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Distributed power generation and cogeneration of heat and power is an attractive way toward a more rational conversion of fossil and bio fuels. Solid oxide fuel cell (SOFC) – gas turbine (GT) hybrid systems are emerging as the most promising candidates enabling the achievement of a cleaner and more efficient conversion of a large variety of resources across a broad power range covering from small to medium scale applications. This thesis introduces an innovative concept of SOFC-GT hybrid system that allows reaching efficiencies higher than the state of the art while enabling the carbon dioxide separation and avoiding fuel cell pressurisation technical issues. Several hybrid system design alternatives based on this concept are analysed through a thermodynamic optimisation approach combining process modelling, advanced process integration techniques and multi-objective optimisation. A number of optimal hybrid system configurations are determined for different design targets. The results consistently demonstrate the higher energy conversion performance and flexibility enabled with respect to the state of the art. The innovative concept analysis is extended to two applications for which SOFC-GT hybrid cycles are expected to provide the most significant impact toward sustainability: the small scale distributed generation and the conversion of renewable resources. A simplified version of the new hybrid system layout is especially developed for small scale distributed generation, typical of residential building applications (5-10 kWel). Experimental data are used to prove the technical feasibility of the system and to assess the performance potentially achievable with currently feasible technologies. The results of the analysis underline that energy conversion efficiencies higher than traditional centralised power generation can be achieved even at such a small scale. A systematic process integration and optimisation approach is used to assess the energy conversion performance of the original SOFC-GT hybrid cycle fuelled with hydrothermally gasified wet waste biomass. The analysis highlights the considerable potential of the integrated system that allows for converting wet waste biomass into electricity with First Law efficiency higher than 60% while simultaneously enabling the separation of the biogenic carbon dioxide.

The constituent countries of the MENA region---defined in this thesis in conformity with the regional definition of the International Energy Agency and encompassing 17 Muslim countries in North Africa, in the Levant, on the Arabian Peninsula, and Iran---have developed very rapidly over the past decade. Two figures best exemplify the region's tremendous transformation: Total population has expanded by more than 20% and its aggregate economic output has more than doubled. As much as this development is desirable, said development trends have also dramatically reshaped the energy policy environment in the MENA region and began causing problems of their own---affecting the region's large oil exporters and its energy importers alike. Having traditionally enjoyed high energy security and handsome resource rents by virtue of their abundant and cheap fossil fuels, new realities in the domestic energy systems demand a new policy focus on domestic energy issues. Energy challenges have emerged which threaten security of supply, fiscal stability, and environmental integrity. The challenges differ in magnitude from country-to-country and reflect the specific national conditions and circumstances. However, given the similarity in the underlying drivers and the governing energy policies, the energy challenges resemble each other across borders. More specifically, ballooning domestic energy demand consumes a rising share of national energy production and thus increasingly imperils the constant flow of the much needed proceeds from oil and gas exports. In the MENA countries with less abundant hydrocarbon resources, domestic demand growth has heightened energy dependence and, to make matters worse, the tighter supply situation in the energy exporting neighbors may eventually also lead to a discontinuation of the preferential supply agreements which they have benefitted from in the past. As a further corollary of demand growth, massive capital-intensive infrastructure investments are necessary to keep pace with the growth on the demand side. The regional tradition to sell energy commodities domestically at prices non-competitive prices or even below cost, however, limits the national energy sectors' own capability of mustering the required capital. Finally, the universally observable heavily fossil fuel-dominated national energy mixes in the region render the study countries vulnerable to supply shocks. The virtually complete reliance on the regionally available hydrocarbons for meeting energy demand is also a principal contributor to environmental degradation and at the core of the large carbon footprint of energy consumption in MENA countries. Given current policies in combination with the emerging demographic and economic trends, these challenges must be expected to become more severe in the years to come. Rising living standards, especially in the region's expanding urban population, are likely to boost per capita energy consumption. The projected, continued demographic and economic growth will further drive commodity demand. And the supply side cannot be counted on to mitigate the challenges under given policies. On the contrary. Although no reliable production projections are available, it stands to reason that production from the region's most prolific oil and gas fields---some of which have been producing for several decades now---will increasingly require the use of costly secondary and tertiary recovery methods and that some will eventually [...]

Although mature technologies at competitive prices are largely available, solar thermal is not yet playing the important role it deserves in the reduction of buildings fossil energy consumption. The generally low architectural quality characterizing existing building integrations of solar thermal systems pinpoints the lack of design as one major reason for the low spread of the technology. As confirmed by the example of photovoltaics, the improvement of the architectural quality of building integrated systems can increase the use of a solar technology even more than price and technique. This thesis investigates the possible ways to enhance the architectural quality of building integrated solar thermal systems, and focuses on integration into façade, where the formal constraints are major and have most impact. The architectural integration problematic is structured into functional, constructive and formal issues, so that integration criteria are given for each architectural category. As the functional and constructive criteria are already recognized by the scientific community, the thesis concentrates on the definition of the formal ones, yet underestimated or misunderstood. The results of a large European survey over architects and engineers perception of building integration quality are presented, showing that for architects formal issues are not a matter of personal taste, but that they relate to professional competences, and consequently can be described. The solar system characteristics having an impact on the formal quality of the integration are identified (formal characteristics), the related integration criteria are assessed, and finally integration guidelines to support architect integration design work are given. The limits imposed by the collectors available in the market are pointed out, showing that the lack of appropriate products is nowadays the main barrier to BIST (Building Integrated Solar Thermal) architectural quality. A methodology for the development of new solar thermal collectors systems responding at the same time to energy production needs and building integration requirements is defined. The importance to ensure, within the design team, the due professional competences in both these fields is stressed. Three progressive levels of system "integrability" are defined in the path leading to the concept of "active envelope systems" and the main role of facade manufacturers is highlighted. The methodology is applied to unglazed and glazed flat plate systems, and new façade system designs are proposed that show the relevance of the proposed approach.

Natural gas is defined as a combustible mixture of hydrocarbons coming from ground deposits and it is mainly used as a source of energy for burners and motors. Its consumption is increasing worldwide, as this represents a cheap and abundant source of energy, while releasing less CO2 emissions than other fossil fuels, in addition to low emissions of particulates. The diversification of the supply sources of gas and the increase of international trading through pipelines and liquefied natural gas (LNG) shipments makes the gas quality vary more than before, which is a rising challenge for the natural gas industry, as currently the vast majority of gas appliances and motors are unable to adapt to changes in gas quality. This will even worsen in the upcoming years with the multiplication of biogas sources and power-to-gas systems that will be added to the pipeline networks. In order to accomodate the appliances to changes in gas quality, compact and low cost natural gas quality transducers have to be developped for the natural gas industry. The present Thesis aimed at investigating the existing methods to determine natural gas quality for combustion, focusing on the determination of the Wobbe Index (WI), which is a key parameter to set up the air-fuel ratio of the combustion in burners and motors, and to qualify a new type of dynamic viscosity transducer developped at Laboratoire de Production Microtechnique (LPM) of EPFL for the determination of the combustion properties. Inference transducers are a new kind of transducers that allow determining the combustion parameters of the gas by relating to fundamental thermo-physical parameters, and not through the determination of the concentration of the gas constituents, as in gas chromatographs and spectrometers. Here, the dynamic viscosity is chosen as the most promising thermo-physical property of a natural gas to relate to the WI and the Higher Heating Value (HHV). The viscometer takes measurements proportional to the resistance to flow of a gas through a capillary under the action of pulses of heat, and it can be therefore be described as a thermal pumping gas viscometer. A mathematical model and a finite element model (FEM) are used to predict the behavior of the system and for thermal optimization, which are combined by a thermal characterization of the system. The miniature heater used to generate the heat pulses inside the viscometer is a key element of the transducer, and after reviewing potential technologies, the design choices are reported and the fabrication process is exposed, followed by a mechanical and thermal characterization. In order to determine and validate the conversion of the WI from the dynamic viscosity, theoretical relations are analyzed and empirical characterizations are done with a test and calibration setup allowing to create given mixes of gases. Finally, the degradation of the transducer to contaminants of natural gas is investigated, and the analysis is focused to the characterization of the corrosion by the sulfur compounds of natural gas. Test vehicles are developed to study the effect of sulfur corrosion on metallic parts, electronic substrates, silicone adhesives and wirebonds materials, and experiments are held with the dedicated test setups developed at LPM of EPFL.

This paper provides a synthesis and comparison of methodologies and results obtained in several studies devoted to the impact of climate change on hydropower. By putting into perspective various case studies, we provide a broader context and improved understanding of climate changes on energy production. We also underline the strengths and weaknesses of the approaches used as far as technical, physical and economical aspects are concerned. Although the catchments under investigation are located close to each other in geographic terms (Swiss and Italian Alps), they represent a wide variety of situations which may be affected by differing evolutions for instance in terms of annual runoff. In this study, we also differentiate between run-of-river, storage and pumping-storage power plants. By integrating and comparing various analyses carried out in the framework of the EU-FP7 ACQWA project, this paper discusses the complexity as well as current and future issues of hydropower management in the entire Alpine region.

Storage capacity is a key aspect when validating potential CO2 sequestration sites. Most CO2 storage projects, for obvious reasons, target conventional aquifers (e.g., saline aquifers, depleted hydrocarbon fields) with good reservoir properties and ample subsurface data. However, non-geological factors, such as proximity to the CO2 source, may require storing CO2 in geologically “less-than-ideal” sites. We here present a first-order CO2 storage resource estimate of such an unconventional storage unit, a naturally fractured, compartmentalized and underpressured siliciclastic aquifer located at 670–1,000 m below Longyearbyen, Arctic Norway. Water injection tests confirm the injectivity of the reservoir. Capacity calculations, based on the US DOE guidelines for CO2 storage resource estimation, were implemented in a stochastic volumetric workflow. All available data were used to specify input parameters and their probability distributions. The areal extent of the compartmentalized reservoir is poorly constrained, encouraging a scenario-based approach. Other high-impact parameters influencing storage resource estimates include CO2 saturation, CO2 density and the storage efficiency factor. The hydrodynamic effects of storing CO2 in a compartmentalized aquifer are accounted for by calculating probable storage efficiency factors (0.04–0.79 %) in a fully closed system. The results are ultimately linked to the chosen scenario, with two orders of magnitude difference between scenarios. The fracture network contributes with up to 2 % to the final volumes. The derived workflow validates CO2 storage sites based on initial feasibility assessments, and may be applied to aid decision making at other unconventional CO2 storage sites with significant data uncertainty.

The recycling of homogeneous acids imposes great challenges to the feasibility of lignocellulose hydrolysis processes. Although heterogeneous catalysts would offer a perspective to circumvent these challenges, conventional solid acids are instable under the hydrothermal conditions typical of hydrolysis processes. In this regard, acid functionalized carbons appear as auspicious alternatives due to the higher perseverance of carbon frameworks. The strong Brønsted acid sites in sulfonated carbons would be particularly well suited to catalyze the hydrolysis of cellulosic biomass. The utilization of these materials has so far been impeded by the controversy regarding the stability of sulfonic acid groups in carbons. Furthermore, it remains uncertain how the constraints imposed on the reaction system by the insolubility of lignocellulose influence the ability of solid acids to function as hydrolysis catalysts. This thesis shows that hydrothermally stable sulfonated carbons can be prepared by utilizing the structure-stability dependence of sulfonic acid groups in carbonaceous materials. The sulfonation of materials featuring a low degree of graphitization resulted in active solid Brønsted acid catalysts that however deactivated through the leaching of sulfonic acid groups. An in-depth physicochemical characterization of the catalysts paired with a systematic study of the stability of model sulfonic acids, revealed that the leaching-tendency is defined by substituent effects. Activating/deactivating substituents control the hydrothermal stability of aryl sulfonic acids by decreasing/increasing the tendency of the carbon-sulfur bond to undergo solvolysis. The presence of stabilizing and destabilizing substituents was found to be tunable by the temperature dependent decomposition of oxygen containing surface groups. Sulfonation of cellulose carbonized at 350°C resulted in a catalyst with 850 µmol g-1 hydrothermally (180 °C) stable sulfonic acid groups. Additionally, a hitherto unknown mode of deactivation was identified that proceeds by the ion-exchange of cationic impurities with protons of the active sites. This mode of deactivation can be fully overcome by implementing countermeasures to reverse or suppress ion-exchange processes. To tackle the limitations of homogeneous acids, the stable sulfonated carbons were used as catalysts in a semi-batch based lignocellulose hydrolysis process. It was found that the chemical recalcitrance and the insolubility of the substrate imposed strong limitations on the reaction with the catalyst and that soluble product formation occurred predominantly via auto-hydrolysis. The propensity of cellulose to undergo auto-hydrolysis could be enhanced by amorphizing its crystal structure through mechanical pretreatment in ball-mill. A heterogeneously catalyzed hydrolysis was achieved through mechanocatalytic processes facilitated by the concerted ball-milling (CBM) of the sulfonated carbon with the substrate. Sulfonic acid groups were pinpointed as active sites during the mechanocatalytic formation of soluble oligosaccharides. The secondary hydrolysis to monosaccharides in the semi-batch reactor was no longer constrained by the insolubility of the substrate. The combination of CBM pretreatment and hydrolysis in the semi-batch reactor was successfully extrapolated to the conversion of spruce fir wood to achieve yields in C5 and C6 derived products that are competitive with state-of-the-art diluted acid processes.

AbstractGlobal biodiversity is eroding due to anthropogenic causes, such as climate change, habitat loss, and trophic simplification of biological communities. Most studies address only isolated causes within a single group of organisms; however, biological groups of different trophic levels may respond in particular ways to different environmental impacts. Our study used natural microcosms to investigate the predicted individual and interactive effects of warming, changes in top predator diversity, and habitat size on the alpha and beta diversity of macrofauna, microfauna, and bacteria. Alpha diversity (i.e., richness within each bromeliad) generally explained a larger proportion of the gamma diversity (partitioned in alpha and beta diversity). Overall, dissimilarity between communities occurred due to species turnover and not species loss (nestedness). Nevertheless, the three biological groups responded differently to each environmental stressor. Microfauna were the most sensitive group, with alpha and beta diversity being affected by environmental changes (warming and habitat size) and trophic structure (diversity of top predators). Macrofauna alpha and beta diversity was sensitive to changes in predator diversity and habitat size, but not warming. In contrast, the bacterial community was not influenced by the treatments. The community of each biological group was not mutually concordant with the environmental and trophic changes. Our results demonstrate that distinct anthropogenic impacts differentially affect the components of macro and microorganism diversity through direct and indirect effects (i.e., bottom‐up and top‐down effects). Therefore, a multitrophic and multispecies approach is necessary to assess the effects of different anthropogenic impacts on biodiversity.