Seawater carbonate chemistry and reproduction of the two calanoid copepods Centropages typicus and Temora longicornis in a laboratory experiment

Some planktonic groups suffer negative effects from ocean acidification (OA), although copepods might be less sensitive. We investigated the effect of predicted CO2 levels (range 480-750 ppm), on egg production and hatching success of two copepod species, Centropages typicus and Temora longicornis. In these short-term incubations there was no significant effect of high CO2 on these parameters. Additionally a very high CO2 treatment, (CO2 = 9830 ppm), representative of carbon capture and storage scenarios, resulted in a reduction of egg production rate and hatching success of C. typicus, but not T. longicornis. In conclusion, reproduction of C. typicus was more sensitive to acute elevated seawater CO2 than that of T. longicornis, but neither species was affected by exposure to CO2 levels predicted for the year 2100. The duration and seasonal timing of exposures to high pCO2, however, might have a significant effect on the reproduction success of calanoid copepods.

CO2 capture by adsorption in post combustion processes

Global concentration of CO2 in the atmosphere is increasing rapidly. CO2 emissions have huge impact on global climate change. Therefore, efficient CO2 emission abatement strategies such as Carbon Capture and Storage (CCS) are required to combat this phenomenon. There are three major approaches for CCS: - Post-combustion capture; - Pre-combustion capture; - Oxyfuel process. Post-combustion capture offers some advantages in terms of cost as existing combustion technologies can still be used without radical changes on them. This makes post-combustion capture easier to implement as a retrofit option compared to the other two approaches. Therefore, post-combustion capture is probably the first technology that will be deployed on a large scale. The aim of this work is to study the adsorption equilibrium of CO2, CH4 and N2 in zeolite 5A at 40ºC. For this, experiments were performed to determine the isotherms of adsorption of CO2, CH4 and N2 near 40ºC with the conditions of the post-combustion capture processes. It has been found that the 5A zeolite adsorbs a significant quantity of CO2 values of about 5 mol/kg at a pressure of 5 bar.

Climate seasonality limits leaf carbon assimilation and wood productivity in tropical forests.

The seasonal climate drivers of the carbon cy- cle in tropical forests remain poorly known, although these forests account for more carbon assimilation and storage than any other terrestrial ecosystem. Based on a unique combina- tion of seasonal pan-tropical data sets from 89 experimental sites (68 include aboveground wood productivity measure- ments and 35 litter productivity measurements), their asso- ciated canopy photosynthetic capacity (enhanced vegetation index, EVI) and climate, we ask how carbon assimilation and aboveground allocation are related to climate seasonal- ity in tropical forests and how they interact in the seasonal carbon cycle. We found that canopy photosynthetic capacity seasonality responds positively to precipitation when rain- fall is < 2000 mm yr-1 (water-limited forests) and to radia- tion otherwise (light-limited forests). On the other hand, in- dependent of climate limitations, wood productivity and lit- terfall are driven by seasonal variation in precipitation and evapotranspiration, respectively. Consequently, light-limited forests present an asynchronism between canopy photosyn- thetic capacity and wood productivity. First-order control by precipitation likely indicates a decrease in tropical forest pro- ductivity in a drier climate in water-limited forest, and in cur- rent light-limited forest with future rainfall < 2000 mm yr-1.

Chemical looping reforming from methane to syngas: investigation on CeO2 oxygen carrier lifetime and optimal process times

Emissions of CO2 are constantly growing since the beginning of industrial era. Interruption of the production of major emitters sectors (energy and agriculture) is not a viable way and reducing all the emission through carbon capture and storage (CCS) is not economically viable and little publicly accepted, therefore, it becomes fundamentals to take actions like retrofitting already developed infrastructure employing cleanest resources, modify the actual processes limiting the emissions, and reduce the emissions already present through direct air capture. The present thesis will deeply discuss the aspects mentioned in regard to syngas and hydrogen production since they have a central role in the market of energy and chemicals. Among the strategies discussed, greater emphasis is given to the application of looping technologies and to direct air capture processes, as they have been the main point of this work. Particularly, chemical looping methane reforming to syngas was studied with Aspen Plus thermodynamic simulations, thermogravimetric analysis characterization (TGA) and testing in a fixed bed reactor. The process was studied cyclically exploiting the redox properties of a Ce-based oxide oxygen carrier synthetized with a simple forming procedure. The two steps of the looping cycles were studied isothermally at 900 °C and 950° C with a mixture of 10 %CH4 in N2 and of 3% O2 in N2, for carrier reduction and oxidation, respectively. During the stay abroad, in collaboration with the EHT of Zurich, a CO2 capture process in presence of amine solid sorbents was investigated, studying the difference in the performance achievable with the use of contactors of different geometry. The process was studied at two concentrations (382 ppm CO2 in N2 and 5.62% CO2 in N2) and at different flow rates, to understand the dynamics of the adsorption process and to define the mass transfer limiting step.

Experimental and numerical characterization of flame instability in hydrogen-containing flames

In the framework of the energy transition, the acquisition of proper knowledge of fundamental aspects characterizing the use of alternative fuels is paramount as well as the development of optimized know-how and technologies. In this sense, the use of hydrogen has been indicated as a promising route for decarbonization at the end-users stage in the energy supply chain. However, the elevated reactivity and the low-density at atmospheric conditions of hydrogen pose new challenges. Among the others, the dilution of hydrogen with carbon dioxide from carbon capture and storage systems represents a possible route. However, the interactions between these species have been poorly studied so far. For these reasons, this thesis, in collaboration between the University of Bologna and Technische Universität Bergakademie of Freiberg in Saxony (Germany), investigates the laminar flame of hydrogen-based premixed gas with the dilution of carbon dioxide. An experimental system, called a heat flux burner, was adopted ad different operating conditions. The presence of the cellularity phenomenon, forming the so-called cellular flame, was observed and analysed. Theoretical and visual methods have allowed for the characterization of the investigated flames, opening new alternatives for sustainable energy production via hydrogen transformation.

Captura e armazenamento de CO2

Dissertação para obtenção do Grau de Mestre em Energia e Bioenergia

Thermo-hydro-mechanical analysis of CO2 injection into deep aquifers

One of the biggest challenges for humanity is global warming and consequently, climate changes. Even though there has been increasing public awareness and investments from numerous countries concerning renewable energies, fossil fuels are and will continue to be in the near future, the main source of energy. Carbon capture and storage (CCS) is believed to be a serious measure to mitigate CO2 concentration. CCS briefly consists of capturing CO2 from the atmosphere or stationary emission sources and transporting and storing it via mineral carbonation, in oceans or geological media. The latter is referred to as carbon capture and geological storage (CCGS) and is considered to be the most promising of all solutions. Generally it consists of a storage (e.g. depleted oil reservoirs and deep saline aquifers) and sealing (commonly termed caprock in the oil industry) formations. The present study concerns the injection of CO2 into deep aquifers and regardless injection conditions, temperature gradients between carbon dioxide and the storage formation are likely to occur. Should the CO2 temperature be lower than the storage formation, a contractive behaviour of the reservoir and caprock is expected. The latter can result in the opening of new paths or re-opening of fractures, favouring leakage and compromising the CCGS project. During CO2 injection, coupled thermo-hydro-mechanical phenomena occur, which due to their complexity, hamper the assessment of each relative influence. For this purpose, several analyses were carried out in order to evaluate their influences but focusing on the thermal contractive behaviour. It was finally concluded that depending on mechanical and thermal properties of the pair aquifer-seal, the sealing caprock can undergo significant decreases in effective stress.

Pore-scale modeling of two-phase flow instabilities in porous media

Les problèmes d'écoulements multiphasiques en média poreux sont d'un grand intérêt pour de nombreuses applications scientifiques et techniques ; comme la séquestration de C02, l'extraction de pétrole et la dépollution des aquifères. La complexité intrinsèque des systèmes multiphasiques et l'hétérogénéité des formations géologiques sur des échelles multiples représentent un challenge majeur pour comprendre et modéliser les déplacements immiscibles dans les milieux poreux. Les descriptions à l'échelle supérieure basées sur la généralisation de l'équation de Darcy sont largement utilisées, mais ces méthodes sont sujettes à limitations pour les écoulements présentant de l'hystérèse. Les avancées récentes en terme de performances computationnelles et le développement de méthodes précises pour caractériser l'espace interstitiel ainsi que la distribution des phases ont favorisé l'utilisation de modèles qui permettent une résolution fine à l'échelle du pore. Ces modèles offrent un aperçu des caractéristiques de l'écoulement qui ne peuvent pas être facilement observées en laboratoire et peuvent être utilisé pour expliquer la différence entre les processus physiques et les modèles à l'échelle macroscopique existants. L'objet premier de la thèse se porte sur la simulation numérique directe : les équations de Navier-Stokes sont résolues dans l'espace interstitiel et la méthode du volume de fluide (VOF) est employée pour suivre l'évolution de l'interface. Dans VOF, la distribution des phases est décrite par une fonction fluide pour l'ensemble du domaine et des conditions aux bords particulières permettent la prise en compte des propriétés de mouillage du milieu poreux. Dans la première partie de la thèse, nous simulons le drainage dans une cellule Hele-Shaw 2D avec des obstacles cylindriques. Nous montrons que l'approche proposée est applicable même pour des ratios de densité et de viscosité très importants et permet de modéliser la transition entre déplacement stable et digitation visqueuse. Nous intéressons ensuite à l'interprétation de la pression capillaire à l'échelle macroscopique. Nous montrons que les techniques basées sur la moyenne spatiale de la pression présentent plusieurs limitations et sont imprécises en présence d'effets visqueux et de piégeage. Au contraire, une définition basée sur l'énergie permet de séparer les contributions capillaires des effets visqueux. La seconde partie de la thèse est consacrée à l'investigation des effets d'inertie associés aux reconfigurations irréversibles du ménisque causé par l'interface des instabilités. Comme prototype pour ces phénomènes, nous étudions d'abord la dynamique d'un ménisque dans un pore angulaire. Nous montrons que, dans un réseau de pores cubiques, les sauts et reconfigurations sont si fréquents que les effets d'inertie mènent à différentes configurations des fluides. A cause de la non-linéarité du problème, la distribution des fluides influence le travail des forces de pression, qui, à son tour, provoque une chute de pression dans la loi de Darcy. Cela suggère que ces phénomènes devraient être pris en compte lorsque que l'on décrit l'écoulement multiphasique en média poreux à l'échelle macroscopique. La dernière partie de la thèse s'attache à démontrer la validité de notre approche par une comparaison avec des expériences en laboratoire : un drainage instable dans un milieu poreux quasi 2D (une cellule Hele-Shaw avec des obstacles cylindriques). Plusieurs simulations sont tournées sous différentes conditions aux bords et en utilisant différents modèles (modèle intégré 2D et modèle 3D) afin de comparer certaines quantités macroscopiques avec les observations au laboratoire correspondantes. Malgré le challenge de modéliser des déplacements instables, où, par définition, de petites perturbations peuvent grandir sans fin, notre approche numérique apporte de résultats satisfaisants pour tous les cas étudiés. - Problems involving multiphase flow in porous media are of great interest in many scientific and engineering applications including Carbon Capture and Storage, oil recovery and groundwater remediation. The intrinsic complexity of multiphase systems and the multi scale heterogeneity of geological formations represent the major challenges to understand and model immiscible displacement in porous media. Upscaled descriptions based on generalization of Darcy's law are widely used, but they are subject to several limitations for flow that exhibit hysteric and history- dependent behaviors. Recent advances in high performance computing and the development of accurate methods to characterize pore space and phase distribution have fostered the use of models that allow sub-pore resolution. These models provide an insight on flow characteristics that cannot be easily achieved by laboratory experiments and can be used to explain the gap between physical processes and existing macro-scale models. We focus on direct numerical simulations: we solve the Navier-Stokes equations for mass and momentum conservation in the pore space and employ the Volume Of Fluid (VOF) method to track the evolution of the interface. In the VOF the distribution of the phases is described by a fluid function (whole-domain formulation) and special boundary conditions account for the wetting properties of the porous medium. In the first part of this thesis we simulate drainage in a 2-D Hele-Shaw cell filled with cylindrical obstacles. We show that the proposed approach can handle very large density and viscosity ratios and it is able to model the transition from stable displacement to viscous fingering. We then focus on the interpretation of the macroscopic capillary pressure showing that pressure average techniques are subject to several limitations and they are not accurate in presence of viscous effects and trapping. On the contrary an energy-based definition allows separating viscous and capillary contributions. In the second part of the thesis we investigate inertia effects associated with abrupt and irreversible reconfigurations of the menisci caused by interface instabilities. As a prototype of these phenomena we first consider the dynamics of a meniscus in an angular pore. We show that in a network of cubic pores, jumps and reconfigurations are so frequent that inertia effects lead to different fluid configurations. Due to the non-linearity of the problem, the distribution of the fluids influences the work done by pressure forces, which is in turn related to the pressure drop in Darcy's law. This suggests that these phenomena should be taken into account when upscaling multiphase flow in porous media. The last part of the thesis is devoted to proving the accuracy of the numerical approach by validation with experiments of unstable primary drainage in a quasi-2D porous medium (i.e., Hele-Shaw cell filled with cylindrical obstacles). We perform simulations under different boundary conditions and using different models (2-D integrated and full 3-D) and we compare several macroscopic quantities with the corresponding experiment. Despite the intrinsic challenges of modeling unstable displacement, where by definition small perturbations can grow without bounds, the numerical method gives satisfactory results for all the cases studied.

Potencial uso de serpentinito no armazenamento mineral do CO2

Rising anthropogenic CO2 emissions are considered a major contributor to the greenhouse effect. There are several options for reducing atmospheric CO2 levels, and among these alternatives, Carbon Capture and Storage (CCS) has been identified as an effective and promising approach. This work investigated the feasibility of using serpentinite as a vehicle for carbon storage presenting a source-sink match. The main results of the work confirmed that serpentinite is appropriate for the carbonation process due to the high concentration of Mg in its composition.

Development of chemical looping combustion process

Chemical looping combustion (CLC) provides a promising technology to help cut carbon dioxide emissions. CLC is based on separated oxidation and reduction processes. Oxygen carrier, which is made from metal and supporting material, is in continuous recirculation between the air and fuel reactors. The CLC process does not require separation unit for carbon dioxide. The fuel reactor can produce an almost pure carbon dioxide feed which decrease costs of carbon capture and storage (CCS). The CLC method is one of the most promising ones for energy efficient carbon capture. A large amount of literature was examined for this study and from it the most promising methods and designs were chosen. These methods and designs were combined as reactor system design which was then sized during the making of this thesis. Sizing was done with a mathematical model that was further improved during the study.

Hiilidioksidin talteenoton mahdollistavat polttotekniikat

Kandidaatintyössä esitellään eri teknologioita hiilidioksidin talteenottamiseksi. Teknologioista esitellään niiden toimintaperiaate, pääpiirteet, heikkoudet ja vahvuudet, sekä nykytila. Työssä käsiteltiin kuutta teknologiaa: hiilidioksidin erotus polton jälkeen, hiilidioksidin erotus ennen polttoa, hiilidioksidin erotus happipoltolla, kemikaalikiertopoltto, kalsiumkiertoprosessi ja yhdistetty kolmen reaktorin kalsium- ja kemikaali kiertopolttoprosessia. Polton jälkeinen hiilidioksidin talteenotto sopii hyvin käytössä olevien laitoksien muuntamiseen niin kuin happipolttokin, mutta erotus ja talteenotto ennen polttoa ei sovellu kun vain uusiin laitoksiin. Kolme viimeisintä käsiteltyä teknologiaa ovat nuoria, kypsymättömiä, niissä paljon etuja ja niiden voi olettaa kehittyvän hyviksi teknologioiksi.

Particle model for simulating limestone reactions in novel fluidised bed energy applications

The development of carbon capture and storage (CCS) has raised interest towards novel fluidised bed (FB) energy applications. In these applications, limestone can be utilized for S02 and/or CO2 capture. The conditions in the new applications differ from the traditional atmospheric and pressurised circulating fluidised bed (CFB) combustion conditions in which the limestone is successfully used for SO2 capture. In this work, a detailed physical single particle model with a description of the mass and energy transfer inside the particle for limestone was developed. The novelty of this model was to take into account the simultaneous reactions, changing conditions, and the effect of advection. Especially, the capability to study the cyclic behaviour of limestone on both sides of the calcination-carbonation equilibrium curve is important in the novel conditions. The significances of including advection or assuming diffusion control were studied in calcination. Especially, the effect of advection in calcination reaction in the novel combustion atmosphere was shown. The model was tested against experimental data; sulphur capture was studied in a laboratory reactor in different fluidised bed conditions. Different Conversion levels and sulphation patterns were examined in different atmospheres for one limestone type. The Conversion curves were well predicted with the model, and the mechanisms leading to the Conversion patterns were explained with the model simulations. In this work, it was also evaluated whether the transient environment has an effect on the limestone behaviour compared to the averaged conditions and in which conditions the effect is the largest. The difference between the averaged and transient conditions was notable only in the conditions which were close to the calcination-carbonation equilibrium curve. The results of this study suggest that the development of a simplified particle model requires a proper understanding of physical and chemical processes taking place in the particle during the reactions. The results of the study will be required when analysing complex limestone reaction phenomena or when developing the description of limestone behaviour in comprehensive 3D process models. In order to transfer the experimental observations to furnace conditions, the relevant mechanisms that take place need to be understood before the important ones can be selected for 3D process model. This study revealed the sulphur capture behaviour under transient oxy-fuel conditions, which is important when the oxy-fuel CFB process and process model are developed.

Production of magnesium carbonates from serpentinites for CO2 mineral sequestration : optimisation towards industrial application

Global warming is one of the most alarming problems of this century. Initial scepticism concerning its validity is currently dwarfed by the intensification of extreme weather events whilst the gradual arising level of anthropogenic CO2 is pointed out as its main driver. Most of the greenhouse gas (GHG) emissions come from large point sources (heat and power production and industrial processes) and the continued use of fossil fuels requires quick and effective measures to meet the world’s energy demand whilst (at least) stabilizing CO2 atmospheric levels. The framework known as Carbon Capture and Storage (CCS) – or Carbon Capture Utilization and Storage (CCUS) – comprises a portfolio of technologies applicable to large‐scale GHG sources for preventing CO2 from entering the atmosphere. Amongst them, CO2 capture and mineralisation (CCM) presents the highest potential for CO2 sequestration as the predicted carbon storage capacity (as mineral carbonates) far exceeds the estimated levels of the worldwide identified fossil fuel reserves. The work presented in this thesis aims at taking a step forward to the deployment of an energy/cost effective process for simultaneous capture and storage of CO2 in the form of thermodynamically stable and environmentally friendly solid carbonates. R&D work on the process considered here began in 2007 at Åbo Akademi University in Finland. It involves the processing of magnesium silicate minerals with recyclable ammonium salts for extraction of magnesium at ambient pressure and 400‐440⁰C, followed by aqueous precipitation of magnesium in the form of hydroxide, Mg(OH)2, and finally Mg(OH)2 carbonation in a pressurised fluidized bed reactor at ~510⁰C and ~20 bar PCO2 to produce high purity MgCO3. Rock material taken from the Hitura nickel mine, Finland, and serpentinite collected from Bragança, Portugal, were tested for magnesium extraction with both ammonium sulphate and bisulphate (AS and ABS) for determination of optimal operation parameters, primarily: reaction time, reactor type and presence of moisture. Typical efficiencies range from 50 to 80% of magnesium extraction at 350‐450⁰C. In general ABS performs better than AS showing comparable efficiencies at lower temperature and reaction times. The best experimental results so far obtained include 80% magnesium extraction with ABS at 450⁰C in a laboratory scale rotary kiln and 70% Mg(OH)2 carbonation in the PFB at 500⁰C, 20 bar CO2 pressure for 15 minutes. The extraction reaction with ammonium salts is not at all selective towards magnesium. Other elements like iron, nickel, chromium, copper, etc., are also co‐extracted. Their separation, recovery and valorisation are addressed as well and found to be of great importance. The assessment of the exergetic performance of the process was carried out using Aspen Plus® software and pinch analysis technology. The choice of fluxing agent and its recovery method have a decisive sway in the performance of the process: AS is recovered by crystallisation and in general the whole process requires more exergy (2.48–5.09 GJ/tCO2sequestered) than ABS (2.48–4.47 GJ/tCO2sequestered) when ABS is recovered by thermal decomposition. However, the corrosive nature of molten ABS and operational problems inherent to thermal regeneration of ABS prohibit this route. Regeneration of ABS through addition of H2SO4 to AS (followed by crystallisation) results in an overall negative exergy balance (mainly at the expense of low grade heat) but will flood the system with sulphates. Although the ÅA route is still energy intensive, its performance is comparable to conventional CO2 capture methods using alkanolamine solvents. An energy‐neutral process is dependent on the availability and quality of nearby waste heat and economic viability might be achieved with: magnesium extraction and carbonation levels ≥ 90%, the processing of CO2‐containing flue gases (eliminating the expensive capture step) and production of marketable products.

Evaluation of the main energy scenarios for the global energy transition

Energy scenarios are used as a tool to examine credible future states and pathways. The one who constructs a scenario defines the framework in which the possible outcomes exist. The credibility of a scenario depends on its compatibility with real world experiences, and on how well the general information of the study, methodology, and originality and processing of data are disclosed. In the thesis, selected global energy scenarios’ transparency and desirability from the society’s point of view were evaluated based on literature derived criteria. The global energy transition consists of changes to social conventions and economic development in addition to technological development. Energy solutions are economic and ethical choices due to far-reaching impacts of energy decision-making. Currently the global energy system is mostly based on fossil fuels, which is unsustainable over the long-term due to various reasons: negative climate change impacts, negative health impacts, depletion of fossil fuel reserves, resource-use conflicts with water management and food supply, loss of biodiversity, challenge to preserve ecosystems and resources for future generations, and inability of fossil fuels to provide universal access to modern energy services. Nuclear power and carbon capture and storage cannot be regarded as sustainable energy solutions due to their inherent risks and required long-term storage. The energy transition is driven by a growing energy demand, decreasing costs of renewables, modularity and scalability of renewable technologies, macroeconomic benefits of using renewables, investors’ risk awareness, renewable energy related attractive business opportunities, almost even distribution of solar and wind resources on the planet, growing awareness of the planet’s environmental status, environmental movements and tougher environmental legislation. Many of the investigated scenarios identified solar and wind power as a backbone for future energy systems. The scenarios, in which the solar and wind potentials were deployed in largest scale, met best the set out sustainability criteria. In future research, energy scenarios’ transparency can be improved by better disclosure on who has ordered the study, clarifying the funding, clearly referencing to used sources and indicating processed data, and by exploring how variations in cost assumptions and deployment of technologies influence on the outcomes of the study.

Life cycle analysis of UK coal fired power plants

This paper examines the life cycle GHG emissions from existing UK pulverized coal power plants. The life cycle of the electricity Generation plant includes construction, operation and decommissioning. The operation phase is extended to upstream and downstream processes. Upstream processes include the mining and transport of coal including methane leakage and the production and transport of limestone and ammonia, which are necessary for flue gas clean up. Downstream processes, on the other hand, include waste disposal and the recovery of land used for surface mining. The methodology used is material based process analysis that allows calculation of the total emissions for each process involved. A simple model for predicting the energy and material requirements of the power plant is developed. Preliminary calculations reveal that for a typical UK coal fired plant, the life cycle emissions amount to 990 g CO2-e/kWh of electricity generated, which compares well with previous UK studies. The majority of these emissions result from direct fuel combustion (882 g/kWh 89%) with methane leakage from mining operations accounting for 60% of indirect emissions. In total, mining operations (including methane leakage) account for 67.4% of indirect emissions, while limestone and other material production and transport account for 31.5%. The methodology developed is also applied to a typical IGCC power plant. It is found that IGCC life cycle emissions are 15% less than those from PC power plants. Furthermore, upon investigating the influence of power plant parameters on life cycle emissions, it is determined that, while the effect of changing the load factor is negligible, increasing efficiency from 35% to 38% can reduce emissions by 7.6%. The current study is funded by the UK National Environment Research Council (NERC) and is undertaken as part of the UK Carbon Capture and Storage Consortium (UKCCSC). Future work will investigate the life cycle emissions from other power generation technologies with and without carbon capture and storage. The current paper reveals that it might be possible that, when CCS is employed. the emissions during generation decrease to a level where the emissions from upstream processes (i.e. coal production and transport) become dominant, and so, the life cycle efficiency of the CCS system can be significantly reduced. The location of coal, coal composition and mining method are important in determining the overall impacts. In addition to studying the net emissions from CCS systems, future work will also investigate the feasibility and technoeconomics of these systems as a means of carbon abatement.