after the desiccation of the area its was held the sowing of bean crop in early December 2014. The experimental design was performed in randomized block, in a split plot scheme, with four repetitions. The plots consisted of four liming rates (0, 1000, 2000 and 4000 kg ha-1) and the subplots of two rates of phosphogypsum (0 to 2100 kg ha-1). The following evaluations were performed: total organic carbon and total soil nitrogen, stock of C and N of the soil, C and N microbial biomass of the soil and the contents of C and N in the dry matter. It were determined the CO2 streams; CH4 and N2O by static chambers in the periods 1; 3; 5; 8; 15; 30 days after sowing of millet and 1; 3; 5; 8; 15; 30; 60; 90 days after sowing the beans, totaling 15 sampling periods. It was observed that the higher CO2 emissions are related to the CMBS content, which is indicative of immobilization / mineralization of the C by the microorganisms. Thus higher the CMBS content, higher the immobilization of the nutrients in the soil, higher the rate of breathing and consequently higher emissions of CO2. The application of gypsum increases the CH4 oxidation in the soil, favoring the mitigation of greenhouse gases. The N2O emission is related to the higher soil acidification and the water content in the soil.

Submitted by Caio Felipe de Paula Santos null (38626554826) on 2016-04-20T17:19:28Z No. of bitstreams: 1 Dissertação_final.pdf: 650643 bytes, checksum: 4c9c3b09b961790fcddd0d2c996feba9 (MD5) / Approved for entry into archive by Felipe Augusto Arakaki (arakaki@reitoria.unesp.br) on 2016-04-26T17:53:46Z (GMT) No. of bitstreams: 1 santos_cfp_me_guara.pdf: 650643 bytes, checksum: 4c9c3b09b961790fcddd0d2c996feba9 (MD5) / Made available in DSpace on 2016-04-26T17:53:46Z (GMT). No. of bitstreams: 1 santos_cfp_me_guara.pdf: 650643 bytes, checksum: 4c9c3b09b961790fcddd0d2c996feba9 (MD5) Previous issue date: 2016-02-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A geração de energia elétrica em usinas termoelétricas de ciclo combinado tem se mostrado muito importante para o Brasil apesar de operar com custo maior do que a geração através de hidroelétricas. Neste trabalho, foram realizadas análises termoeconômica e ecológica, baseadas nos princípios da Termodinâmica (energia e exergia), aplicados em usina termoelétrica de ciclo combinado de 500 MW. Para este trabalho foram consideradas duas configurações para a planta: a primeira configuração é a padrão (sem considerar equipamento de redução de emissão de CO2), e a segunda que considera a implementação do processo de captura, armazenamento e compressão de CO2 (CAC). O principal objetivo do trabalho é estudar e comparara as diferenças nas eficiências termodinâmicas e ecológicas da planta (operando nas duas condições) e as alterações nos custos de produção de energia elétrica gerada, em vista da instalação do processo de CAC. / The Electric Power Generation in combined cycle power plants has been very important for Brazil despite having a higher cost than the generation through hydropower plants. In this work, there were performed thermeconomical and ecological analyzes, based on thermodynamic principles (energy and exergy) in a 500 MW combined cycle power plant. For this work there were considered two settings for this plant: first a standard configuration (without to consider equipments for CO2 emission reduction), and the second considering the implementation of a process of capture, storage and compression of carbon dioxide (CSC). The main objective of this analysis is to study and compare the differences in thermodynamic and ecological efficiencies (operating in both conditions) and the alterations in the electrical energy cost, in view of the installation of the CSC process.

This thesis’s main focus is a CO2 capture technology known as chemical looping combustion (CLC). The technology is a novel form of combustion and fuel processing that can be applied to gas, solid and liquid fuels. By using two interconnected fluidised-bed reactors, with a bed material capable of transferring oxygen from air to the fuel, a stream of almost pure CO2 can be produced. This stream is undiluted with nitrogen and is produced without any direct process efficiency loss from the overall combustion process. The heart of the process is the oxygen carrier bed material, which transfers oxygen from an air to fuel reactor for the conversion of the fuel. Oxygen carrier materials and their production should be of low relative cost for use in large-scale systems. The first part of this research centres on development and investigative studies conducted to assess the use of low-cost materials as oxygen carriers and as supports. Mixed-oxide oxygen carriers of modified manganese ore and iron ore were produced by impregnation. While copper (II) oxide supported on alumina cement and CaO have been produced by pelletisation. These oxygen carriers were investigated for their ability to convert gaseous fuels in a lab-scale fluidised bed, and characterised for their mechanical and chemical suitability in the CLC process. The modified ores and pelletised copper-based oxygen carriers’ mechanical properties were enhanced by their production methods and in the case of the modified iron ore, significant oxygen uncoupling was observed. The copper-based oxygen carriers particularly those containing alumina cement showed high conversion rates of gaseous fuels and improved mechanical stability. The second part of this research thesis focuses on the design philosophy, commissioning and operation of a dual-fast bed chemical looping pilot reactor. Based on the operational experience, recommendations for modifications to the CLC system are discussed. In support, a parallel hydrodynamic investigation has been conducted to validate control and operational strategies for the newlydesigned reactor system. It was determined that the two fast bed risers share similar density and pressure profiles. Stable global circulation rate is flexible and could be maintained despite being pneumatically controlled. Reactor-reactor leakage via the loop-seals is sensitive to loop seal bed-height, and inlet fluid velocity but can be maintained as such to ensure no leakage is encountered.

Adsorption in porous materials is a promising technology for CO2 capture and storage. Particularly important applications are adsorption separation of streams associated with the fossil fuel power plants operation, as well as natural gas sweetening. High surface area activated carbons are a promising family of materials for these applications, especially in the high pressure regimes. As the streams under consideration are generally multi-component mixtures, development and optimization of adsorption processes for their separation would substantially benefit from predictive simulation models. In this project we combine experimental data and molecular simulations to systematically develop a model for a high surface area carbon material, taking activated carbon Maxsorb MSC-30 as a reference. Our study starts from the application of the well-established slit pore model, and then evolves through the development of a more realistic model, based on a random packing of small graphitic fragments. In the construction of the model, we introduce a number of constraints, such as the value of the accessible surface area, concentration of the surface groups and pore volume, to bring the properties of the model structure close to the reference porous material. Once a plausible model is developed, its properties are further tuned through comparison between simulated and experimental results for carbon dioxide and methane. The model is then validated by predictions for the same species at different conditions and by prediction of other species involved in the carbon capture processes. The model is applied to simulate the separations involved in pre and post combustion capture processes and sweetening of sour natural gas, using realistic conditions and compositions for the multicomponent mixtures. Finally, it is used to explore the effect of water in pre and post combustion separations.

Carbon capture and storage technologies (CCS) are expected to play a key role in the future energy matrix. Different gas separation processes are under investigation with the purpose of becoming a more economical alternative than solvent based post combustion configurations. Previous works have proved that pressure swing adsorption (PSA) cycles manage to reach similar carbon capture targets than conventional amine process but with approx. a 50% lower specific energy consumption when they are applied at lab scale. These encouraging results suggest that research must be undertaken to study the feasibility of this technology at a low to medium power plant scale. The simulation of PSA cycles is a computationally challenging and time consuming task that requires as well a large set of experimentally measured data as input parameters. The assumption of Equilibrium Theory reduces the amount of empirically determined input variables that are necessary for modelling adsorption dynamics as well as enabling a simpler code implementation for the simulators. As part of this work, an Equilibrium Theory PSA cycle solver (Esim) was developed, the novel tool enables the quantification of the thermodynamic limit for a given PSA cycle allowing as well a pre-selection of promising operating conditions and configurations (high separation efficiency) for further investigation by using full governing equation based software The tool presented in this thesis is able to simulate multi-transition adsorption systems that obey any kind of equilibrium isotherm function without modifying its main code. The second part of this work is devoted to the design, simulation and optimisation of two stage two bed Skarmstrom PSA cycles to be applied as a pre-combustion process in a biomass gasification CHP plant. Simulations were carried out employing an in house software (CySim) in which full governing equations have been implemented. An accurate analysis of the operating conditions and cycle configurations was undertaken in order to improve the performance of the carbon capture unit. It was estimated that the energy penalty associated with the incorporation of the adsorptive pre combustion process was lower for a conventional post combustion solvent unit, leading as well to lower specific energy consumption per unit of captured CO2 and higher overall efficiencies for the CHP plant with installed pre-combustion PSA cycles. This work is pioneer in its kind as far as modelling, simulation, optimisation and integration of PSA units in energy industries is concerned and its results are expected to contribute to the deployment of this technology in the future energy matrix.

Utilisation of biomass resources and CO2 abatement systems in currently exploited fossil resource based energy systems are the key strategies in resolving energy sustainability issue and combating against global climate change. These strategies are affected by high energy penalty and high investment. Therefore, it is imperative to assess the viability of these energy systems and further identify niche problem areas associated with energy efficiency and economic performance improvement. The current research work has two parts. The first part presents techno-economic investigation of thermochemical conversion of biomass into the production of fuels (Fischer-Tropsch liquid or methanol) and electricity. The work encompasses centralised bio-oil integrated gasification plant, assuming that the bio-oil is supplied from distributed pyrolysis plant. Bio-oil is a high energy density liquid derived from biomass fast pyrolysis process, providing advantages in transport and storage. Various bio-oil based integrated gasification system configurations were studied. The configurations were varied based on oxygen supply units, once-through and full conversion configurations and a range of capacities from small to large scale. The second part of this thesis considers integration of various CO2 abatement strategies in coal integrated gasification systems. The CO2 abatement strategies under consideration include CO2 capture and storage, CO2 capture and reuse as well as CO2 reuse from flue gas. These facilities are integrated into cogeneration or polygeneration systems. The cogeneration concept refers to the production of combined heat and power while polygeneration concept is an integrated system converting one or more feedstocks into three or more products. Polygeneration is advocated in this work attributed to its high efficiency and lower emission. Furthermore, it can generate a balanced set of products consisting of fuels, electricity and chemicals. It is regarded as a promising way of addressing the future rapidly growing energy demands. A holistic approach using systematic analytical frameworks comprising simulation modelling, process integration and economic analysis has been developed and adopted consistently throughout the study for the techno-economic performance evaluation of decarbonised fossil and bio-oil based systems. Important design methodology, sensitivity analysis of process parameters and process system modifications are proposed. These are to enhance the efficiency as well as lower the economic and environmental impacts of polygeneration systems. A shortcut methodology has also been developed as a decision-making tool for effective selection from a portfolio of CO2 abatement options and integrated systems. Critical and comprehensive analyses of all the systems under considerations are presented. These embrace the impact of carbon tax, product price evaluation and recommendations for sustainability of low carbon energy systems.