L’étude de matériaux conducteur mixtes (ionique et électronique) connait un intérêt croissant depuis plusieurs années dans le domaine de l’énergie, principalement lié au développement des électrodes pour les piles à combustible de type SOFC (Solid Oxide Fuel Cell) ou des réacteurs catalytiques membranaires (CMR) pour le réformage du méthane de synthèse ou pour le procédé d’oxycombustion. Dans ce dernier cas, la réalisation de membranes conductrices mixtes de structure pérovskite du type La1-xAxFe1-yByO3- permet la séparation de l’oxygène de l’air à haute température (900°C) avec une sélectivité quasiment infinie sans circuit électrique extérieur. Les mécanismes limitant le transport de l’oxygène à travers la membrane ont été étudiés à l’aide d’un dispositif de caractérisation original composé d’électrodes, permettant la mesure du potentiel électrochimique de l’oxygène à la surface de la membrane. L’influence de la substitution du cation en site A puis en site B sur les propriétés de semi-perméabilité à l’oxygène a été étudiée au sein des matériaux pérovskites La0,5A0,5Fe0,7B0,3O3-(A = Ca, Sr, Ba et B = Al, Co, Cu, Ga, Mg, Mn, Ni, Sn, Ti, Zn). Les résultats obtenus avec cette technique originale nous ont permis de mieux cerner les mécanismes limitant le transport d’oxygène à travers la membrane. L’influence de la microstructure de la membrane sur les propriétés de semi-perméabilité à l’oxygène a également été étudiée et un modèle d’évolution des propriétés de semi-perméabilité en fonction de la microstructure a été proposé. Cette compréhension des mécanismes de transport nous a permis d’orienter les recherches vers l’élaboration de nouvelles architectures de membranes. / Since few years, the study of mixed conducting materials (ionic and electronic) knows an increasing interest in the energy area, especially with the development of electrodes for Solid Oxide Fuel Cell (SOFC) or Catalytic Membrane Reactors (CMR) for the methane reforming in synthesis gas or for oxyfuel process. In this latter case, the mixed conductor membrane with La1-xAxFe1-yByO3- perovskite structure allows the separation of oxygen from air at high temperature (900°C) with a quasi-infinite selectivity without outside electric circuit, with an interesting economical cost. The oxygen transport mechanisms through the membrane are studied thanks to an original electrodes system composed of a zirconia point micro-electrode and a metallic reference electrode. This system allows the measurement of the oxygen electrochemical potential at the membrane surface. The influence of cation substitution in A-site then B-site in La0.5A0.5Fe0.7B0.3O3-(A = Ca, Sr, Ba and B = Al, Co, Cu, Ga, Mg, Mn, Ni, Sn, Ti, Zn) perovskite materials has been studied. The results obtained by this original system led us to a better understanding and a identification of the rate determining step of oxygen transport mechanism through the membrane. The influence of the microstructure on oxygen semi-permeation has been studied and an evolution model of semi-permeation properties with microstructure has been shown. The understanding of oxygen transport mechanisms led to the development and the elaboration of news architectures of membranes.

Les progrès technologiques des dispositifs expérimentaux ainsi que les récentes avancées pour la simulation des spectres Raman à haute température rendent aujourd’hui possible la mise en oeuvre d’une technique de mesures multi-espèces de température et de concentration uniquement fondée sur l’ajustement des spectres mono-coups de diffusion Raman spontanée collectés au sein des flammes turbulentes. Dans cette étude, cette stratégie de post-traitement, associée à une chaîne de mesure spécifique, est développée selon plusieurs axes pour permettre l’extension des mesures à des cas de flammes ordinairement hostiles aux mesures classiques Rayleigh/Raman résolues par inversion matricielle ou par méthode hybride. Dans une flamme diphasique d’éthanol, une thermométrie fondée sur l’ajustement des spectres de N2 a été mise en place afin de s’affranchir des contraintes liées à la diffusion de Mie des gouttes. L’intégration d’une thermométrie Raman à partir du spectre du méthane ainsi que d’une procédure de minimisation de l’émission de C2 dans le post-traitement des spectres ont permis la réalisation de cartographies multi-scalaires (température et toutes espèces majoritaires) dans toute la zone de recirculation d’une flamme turbulente légèrement fuligineuse générée par un brûleur bluff-body. Une thermométrie fondée sur la minimisation du spectre Raman de CO2 a également été développée et éprouvée au cours d’une campagne de mesures dans une installation d’échelle semi-industrielle reproduisant les conditions d’oxycombustion des cycles de turbines à gaz dans l’objectif de la capture et de la séquestration du CO2. / Recent progress in experimental devices and simulation of high-temperature Raman spectra enable the implementation of a spectral fitting method to solve single-shot Spontaneous Raman Scattering spectra collected in turbulent flames. In this study, this post-processing method, associated to a specific experimental set-up, has been developed to extend measurements to several cases of non-Raman friendly flames where matrix inversion or hybrid methods are usually limited. In a two-phase flame, N2 Raman thermometry has been used to overcome issues from Mie scattering of droplets. The implementation of a CH4 Raman thermometry and a minimization procedure of C2 emission in the data post-processing allowed the achievement of multi-scalar cartographies (temperature and all major species) throughout the recirculation zone of a slightly sooting turbulent flame stabilized on a bluff-body burner. A thermometry based on the minimization of CO2 Raman spectrum has also been developed and tested during a measurement campaign in a semi-industrial scale installation designed for the study of oxyfuel gas turbine cycle in the aim of carbon capture and sequestration.

Global energy demand is predicted to rise in the coming decades, necessitating a shift to renewable energy sources to mitigate greenhouse gas emissions. However, due to the inability to supply renewable energy around the clock, it is estimated that only by adding an important technology, carbon capture and storage (CCS), it could be possible to reduce 80% of the 1990s greenhouse gas emissions. CCS aims to reduce anthropogenic carbon emissions by capturing CO2 from flue gases, transporting, and permanently storing or reutilizing industrially. The CCS approach includes three technologies: post-combustion capture, pre-combustion capture, and oxyfuel combustion, with the latter being the emphasis of this thesis. Based on the case study of Mälarenergi’s Refused-derived waste-fired CHP plant, this thesis investigates the viability of converting existing non-fossil fueled CHP plants to oxyfuel combustion. A thorough technical investigation based on analyzing the impact of oxyfuel combustion on system performance was conducted through system modeling using a process simulator, Aspen plus. The model in this thesis considers the development of an air separation unit (ASU), a CHP plant, and a cryogenic CO2 purification unit (CPU). All of which are validated through calibration and comparison with real-world data and similar work. To investigate the influence of employing oxyfuel combustion on the generation of both heat and electricity, two different scenarios were comprised, including recirculating flue gas before and after flue gas condensation. In addition, an analysis of the oxygen purity was conducted to assess the most optimal parameters with the least impact on system performance. Moreover, a detailed eco- nomic assessment comprising the costs of integrating oxyfuel combustion was also conducted. The findings of this thesis show that integrating waste incineration CHP plants with oxyfuel combustion for CO2 capture entails promising features under the condition of 97% oxygen purity and a flue gas recirculation system taking place after flue gas condensation. This is owing to (i) modest imposed energy penalty of approximately 8.7%, (ii) high CO2 recovery ratio, around 92.4%, (iii) total investment cost of approximately 554 M$ during a 20-year lifetime, and (iv) cost of captured CO2 of around 76 $/ton. Aside from system modeling, this thesis pre- sents an overview of the current state-of-the-art technology on the different separation and capture mechanisms. It is important to highlight that the goal of this thesis is not to provide a comprehensive review but rather to present an overall picture of the maturity of the different mechanisms. The findings point to the cryogenic separation mechanism as the most mature technology for both oxygen production and capturing of CO2 during oxyfuel combustion.

I denna rapport har ett projekt utförts tillsammans med Gränges AB. Projektet behandlade en energianalys av deras två oxyfuel-smältugnar för smältning av aluminium. Aluminiumsmältan består till stor del av återvunnet skrot, denna metod kallas omsmältning. Ett omsmältverk kräver enorma mängder energi och därför är en minimering av ugnarnas energiförbrukning önskvärd. Smältugnarna har liknande uppbyggnad där den stora skillnaden är deras smältkapacitet, 25 ton respektive 45 ton. Trots sina likheter påvisas en skillnad i energiförbrukning mellan ugnarna vilket även skapar ett intresse för en jämförelse av ugnarna. Med en historisk datamängd som innehöll mätvärden på ett flertal parametrar togs energiförbrukningar för varje smältcykel fram. Vid jämförelser användes energiförbrukning i enheten kWh/ton. Smältcyklarnas energiförbrukning sattes in ett histogram för jämförelse mellan ugnarna. En energibalans för vardera ugn gjordes och gav förståelse var de stora förlusterna sker. Energibalansen gavs av brännarnas totalt förbrukade energi, avgasförluster, väggförluster, askaförluster, sumpförluster, nyttiga energin till aluminiet och övriga förluster. I övriga förluster inkluderades förluster vid dörröppning vilket också beräknades. Ytterligare undersöktes parametrarna dörröppningstid, sumpvikt, körningstid och vikt på tungt aluminium individuellt för att fastställa vad som påverkar energiförbrukningen mest. Detta genom att jämföra smältcyklar där endast en parameter varierar. Parametern dörröppningstid undersöktes på en djupare nivå då denna parameter kan minimeras. Resultaten påvisade att ena ugnen hade mer oregelbunden energiförbrukning än den andra vilket berodde på att den tillverkar en större variation av aluminiumlegeringar och har tillgång till en förvärmningsugn. De största förlusterna var avgasförlusterna, sumpförlusterna och övriga förluster. En stor del av övriga förluster var förluster vid dörröppning. Väggförlusterna var märkbara och askaförlusterna var minimala. Undersökning av dörröppningstid visade att dörröppningstiden påverkade energiförbrukningen markant. / A project has been carried out together with Gränges AB which treated an energy analysis of their two oxyfuel furnaces for aluminium melting. The aluminium melt largely consists of recycled scrap and this method is called secondary melting. These secondary melting plants consumes a huge amount of energy and that is why a minimization of the furnace’s energy consumption is needed. The two furnaces have similar construction, and the main difference is their melting capacity, 25 and 45 tonnes respectively. Despite their similarities a difference in energy consumption is shown which creates an interest for a comparison of the furnaces. With a collection of earlier measurement data of several parameters the energy consumption of every melting cycle could be calculated. For comparisons of energy consumptions, the unit kWh/tonne was used. The energy consumption of every melting cycle was placed in a histogram for simple comparison. An energy balance of each furnace was done which gave understanding of their major losses. The energy balance consisted of the total used energy from the burners, the flue gas losses, the wall losses, the dross losses, the slag losses, the useful energy output for aluminium and the miscellaneous heat losses. One part of the miscellaneous heat losses is the losses from door opening which also was accounted to. Furthermore, the parameters door opening duration, slag weight, the melting cycle duration and heavy aluminium weight was examined individually to understand its impact on the furnace energy consumption. This was done by comparing the melting cycles consumed energy when only one of the parameters varied. The parameter door opening duration was examined more profound because it is a parameter that can be minimized. The results showed that one of the furnaces had more irregular energy consumption. This was due to this furnace producing a higher variety of aluminium alloys and utilizing a preheating furnace. The major energy losses were flue gas losses, the slag losses, and the miscellaneous losses. The door opening duration was a major part of the miscellaneous losses. The wall losses were noticeable, and the dross losses were minimal. The examination of the parameter door opening duration showed that this parameter largely affected the furnace consumed energy.

The topic of this thesis is carbon dioxide (CO2) capture and storage (CCS), which is a technology that is currently being promoted by industries, scientists and governments, among others, in order to mitigate climate change despite a continued use of fossil fuels. Because of the complex nature of CCS and the risks it entails, it is controversial. The aim of this thesis is to analyse how the technology may be further developed in a responsible manner. In the first part of the thesis different methods for capturing CO2 from industrial processes as well as power plants are analysed. The aim is to identify early opportunities for CO2 capture, which is considered important because of the urgency of the climate change problem. Three potential early opportunities are studied: i) capturing CO2 from calcining processes such as cement industries by using the oxyfuel process, ii) capturing CO2 from pressurised flue gas, and iii) capturing CO2 from hybrid combined cycles. Each opportunity has properties that may make them competitive in comparison to the more common alternatives if CCS is realised. However, there are also drawbacks. For example, while capturing CO2 from pressurised flue gas enables the use of more compact capture plant designs as well as less expensive and less toxic absorbents, the concept is neither suitable for retrofitting nor has it been promoted by the large and influential corporations. The second part of the thesis has a broader scope than the first and is multidisciplinary in its nature with inspiration from the research field of Science and Technology Studies (STS). The approach is to critically analyse stakeholder percep-tions regarding CCS, with a specific focus on the CCS experts. The thesis sheds new light on the complexity and scientific uncertainty of CCS as well as on the optimism among many of its proponents. Because of the uncertain development when it comes to climate change, fossil fuel use and greenhouse gas emissions, the conclusion is that CCS has to be further developed and demonstrated. A responsible strategy for a future development of CCS would benefit from: i) a search for win-win strategies, ii) increasing use of appropriate analytical tools such as life-cycle analysis, iii) a consideration of fossil fuel scarcity and increasing price volatility, iv) funding of unbiased research and v) increasing simultaneous investments in long-term solutions such as renewable energy alternatives and efficiency improvements. / QC 20100727