Matching CO2 large point sources and potential geological storage sites in mainland Portugal

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia do Ambiente, Perfil Gestão e Sistemas Ambientais

Experimental Gravimetric Adsorption Equilibrium of n-Alkanes and Alkenes, Carbon Dioxide and Nitrogen in MIL-53(Al) and Zeolite 5A

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

Towards sustainable Iron- and steelmaking with economic optimization

The iron and steelmaking industry is among the major contributors to the anthropogenic emissions of carbon dioxide in the world. The rising levels of CO2 in the atmosphere and the global concern about the greenhouse effect and climate change have brought about considerable investigations on how to reduce the energy intensity and CO2 emissions of this industrial sector. In this thesis the problem is tackled by mathematical modeling and optimization using three different approaches. The possibility to use biomass in the integrated steel plant, particularly as an auxiliary reductant in the blast furnace, is investigated. By pre-processing the biomass its heating value and carbon content can be increased at the same time as the oxygen content is decreased. As the compression strength of the preprocessed biomass is lower than that of coke, it is not suitable for replacing a major part of the coke in the blast furnace burden. Therefore the biomass is assumed to be injected at the tuyere level of the blast furnace. Carbon capture and storage is, nowadays, mostly associated with power plants but it can also be used to reduce the CO2 emissions of an integrated steel plant. In the case of a blast furnace, the effect of CCS can be further increased by recycling the carbon dioxide stripped top gas back into the process. However, this affects the economy of the integrated steel plant, as the amount of top gases available, e.g., for power and heat production is decreased. High quality raw materials are a prerequisite for smooth blast furnace operation. High quality coal is especially needed to produce coke with sufficient properties to ensure proper gas permeability and smooth burden descent. Lower quality coals as well as natural gas, which some countries have in great volumes, can be utilized with various direct and smelting reduction processes. The DRI produced with a direct reduction process can be utilized as a feed material for blast furnace, basic oxygen furnace or electric arc furnace. The liquid hot metal from a smelting reduction process can in turn be used in basic oxygen furnace or electric arc furnace. The unit sizes and investment costs of an alternative ironmaking process are also lower than those of a blast furnace. In this study, the economy of an integrated steel plant is investigated by simulation and optimization. The studied system consists of linearly described unit processes from coke plant to steel making units, with a more detailed thermodynamical model of the blast furnace. The results from the blast furnace operation with biomass injection revealed the importance of proper pre-processing of the raw biomass as the composition of the biomass as well as the heating value and the yield are all affected by the pyrolysis temperature. As for recycling of CO2 stripped blast furnace top gas, substantial reductions in the emission rates are achieved if the stripped CO2 can be stored. However, the optimal recycling degree together with other operation conditions is heavily dependent on the cost structure of CO2 emissions and stripping/storage. The economical feasibility related to the use of DRI in the blast furnace depends on the price ratio between the DRI pellets and the BF pellets. The high amount of energy needed in the rotary hearth furnace to reduce the iron ore leads to increased CO2 emissions.

Gross direct and embodied carbon sinks for urban inventories

Cities and urban regions are undertaking efforts to quantify greenhouse (GHG) emissions from their jurisdictional boundaries. Although inventorying methodologies are beginning to standardize for GHG sources, carbon sequestration is generally not quantified. This article describes the methodology and quantification of gross urban carbon sinks. Sinks are categorized into direct and embodied sinks. Direct sinks generally incorporate natural process, such as humification in soils and photosynthetic biomass growth (in urban trees, perennial crops, and regional forests). Embodied sinks include activities associated with consumptive behavior that result in the import and/or storage of carbon, such as landfilling of waste, concrete construction, and utilization of durable wood products. Using methodologies based on the Intergovernmental Panel on Climate Change 2006 guidelines (for direct sinks) and peer-reviewed literature (for embodied sinks), carbon sequestration for 2005 is calculated for the Greater Toronto Area. Direct sinks are found to be 317 kilotons of carbon (kt C), and are dominated by regional forest biomass. Embodied sinks are calculated to be 234 kt C based on one year's consumption, though a complete life cycle accounting of emissions would likely transform this sum from a carbon sink to a source. There is considerable uncertainty associated with the methodologies used, which could be addressed with city-specific stock-change measurements. Further options for enhancing carbon sink capacity within urban environments are explored, such as urban biomass growth and carbon capture and storage.

Gas composition, concentration and stable isotope ratios (Table 2, 3, 4)

The deployment of CCS (carbon capture and storage) at industrial scale implies the development of effective monitoring tools. Noble gases are tracers usually proposed to track CO2. This methodology, combined with the geochemistry of carbon isotopes, has been tested on available analogues. At first, gases from natural analogues were sampled in the Colorado Plateau and in the French carbogaseous provinces, in both well-confined and leaking-sites. Second, we performed a 2-years tracing experience on an underground natural gas storage, sampling gas each month during injection and withdrawal periods. In natural analogues, the geochemical fingerprints are dependent on the containment criterion and on the geological context, giving tools to detect a leakage of deep-CO2 toward surface. This study also provides information on the origin of CO2, as well as residence time of fluids within the crust and clues on the physico-chemical processes occurring during the geological story. The study on the industrial analogue demonstrates the feasibility of using noble gases as tracers of CO2. Withdrawn gases follow geochemical trends coherent with mixing processes between injected gas end-members. Physico-chemical processes revealed by the tracing occur at transient state. These two complementary studies proved the interest of geochemical monitoring to survey the CO2 behaviour, and gave information on its use.

Diffuse Soil Co2 Flux To Assess The Reliability Of Co2 Storage In The Mazarrón-Gañuelas Tertiary Basin (Spain)

Geological storage of CO2 is nowadays internationally considered as the most effective method for greenhouse gas emission mitigation, in order to minimize its effects on the global climatology. One of the main options is to store the CO2 in deep saline aquifers at more than 800 m depth, because it achieves its supercritical state. Among the most important aspects concerning the performance assessment of a deep CO2 geological repository is the evaluation of the CO2 leakage rate from the chosen storage geological formation. Therefore, it is absolutely necessary to increase the knowledge on the interaction among CO2, storage and sealing formations, as well as on the flow paths for CO2 and the physico-mechanical resistance of the sealing formation. Furthermore, the quantification of the CO2 leakage rate is essential to evaluate its effects on the environment. One way to achieve this objective is to study of CO2 leakage on natural analogue systems, because they can provide useful information about the natural performance of the CO2, which can be applied to an artificial CO2 geological storage. This work is focused on the retention capacity of the cap-rock by measuring the diffuse soil CO2 flux in a site selected based on: i) the presence of a natural and deep CO2 accumulation; ii) its structural geological characteristics; and iii) the nature of the cap-rocks. This site is located in the so-called Mazarrón-Gañuelas Tertiary Basin, in the Guadalentin Valley, province of Murcia (Spain) Therefore the main objective of this investigation has been to detect the possible leakages of CO2 from a deep saline aquifer to the surface in order to understand the capability of this area as a natural analogue for Carbon Capture and Sequestration (CCS). The results obtained allow to conclude that the geological sealing formation of the basin seems to be appropriate to avoid CO2 leakages from the storage formation.

Geochemical monitoring in the Hontomín (Burgos, Spain) injection site: preliminary results and perspectives

CO2 capture and storage (CCS) projects are presently developed to reduce the emission of anthropogenic CO2 into the atmosphere. CCS technologies are expected to account for the 20% of the CO2 reduction by 2050. One of the main concerns of CCS is whether CO2 may remain confined within the geological formation into which it is injected since post-injection CO2 migration in the time scale of years, decades and centuries is not well understood. Theoretically, CO2 can be retained at depth i) as a supercritical fluid (physical trapping), ii) as a fluid slowly migrating in an aquifer due to long flow path (hydrodynamic trapping), iii) dissolved into ground waters (solubility trapping) and iv) precipitated secondary carbonates. Carbon dioxide will be injected in the near future (2012) at Hontomín (Burgos, Spain) in the frame of the Compostilla EEPR project, led by the Fundación Ciudad de la Energía (CIUDEN). In order to detect leakage in the operational stage, a pre-injection geochemical baseline is presently being developed. In this work a geochemical monitoring design is presented to provide information about the feasibility of CO2 storage at depth.

Gas monitoring methodology and application to CCS projects as defined by atmospheric and remote sensing survey in the natural analogue of Campo de Calatrava

CO2 capture and storage (CCS) projects are presently developed to reduce the emission of anthropogenic CO2 into the atmosphere. CCS technologies are expected to account for the 20% of the CO2 reduction by 2050. Geophysical, ground deformation and geochemical monitoring have been carried out to detect potential leakage, and, in the event that this occurs, identify and quantify it. This monitoring needs to be developed prior, during and after the injection stage. For a correct interpretation and quantification of the leakage, it is essential to establish a pre-injection characterization (baseline) of the area affected by the CO2 storage at reservoir level as well as at shallow depth, surface and atmosphere, via soil gas measurements. Therefore, the methodological approach is important because it can affect the spatial and temporal variability of this flux and even jeopardize the total value of CO2 in a given area. In this sense, measurements of CO2 flux were done using portable infrared analyzers (i.e., accumulation chambers) adapted to monitoring the geological storage of CO2, and other measurements of trace gases, e.g. radon isotopes and remote sensing imagery were tested in the natural analogue of Campo de Calatrava (Ciudad Real, Spain) with the aim to apply in CO2 leakage detection; thus, observing a high correlation between CO2 and radon (r=0,858) and detecting some vegetation indices that may be successfully applied for the leakage detection.

Atmospheric and remote sensing surveys evaluated at the natural analogue "Campo de Calatrava" and its relation with isotopic Radon activity and CO2 flux as strategy for CCS projects

C0 capture and storage (CCS) projects are presently developed to reduce the emission of anthropogenic co2 into the atmosphere. CCS technologies are expected to account for the 20% of the C0 reduction by 2050.The results of this paper are referred to the OXYCFB300 Compostilla Project (European Energy Program for Recover). Since the detection and control of potential leakage from storage formation is mandatory in a project of capture and geological storage of C02 (CCS), geophysical , ground deformation and geochemical monitoring have been carried out to detect potentialleakage, and, in the event that this occurs, identify and quantify it. This monitoring needs to be developed prior, during and after the injection stage. For a correct interpretation and quantification of the leakage, it is essential to establish a pre-injection characterization (baseline)of the area affected by the C02 storage at reservoir level as well as at shallow depth, surface and atmosphere, via soil gas measurements.

In-situ infrared spectroscopy as a non-invasive technique to study carbon sequestration at high pressure and high temperature

We would like to thank EPSRC for a Doctoral Training Grant (G.A.M) and the Erasmus programme for supporting the study visit to Turin (R.W). We would also like to thank Dr. Federico Cesano for SEM/EDX measurements and for fruitful discussion. Dr. Jo Duncan is thanked for his tremendous insight during XRD interpretation.

Captura e armazenamento de CO2

Dissertação para obtenção do Grau de Mestre em Energia e Bioenergia

HIV-1 capture and transmission by dendritic cells: the role of viral glycolipids and the cellular receptor Siglec-1.

Dendritic cells (DCs) are essential in order to combat invading viruses and trigger antiviral responses. Paradoxically, in the case of HIV-1, DCs might contribute to viral pathogenesis through trans-infection, a mechanism that promotes viral capture and transmission to target cells, especially after DC maturation. In this review, we highlight recent evidence identifying sialyllactose-containing gangliosides in the viral membrane and the cellular lectin Siglec-1 as critical determinants for HIV-1 capture and storage by mature DCs and for DC-mediated trans-infection of T cells. In contrast, DC-SIGN, long considered to be the main receptor for DC capture of HIV-1, plays a minor role in mature DC-mediated HIV-1 capture and trans-infection.

HIV-1 Capture and Transmission by Dendritic Cells: The Role of Viral Glycolipids and the Cellular Receptor Siglec-1

Dendritic cells (DCs) are essential in order to combat invading viruses and trigger antiviral responses. Paradoxically, in the case of HIV-1, DCs might contribute to viral pathogenesis through trans-infection, a mechanism that promotes viral capture and transmission to target cells, especially after DC maturation. In this review, we highlight recent evidence identifying sialyllactosecontaining gangliosides in the viral membrane and the cellular lectin Siglec-1 as critical determinants for HIV-1 capture and storage by mature DCs and for DC-mediated trans-infection of T cells. In contrast, DC-SIGN, long considered to be the main receptor for DC capture of HIV-1, plays a minor role in mature DC-mediated HIV-1 capture and trans-infection.

Carbonation of Mg(OH)2 in a pressurised fluidised bed for CO2 sequestration

I takt med den ekonomiska tillväxten har CO2-utsläppen till atmosfären ständigt ökat, och utan kraftiga åtgärder kommer de att fortsätta att öka i allt snabbare takt. Konsekvenserna av en påtagligt förhöjd atmosfärisk CO2-halt är fortfarande osäkra (men eventuellt katastrofala) och fenomenet går under namnet global uppvärmning eller klimatförändring. CCS från engelskans ”carbon dioxide capture and storage” framstår som ett alternativ för att bekämpa de ständigt ökande CO2-utsläppen. Ett av de mer intressanta, och för Finlands del ända CCS-alternativet, baserar sig på naturens egna sätt att begränsa atmosfärisk CO2, nämligen vittring. Naturlig vittring, som förenklat innefattar nedbrytningen av sten/berg (även känd som erosion) och de därpå följande reaktionerna med CO2-mättat regnvatten. Slutresultatet är en utfällning av fasta mineraler som nu bundit CO2 i form av kalcium- och magnesiumkarbonat. Kalciumkarbonat är även bättre känt som kalksten, d.v.s. CO2 blir bundet i sten. Det gäller dock att snabba upp denna process, som i naturen är ytterst långsam, på ett ekonomiskt och miljömässigt hållbart sätt. Hittills har ett antal metoder för att påskynda naturlig vittring, eller med andra ord öka CO2-upptagningsförmågan av olika mineraler föreslagits. De mera etablerade uttrycken (lånade från engelskan) talar om mineralkarbonatisering och CO2-mineralisering. Till skillnad från många andra CO2-mineraliseringsalternativ är det alternativ som behandlas i denna avhandling i hög grad baserat på möjligheten att utnyttja den värme som frigörs vid karbonatisering. I teorin är det möjligt att föreställa sig en mineraliseringsprocess som inte kräver extern energi, men tillsvidare har man dock inte lyckats uppnå detta mål. Den process som presenteras i denna avhandling går ut på att man utvinner magnesium ur i naturen vanligt förekommande magnesiumrika mineraler, konverterar det till magnesiumhydroxid och därefter karbonatiserar det till magnesiumkarbonat. I rätta förhållanden kan magnesiumhydroxid reagera med CO2 mycket snabbt och i nuläget har processen potential att minska CO2-utsläppen från industri där spillvärme finns till förfogande (t.ex. cement- och stålindustrin). Fortsatt forskning är dock ett måste för att kunna påverka CO2-utsläppen i en globalt signifikant skala.

Analysis and modelling of chemical looping combustion process with and without oxygen uncoupling

Effective control and limiting of carbon dioxide (CO₂) emissions in energy production are major challenges of science today. Current research activities include the development of new low-cost carbon capture technologies, and among the proposed concepts, chemical combustion (CLC) and chemical looping with oxygen uncoupling (CLOU) have attracted significant attention allowing intrinsic separation of pure CO₂ from a hydrocarbon fuel combustion process with a comparatively small energy penalty. Both CLC and CLOU utilize the well-established fluidized bed technology, but several technical challenges need to be overcome in order to commercialize the processes. Therefore, development of proper modelling and simulation tools is essential for the design, optimization, and scale-up of chemical looping-based combustion systems. The main objective of this work was to analyze the technological feasibility of CLC and CLOU processes at different scales using a computational modelling approach. A onedimensional fluidized bed model frame was constructed and applied for simulations of CLC and CLOU systems consisting of interconnected fluidized bed reactors. The model is based on the conservation of mass and energy, and semi-empirical correlations are used to describe the hydrodynamics, chemical reactions, and transfer of heat in the reactors. Another objective was to evaluate the viability of chemical looping-based energy production, and a flow sheet model representing a CLC-integrated steam power plant was developed. The 1D model frame was succesfully validated based on the operation of a 150 kWth laboratory-sized CLC unit fed by methane. By following certain scale-up criteria, a conceptual design for a CLC reactor system at a pre-commercial scale of 100 MWth was created, after which the validated model was used to predict the performance of the system. As a result, further understanding of the parameters affecting the operation of a large-scale CLC process was acquired, which will be useful for the practical design work in the future. The integration of the reactor system and steam turbine cycle for power production was studied resulting in a suggested plant layout including a CLC boiler system, a simple heat recovery setup, and an integrated steam cycle with a three pressure level steam turbine. Possible operational regions of a CLOU reactor system fed by bituminous coal were determined via mass, energy, and exergy balance analysis. Finally, the 1D fluidized bed model was modified suitable for CLOU, and the performance of a hypothetical 500 MWth CLOU fuel reactor was evaluated by extensive case simulations.