Att begränsa globala uppvärmningen till 1,5°C kommer kräva negativa koldioxidutsläpp. En metod för att generera negativa koldioxidutsläpp är så kallad Bio-Energy Carbon Capture and Storage (BECCS). En direkt implementering av BECCS är att fånga in CO2 från rökgas som genereras vid förbränning av biomassa i en så kallad post-combustion capture-konfigurering. Post-combustion BECCS har skapat en stor resonans hos kraftverksoperatörer och pappersproducenter. Stockholm Exergi, som ägs av Fortum och Stockholms Stad, siktar på att fånga in upp till 800 kt CO2 per år från deras biomass-eldade CHP-anläggning i Värtaverket vid 2024. Planen är att fånga in CO2 från rökgasen genom en absorptionsprocess och sedan skeppa det till Norge för geologisk förvaring. Mastersexamensarbetet följde en experimentskampanj driven av Stockholm Exergi som siktade på att uppnå experimentell validering av en absorptionsprocess för koldioxidinfångning från rökgas vid förbränning av biomassa. En testenhet konstruerades och tester genomfördes från december 2019 till maj 2020. Examensarbetet fokuserade på rollen absorptionsmedlet hade på infångningshastigheten. Tester med tre olika lösningsmedel genomfördes och de experimentella resultaten analyserades genom en kombination av jämviktsmodeller och Murphree-effektiviteter. Resultatet visar att ett absorptionsmedel baserat på vattenlöslig K2CO3 är kompatibel med rökgas från förbränning av biomassa, eftersom infångningshastigheter mellan 5 och 13 % uppmättes. De undersökta hastighetspromotorerna (3 vikt% H3BO3 + 1 vikt% V2O5) visade dock inte den förväntade effekten på infångningshastigheter, och på grund av tidsbegränsningar testades inte olika vikt% av promotorn under det här examensarbetet. Ingen tydlig slutsats drogs därför med hänsyn till promotorer. Baserat på Murphree-effektiviteterna som beräknats genom experimenten med konstant förhållande mellan vätske- och gasflöde uppskattas en 28–35 m hög kolonn fånga 90% av CO2 i rökgasen. / Limiting global warming to 1.5°C will require negative carbon emissions. One way for generating negative carbon emissions is through bio-energy carbon capture and storage (BECCS). A direct implementation of BECCS is to capture CO2 from the flue gas originating from the combustion of biomass in a post-combustion capture configuration. Post-combustion BECCS has generated considerable resonance among power plant operators and paper manufactures. Stockholm Exergi, owned by Fortum and Stockholm Stad, aims at capturing up to 800 kt CO2 per year from their biomass-fired CHP plant in Värtaverket by 2024. The plan foresees to capture CO2 from the flue gas utilizing an absorption process and shipment of the captured CO2 to Norway for geological storage. The Master thesis project followed an experimental campaign run by Stockholm Exergi that aimed at experimental validation of an absorption process for carbon capture from flue gas originating from the combustion of biomass. A test unit was constructed, and test trials were run from Dec. 2019 to May 2020. The thesis focused on the role of the absorption solvent on the capture rate. Test trails with three different solvents were conducted, and the experimental results were analyzed using equilibrium models combined with Murphree efficiencies. The results show that an absorption solvent based on aqueous K2CO3 is compatible with the flue gas derived from biomass combustion, i.e., capture rates ranging from 5 to 13 % were measured. However, the investigated rate promoters (3 wt.% H3BO3 + 1 wt.% V2O5) did not show the expected effect with regards to capture rates and due to time constrain different wt.% of the promoter were not tested within the scope of this thesis. Therefore, no firm conclusion was given with regards to promoters. Based on the Murphree efficiency calculated from the experiment with keeping a constant liquid to gas flow ratio, a column height of 28-35 m is estimated to capture 90% of CO2 from the flue gas.

Im Rahmen dieser Doktorarbeit wurden die Hangkarbonate von zwei miozänen heterozoischen Karbonatsystemen näher untersucht: die Malta Inselgruppe (zentrales Mittelmeer) und das Marion Plateau (Nordost Australien, ODP Leg 194). Die Auswirkungen der mittelmiozänen Abkühlung (Mi3), die auf 13.6 Ma datiert wird und starken Einfluß auf die Sauerstoffisotopenkurve hatte, in den oben genannten Flachwassersystemen stellten das Ziel dieser Arbeit dar. Dieses Abkühlungsereignis beeinflußte außerdem sehr stark die ozeanographischen und klimatischen Muster, die im weiteren Verlauf zum modernen Eishausklima führten. So steht insbesondere die Vereisung von Ostantarktika mit diesem Ereignis in Verbindung. Diese Arbeit untersucht den Einfluß dieses Ereignisses auf Flachwassersysteme, um vorliegende Untersuchungen in Tiefwassersystemen zu ergänzen und so zum globalen Verständnis des miozänen Klimawechsels beizutragen.<br /> <br /> Die Profile auf der Maltainselgruppe wurden mit Hilfe von Kohlenstoff- und Sauerstoffisotopen Auswertungen im Gesamtgestein, Gesamtgesteinmineralogie, Tonmineralanalyse und organischer Geochemie untersucht. Durch einen Wechsel von karbonatischeren zu tonigeren Sedimenten beeinflußte das mittelmiozäne Abkühlungsereignis die Sedimentation in diesem Gebiet sehr stark. Weiterhin wurde beobachtet, daß jede Phase der antarktischen Vereisung, nicht nur das mittelmiozäne Hauptereignis, zu einem erhöhten terrigenen Eintrag in den Hangsedimenten der Maltainselgruppe führte. Akkumulationsraten zeigen, daß dieser erhöhte terrigene Eintrag den einzelnen Vereisungsperioden zusammenhängt und die karbonatischen Sedimente durch tonreiche Sedimente &ldquo;verunreinigt&rdquo; wurden. Das daraufhin entwickelte Modell erklärt diesen erhöhten terrigenen Eintrag mit einer nordwärtigen Verlagerung der innertropischen Konvergenzzone durch die Bildung von kalten, dichten Luftmassen, die zu verstärkten Niederschlägen in Nordafrika führten. Diese verstärkten Niederschläge (oder verstärkter afrikanischer Monsun) beeinflußten die kontinentale Verwitterung und den Eintrag, mit der Folge, daß verstärkt terrigene Sedimente im Bereich der Hangsedimente der Maltainselgruppe abgelagert wurden. Die tonreichen Intervalle weisen Ähnlichkeiten zu sapropelischen Ablagerungen auf, was mit Hilfe der Spektral analyse des Karbonatgehalts und der geochemischen Analyse des organischen Materials gezeigt wurde. <br /> <br /> Auf dem Marion Plateau wurden die Sauerstoff- und Kohlenstoffisotopenkurven anhand von Foraminiferen der Gattung Cibicidoides spp. rekonstruiert. Der Karbonatgehalt wurde mit Hilfe einer chemischen Methode (Coulometer) ermittelt. Genauso wie die Sedimente der Maltainselgruppe beeinflußte das mittelmiozäne Abkühlungsereignis (Mi3) auch die Sedimente auf dem Marion Plateau. So kam es bei 13,8 Ma, in etwa zur Zeit der Vereisung von Ostantarktika, zu einem Abfall der Karbonatakkumulationsraten. Weiterhin traten Änderungen in der Zusammensetzung der Sedimente auf, so nehmen neritische Karbonatfragmente ab, der planktische Foraminiferengehalt nimmt zu und es wurden verstärkt Quarz und Glaukonit abgelagert. Ein überraschendes Ergebnis ist die Tatsache, daß der große N12-N14 Meeresspiegelabfall um 11,5 Ma die Akkumulationsraten der Karbonate auf dem Hang nicht beeinflußte. Dieses Ergebnis ist umso erstaunlicher, da Karbonatplattformen normalerweise sehr sensitiv auf Meeresspiegeländerungen reagieren. Der Grund, warum sich die Karbonatakkumulationsraten schon um 13,6 Ma (Mi3) und nicht erst um 11,5 Ma (N12-N14) verringerten, liegt in der Tatsache, daß die ozeanischen Strömungen die Karbonatsedimentation auf dem Hang des Marion Plateau schon im Miozän kontrollierten. Das mittelmiozäne Ereignis (Mi3) erhöhte die Stärke diese Strömungen und als eine Ursache wurde die Karbonatakkumulation auf den Hängen reduziert. Die Amplitude des N12-N14 Meeresspiegelabfalls liegt bei 90 m unter der Berücksichtigung der Sauerstoffisotopendaten aus der Tiefsee und Berechnungen des Meeresspiegels anhand des &ldquo;coastal onlaps&rdquo;, die während Leg 194 gemacht wurden. Die Isotopendaten dieser Arbeit weisen hingegen auf einen verringerten Meeresspiegelabfall von 70 m hin.<br /> <br /> Als allgemeine Schlußfolgerung kann gesagt werden, daß der mittelmiozäne Klimaumschwung die Karbonatsysteme zumindest an den beiden untersuchten Lokalitäten beeinflußt hat. Allerdings waren die Auswirkungen sehr von den unterschiedlichen lokalen Gegebenheiten abhängig. Insbesondere wirkten sich die Anwesenheit einer Landmasse (Malta) und die Abwesenheit einer Barriere vor den Einflüssen des offenen Ozeans (Marion Plateau) stark auf die Ablagerung der Karbonate aus. / This study investigated the slope carbonates of two Miocene carbonate systems: the Maltese Islands (in the Central Mediterranean) and the Marion Plateau (Northeastern Australia, drilled during ODP Leg 194). The aim of the study was to trace the impact of the Miocene cooling steps (events Mi1-Mi6) in these carbonate systems, especially the Mi3 event, which took place around 13.6 Ma and deeply impacted the marine oxygen isotope record. This event also profoundly impacted oceanographic and climatic patterns, eventually leading to the establishment of the modern ice-house world. In particular, East Antarctica became ice covered at that period. The rational behind the present study was to investigate the impact that this event had on shallow water systems in order to complement the deep-sea record and hence acquire a more global perspective on Miocene climate change.<br /> <br /> The Maltese Islands were investigated for trends in bulk-rock carbon and oxygen isotopes, as well as bulk-rock mineralogy, clay minerals analysis and organic geochemisty. Results showed that the mid Miocene cooling event deeply impacted sedimentation at that location by changing sedimentation from carbonate to clay-rich sediments. Moreover, it was discovered that each phase of Antarctic glaciation, not just the major mid Miocene event, resulted in higher terrigenous input on Malta. Mass accumulation rates revealed that this was linked to increased runoff during periods when Antarctica was glaciated, and thus that the carbonate sediments were &ldquo;diluted&rdquo; by clay-rich sediments. The model subsequently developed to explain this implies feedback from Antarctic glaciations creating cold, dense air masses that push the ITCZ Northward, thus increasing precipitation on the North African subcontinent. Increased precipitation (or stronger African monsoon) accelerated continental weathering and runoff, thus bringing more terrigenous sediment to the paleo-location of the slope sediments of Malta. Spectral analysis of carbonate content and organic matter geochemical analysis furthermore suggest that the clay-rich intervals are similar to sapropelic deposits.<br /> <br /> On the Marion Plateau, trends in oxygen and carbon isotopes were obtained by measuring Cibicidoides spp foraminifers. Moreover, carbonate content was reconstructed using a chemical method (coulometer). Results show that the mid Miocene cooling step profoundly affected this system: a major drop in accumulation rates of carbonates occurs precisely at 13.8 Ma, around the time of the East Antarctic ice sheet formation. Moreover, sedimentation changes occurred at that time, carbonate fragments coming from neritic environments becoming less abundant, planktonic foraminifer content increasing and quartz and reworked glauconite being deposited. Conversely, a surprising result is that the major N12-N14 sea-level fall occurring around 11.5 Ma did not impact the accumulation of carbonates on the slope. This was unexpected since carbonate platform are very sensitive to sea-level changes. The model developed to explain that mass accumulation rates of carbonates diminished around 13.6 Ma (Mi3 Event) instead of 11.5 Ma (N12-N14 event), suggests that oceanic currents were controlling slope carbonate deposition on the Marion Plateau prior to the mid-Miocene, and that the mid Miocene event considerably increase their strength, hence reducing the amount of carbonate being deposited on slope sites. Moreover, by combining results from deep-sea oxygen isotopes with sea-level estimates based on coastal onlaps made during Leg 194, we constrain the amplitude of the N12-N14 sea-level fall to 90 meters. When integrating isotopic results from this study, this amplitude is lowered to 70 meters.<br /> <br /> A general conclusion of this work is that the mid Miocene climatic shift did impact carbonate systems, at least at the two locations studied. However, the nature of this response was highly dependant on the regional settings, in particular the presence of land mass (Malta) and the absence of a barrier to shelter from the effects of open ocean (Marion Plateau).

The one of the most important Eras of the Earth history, i.e. Neoproterozoic (1000-542 Ma),<p>was an enigmatic period characterized by the development of the first stable long-lived ~1.1-<p>0.9 Ga Rodinia and 550-500 Ma Gondwana supercontinents, global-scale orogenic belts,<p>extreme climatic changes (cf. Snowball Earth Hypothesis), the development of microbial<p>organisms facilitating the oxidizing atmosphere and explosion of eukaryotic forms toward the<p>first animals in the terminal Proterozoic. This thesis presents a multidisciplinary study of two<p>Neoproterozoic basins, i.e. Bas-Congo and Sankuru-Mbuji-Mayi-Lomami-Lovoy, in and around the Congo Craton including sedimentology, geochemistry, diagenesis, chemostratigraphy and radiometric dating of carbonate deposits themselves.<p><p>The Mbuji-Mayi Supergroup sequence deposited in a SE-NW trending 1500 m-thick siliciclastic-carbonate intracratonic failed-rift basin, extends from the northern Katanga Province towards the centre of the Congo River Basin. The 1000 m-thick carbonate succession is related to the evolution of a marine ramp submitted to evaporation, with ‘deep’ shaly basinal and low-energy carbonate outer-ramp environments, marine biohermal midramp (MF6) and ‘very shallow’ restricted tide-dominated lagoonal inner-ramp (MF7-MF9) settings overlain by lacustrine (MF10) and sabkha (MF11) environments, periodically<p>submitted to a river water source with a possible freshwater-influence. The sequence stratigraphy shows that the sedimentation is cyclic in the inner ramp with plurimetric ‘thin’ peritidal cycles (± 4 m on average) recording a relative sea level of a maximum of 4 m, with fluctuations in the range of 1-4 m. The outer/mid ramp subtidal facies are also cyclic with ‘thick’ subtidal cycles characterized by an average thickness of ± 17 m, with a probable sealevel<p>fluctuations around 10 to 20 m. The geochemistry approach, including isotopic and major/trace and REE+Y data, allows to infer the nature of the dolomitization processes operating in each carbonate subgroup, i.e dolomitization may be attributed to evaporative reflux of groundwater or to mixing zones of freshwater lenses. The latest alteration processes occured during the uplift of the SMLL Basin. New ages, including LA-ICP-MS U-Pb laser ablation data on detrital zircon grains retrieved in the lower arenaceous-pelitic sequence (BI group), combined with carbon and strontium isotopic analyses, yielded a new depositional time frame of the Mbuji-Mayi Supergroup between 1176 and 800 Ma reinforcing the formerly suggested correlation with the Roan Group in the Katanga Province.<p><p>In the Democratic Republic of Congo, the Sturtian-Marinoan interglacial period was previously related to pre-glacial carbonate-dominated shallow marine sedimentation of the Haut-Shiloango Subgroup with stromatolitic reefs at the transition between greenhouse (warm) and icehouse (cold) climate periods, commonly marked by worldwide glacigenic diamictites and cap carbonates. This thesis highlights that these deposists record as a deepening-upward evolution from storm-influenced facies in mid- and outer-ramps to deepwater environments, with emplacement of mass flow deposits in toe-of-slope settings controlled by synsedimentary faults. In absence of diagnostic glacial features, the marinoan Upper Diamictite Formation is interpreted as a continuous sediment gravity flow deposition along carbonate platform-margin slopes, which occurred along tectonically active continental margins locally influenced by altitude glaciers, developed after a rift–drift transition. The maximum depth of the deepening-upward facies is observed in the C2a member. The<p>shallowing-upward facies exibit a return of distally calcareous tempestites and semi-restricted to restricted peritidal carbonates associated with shallow lagoonal subtidal and intertidal zones submitted to detrital fluxes in the upper C2b to C3b members.<p>The geochemistry highlights (i) the existence of a δ13C-depth gradient of shallow-water and deep-water carbonates; (ii) the carbonate systems were deposited in oxic to suboxic conditions; and (iii) all samples have uniform flat non-marine shale-normalized REE+Y distributions reflecting<p>continental detrital inputs in nearshore environments, or that the nearshore sediments were<p>reworked from ’shallow’ inner to mid-ramp settings in deep-water slope and outer-ramp<p>environments, during the rift-drift transition in the basin. The pre-, syn- and post-glacial<p>carbonate systems could record a distally short-lived regional synrift freshwater-influenced<p>submarine fan derived from nearshore sediments, including gravity flow structures, which are<p>attributed to regional tectonic processes due to a sudden deepening of the basin caused by<p>differential tilting and uplifting of blocks, related to the 750-670 Ma oceanic spreading of the<p>central-southern Macaúbas Basin.<p><p>Combining sedimentology, isotopes and trace elemental geochemistry, the thesis highlights<p>that the δ13C variations in the Neoproterozoic carbonates are complex to interpret, and can be<p>related to: (i) the existence of a δ13C-depth gradient; (ii) the exchange between isotopically<p>light carbon in meteoric waters and carbonate during lithification and early diagenesis; and<p>(iii) isotopic perturbations due to regional metamorphism. Considering the possible englaciation of the Earth (Snowball Earth hypothesis), the Mbuji-Mayi Supergroup and West<p>Congolian Group seem reflected the intimate relationship between glaciations and tectonic<p>activity during the break-up of the Rodinia supercontinent, followed by the rift–drift<p>transition, and finally the pre-orogenic period on the passive continental margin. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished