Treatment of natural gas streams with ionic liquids

Being of high relevance for many technological applications, the solubility of sour gases in solvents of low volatility is still poorly described and understood. Aiming at purifying natural gas streams, the present work contributes for a more detailed knowledge and better understanding of the solubility of sour gases in these fluids, in particularly on ionic liquids. A new apparatus, developed and validated specially for phase equilibria studies of this type of systems, allowed the study of the solvent basicity, molecular weight and polarity influence on the absorption of carbon dioxide and methane. The non ideality of carbon dioxide solutions in ionic liquids and other low volatile solvents, with which carbon dioxide is known to form electron donor-acceptor complexes, is discussed, allowing the development of a correlation able to describe the carbon dioxide solubility in low volatile solvents. Furthermore, the non ideality of solutions of light compounds, such as SO2, NH3 and H2S, in ionic liquids is also investigated and shown to present negative deviations to the ideality in the liquid phase, that can be predicted by the Flory-Huggins model. For last, the effect of the ionic liquid polarity, described through the Kamlet-Taft parameters, on the CO2/CH4 and H2S/CH4 selectivities is also evaluated and shown to stand as a viable tool for the selection of ionic liquids with enhanced selectivities.

Accidental release of hazardous gases: modelling and assessing risk

The renewed concern in assessing risks and consequences from technological hazards in industrial and urban areas continues emphasizing the development of local-scale consequence analysis (CA) modelling tools able to predict shortterm pollution episodes and exposure effects on humans and the environment in case of accident with hazardous gases (hazmat). In this context, the main objective of this thesis is the development and validation of the EFfects of Released Hazardous gAses (EFRHA) model. This modelling tool is designed to simulate the outflow and atmospheric dispersion of heavy and passive hazmat gases in complex and build-up areas, and to estimate the exposure consequences of short-term pollution episodes in accordance to regulatory/safety threshold limits. Five main modules comprising up-to-date methods constitute the model: meteorological, terrain, source term, dispersion, and effects modules. Different initial physical states accident scenarios can be examined. Considered the main core of the developed tool, the dispersion module comprises a shallow layer modelling approach capable to account the main influence of obstacles during the hazmat gas dispersion phenomena. Model validation includes qualitative and quantitative analyses of main outputs by the comparison of modelled results against measurements and/or modelled databases. The preliminary analysis of meteorological and source term modules against modelled outputs from extensively validated models shows the consistent description of ambient conditions and the variation of the hazmat gas release. Dispersion is compared against measurements observations in obstructed and unobstructed areas for different release and dispersion scenarios. From the performance validation exercise, acceptable agreement was obtained, showing the reasonable numerical representation of measured features. In general, quality metrics are within or close to the acceptance limits recommended for ‘non-CFD models’, demonstrating its capability to reasonably predict hazmat gases accidental release and atmospheric dispersion in industrial and urban areas. EFRHA model was also applied to a particular case study, the Estarreja Chemical Complex (ECC), for a set of accidental release scenarios within a CA scope. The results show the magnitude of potential effects on the surrounding populated area and influence of the type of accident and the environment on the main outputs. Overall the present thesis shows that EFRHA model can be used as a straightforward tool to support CA studies in the scope of training and planning, but also, to support decision and emergency response in case of hazmat gases accidental release in industrial and built-up areas.

Características de cinzas e sua aplicação no tratamento de gases durante a gasificação de biomassa

Na procura de melhores combustíveis para a produção de energia térmica e energia elétrica, a biomassa apresenta-se como uma das fontes de energia renováveis menos prejudiciais ao meio ambiente, esta é considerada como um recurso neutro do ponto de vista de emissões de dióxido de carbono. Atualmente, a tecnologia predominante no domínio da conversão energética de biomassa por via termoquímica é a combustão. Contudo, verifica-se a procura de combustíveis de melhor qualidade produzidos a partir de biomassa, como por exemplo na forma gasosa (gás de combustível). A produção deste tipo de combustíveis gasosos envolvendo processos de gasificação carece do desenvolvimento de tecnologia que permita obter um gás combustível com características adequadas às utilizações pretendidas. Os problemas mais relevantes relacionados com a conversão termoquímica da biomassa incluem a produção de cinzas e de alcatrões, estes podem levar a vários problemas operatórios. O presente trabalho teve dois objetivos, a caracterização das cinzas resultantes do processo de combustão de biomassa e o estudo do efeito da aplicação das cinzas para melhorar as propriedades do gás produzido durante o processo de gasificação de biomassa, principalmente na redução de compostos condensáveis (alcatrões). As cinzas volantes da combustão de biomassa analisadas apresentam na sua constituição elementos químicos característicos da biomassa, onde o cálcio apresenta-se em concentrações mais elevadas. Em menores concentrações encontram-se sódio, magnésio, fósforo, enxofre, cloro, potássio, manganês e ferro. As cinzas de fundo, pelo contributo que a areia do leito tem, são caracterizadas por conterem grandes concentrações de silício. Durante os processos de gasificação de biomassa a concentração de compostos condensáveis diminuiu com o aumento da razão de equivalência. As cinzas, colocadas no reator de leito fixo, apresentam um efeito positivo sobre a qualidade do gás, nomeadamente um aumento de 47,8% no teor de H2 e de 11% de CO, consequentemente obteve-se um gás combustível com PCI (poder calorífico inferior) mais elevado.