The thesis focuses on CCS and CCU technologies, which could find application in industry and other sectors in the future. These technologies are used to reduce CO2 emissions, mainly from point sources. This thesis provides a comprehensive overview and division of CCS and CCU technologies and points out negative effects of its installation. Part of the work is also a comparison of individual steps of technology, both from an energetic and financial point of view. The aim is to show a wide range of influences on the final price and a significant discrepancy in the results of some scientific works. At the same time, in some parts, you can find a detailed description of individual parts of the technology.

ABSTRACT Modeling Diffusion and Buoyancy-Driven Convection with Application to Geological CO2 Storage Rebecca Allen Geological CO2 storage is an engineering feat that has been undertaken around the world for more than two decades, thus accurate modeling of flow and transport behavior is of practical importance. Diffusive and convective transport are relevant processes for buoyancy-driven convection of CO2 into underlying fluid, a scenario that has received the attention of numerous modeling studies. While most studies focus on Darcy-scale modeling of this scenario, relatively little work exists at the pore-scale. In this work, properties evaluated at the pore-scale are used to investigate the transport behavior modeled at the Darcy-scale. We compute permeability and two different forms of tortuosity, namely hydraulic and diffusive. By generating various pore ge- ometries, we find hydraulic and diffusive tortuosity can be quantitatively different in the same pore geometry by up to a factor of ten. As such, we emphasize that these tortuosities should not be used interchangeably. We find pore geometries that are characterized by anisotropic permeability can also exhibit anisotropic diffusive tortuosity. This finding has important implications for buoyancy-driven convection modeling; when representing the geological formation with an anisotropic permeabil- ity, it is more realistic to also account for an anisotropic diffusivity. By implementing a non-dimensional model that includes both a vertically and horizontally orientated 5 Rayleigh number, we interpret our findings according to the combined effect of the anisotropy from permeability and diffusive tortuosity. In particular, we observe the Rayleigh ratio may either dampen or enhance the diffusing front, and our simulation data is used to express the time of convective onset as a function of the Rayleigh ratio. Also, we implement a lattice Boltzmann model for thermal convective flows, which we treat as an analog for CO2 storage modeling. Our model contains the multiple- relaxation-time scheme and moment-based boundary conditions to avoid the numer- ical slip error that is associated with standard bounce-back. The model’s accuracy and robustness is demonstrated by an excellent agreement between our results and benchmark data for thermal flows ranging from Ra = 103 to 108. Our thermal model captures analogous flow behavior to that of CO2 through fluid-filled porous media, including the transition from diffusive transport to initiation and development of convective fingering.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18570号 / 工博第3931号 / 新制||工||1604(附属図書館) / 31470 / 京都大学大学院工学研究科都市社会工学専攻 / (主査)教授 松岡 俊文, 教授 小池 克明, 准教授 岸田 潔 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Tracertests stellen heute einen integralen Bestandteil im Repertoire der hydro(geo)logischen Charakterisierungstechniken dar. Insbesondere konservative Stoffe werden zur Bestimmung von hydraulischen Reservoir- und Aquiferparametern eingesetzt. Diese Stoffe verhalten sich weitestgehend inert und unterliegen somit nur vernachlässigbaren physikochemischen Wechselwirkungen während ihrer Verweilzeit im untersuchten Geosystem. Im Gegensatz dazu stellt der Einsatz nicht-konservativer organischer Stoffe als Tracer einen relativ neuen Ansatz dar, welcher das Potential birgt, zusätzliche Informationen zu ablaufenden Untergrundprozessen zu gewinnen, sofern die Wechselwirkungsarten und somit das Tracerverhalten bekannt sind. Folglich ist die genaue Kenntnis potentieller Transportprozesse und deren Abhängigkeiten eine unabdingbare Voraussetzung für eine erfolgreiche Interpretation dieser Tracer. In diesem Zusammenhang ist die Sorption an Festphasen für zahlreiche gelöste organische Verbindungen der wohl bedeutendste physikochemische Transportprozess. Aus diesem Grund ist die systematische Untersuchung von Sorptionsprozessen und deren Abhängigkeiten von den Moleküleigenschaften bzw. Randbedingungen ein Hauptbestandteil der hier vorgestellten, kumulativen Dissertationsschrift. Die aus den Sorptions-untersuchungen abgeleiteten Schlussfolgerungen wurden in die Entwicklung eines neuen, reaktiven Reservoir-Tracers für die geologische Speicherung von CO2 mit einbezogen. Um einen Überblick über das Sorptionsverhalten organischer Verbindungen mit unterschiedlichen Funktionalitäten zu gewinnen, wurde zunächst der pH-abhängige Stofftransport mehrerer dissoziierbarer Arzneimittelwirkstoffe (Säuren, Basen, Zwitter) mit Hilfe von Sedimentsäulenexperimenten untersucht. Hierzu wurden die Sorptionskoeffizienten bestimmt und mit den vorausberechneten Ergebnissen zweier Korrelationsansätze verglichen. Eine starke pH-Abhängigkeit zeigte die Sorption für alle Moleküle mit einem pKS-Wert im oder nahe des untersuchten pH-Bereiches. Eine zufriedenstellende Vorhersage war nur für neutrale und anionsche (saure) Verbindungen möglich. Im Gegensatz dazu war die Sorption der kationischen (basischen) und zwitter-ionischen Verbindungen stärker als erwartet. Als Ursache dafür kann das Auftreten zusätzlicher, elektrostatischer Sorptionsmechanismen angesehen werden, welche in den konventionellen Korrelationsansätzen nicht berücksichtigt werden. Somit konnte unter anderem erwartet werden, dass auch Kationenaustausch einen signifikanten Prozess für die Retardation organischer Kationen im Untergrund darstellt. Mit zwei kationischen Beta-Blockern durchgeführte Säulenversuche belegen die dominierende Rolle von Kationenaustauschprozessen. Steigende Konzentrationen anorganischer Kationen führen aufgrund der verstärkten Konkurrenz um die Austauscherplätze des Sorbens zu einer geringeren Sorption der organischen Kationen. Der Beitrag nicht-hydrophober Wechselwirkungen zur Gesamtsorption konnte mit >99% abgeschätzt werden. Aufgrund der großen Bedeutung von Kationenaustauschprozessen sollten weitere Einflussfaktoren berücksichtigt werden, um den Transport organischer Kationen zuverlässig vorhersagen zu können. Daher wurde anschließend der Einfluss konkurrierender anorganischer Kationen auf die Sorption organischer Kationen in Wasser/Sediment-Batchtests systematisch untersucht. Die bei verschiedenen Hintergrundkonzentrationen an anorganischen Kationen aufgenommenen Sorptionsisothermen des kationischen Beta-Blockers Metoprolol zeigten eine deutlich stärkere Beeinflussung der Sorption durch Ca2+ als durch Na+. Durch die gefundene Korrelation zwischen dem Freundlich-Koeffizienten und der Konzentration anorganischer Kationen wird eine Vorhersage der Metoprolol-Sorption im Bereich der untersuchten Randbedingungen möglich. Zudem konnte der Beitrag sorptiver Wechselwirkungen zum organischen Kohlenstoff des Sediments als vernachlässigbar bestimmt werden. Insgesamt liefern die erzielten Ergebnisse einen weiteren wichtigen Beitrag zur Prozessbeschreibung der Sorption und helfen somit, die Vorhersage des Stofftransportes organischer Kationen im Untergrund zu verbessern. Im letzten Teil der Arbeit werden das Konzept und die Entwicklung eines neuen, reaktiven Tracers (KIS-Tracer) zur Charakterisierung von Grenzflächen während Injektionen von überkritischem CO2 in tiefe salinare Aquifere beschrieben. Durch eine Hydrolysereaktion an der CO2/Wasser-Grenzfläche mit bekannter Kinetik wird ein Zusammenhang zur zeitlichen Änderung der Grenzflächengröße geschaffen. Basierend auf den vorangegangenen Untersuchungen zur Sorption, wurde das konservative, organische Anion Naphthalinsulfonat als Basisstruktur für die Tracersynthese (Veresterung) und somit auch als gewünschtes Hydrolyseprodukt ausgewählt. Neben der Definition notwendiger Tracereigenschaften wurden bereits erste Verbindungen synthetisiert, im Labor getestet und mit einem neuentwickelten, makroskopischen Modell ausgewertet. Abschließend wurde das Tracerverhalten exemplarisch für verschiedene hypothetische Funktionen der zeitlichen Grenzflächenänderung numerisch modelliert. Die bisher erzielten Ergebnisse sind sehr vielversprechend und gewähren einen ersten Einblick in das Potential von KIS-Tracern.

A reactive transport model is proposed to simulate the reactivity of cement based material in contact with CO2-saturated brine and supercritical CO2 (scCO2) under CO2 geological storage conditions. This code is developed to solve simultaneously transport and chemistry by a global coupled approach, considering the effect of temperature and pressure. The variability of scCO2 properties with pressure and temperature, such as solubility in water, density and viscosity are taken into account. It is assumed that all chemical processes are in thermodynamical equilibrium. Dissolution and precipitation reactions for portlandite (CH) and calcite (CC) are described by mass action laws and threshold of ion activity products in order to account for complete dissolved minerals. A chemical kinetics for the dissolution and precipitation of CH and CC is introduced to facilitate numerical convergence. One properly chosen variable is able to capture the precipitation and dissolution of the relevant phase. A generalization of the mass action law is developed and applied to calcium silicate hydrates (C-S-H) to take into account the continuous variation (decrease) of the Ca/Si ratio during the dissolution reaction of C-S-H. The changes in porosity and microstructure induced by the precipitation and dissolution reactions are also taken into account. Couplings between transport equations and chemical reactions are treated thanks to five mass balance equations written for each atom (Ca, Si, C, K, Cl) as well as one equation for charge balance and one for the total mass. Ion transport is described by using the Nernst-Plank equation as well as advection, while gas and liquid mass flows are governed by advection. Effect of the microstructure and saturation change during carbonation to transport properties is also considered. The model is implemented within a finite-volume code, Bil. Principles of this method and modeling approach are discussed and illustrated with the help of a simple example. This model, with all the efforts above, is able to simulate the carbonation processes for cement based materials, at both saturated and unsaturated conditions, in a wide CO2 concentration, temperature and pressure range. Several sets of experiments, including sandstone-like conditions, limestone-like conditions, supercritical CO2 boundary and unsaturated conditions reported in the literature are simulated. Good predictions are provided by the code when compared with experimental observations. Some experimental observed phenomena are also explained by the model in terms of calcite precipitation front, CH dissolution front, porosity profile, etc

Un modèle de transport réactif est proposé pour simuler la réactivité des matériaux à base de ciment en contact avec une saumure saturée en CO2 et/ou le CO2 supercritique (CO2sc) dans les conditions de stockage géologique du CO2. Un code a été développé pour résoudre simultanément le transport et la chimie par une approche globale couplée, compte tenu de l'effet de la température et de la pression. La variabilité des propriétés du CO2sc avec la pression et la température, telles que la solubilité dans l'eau, la densité et la viscosité sont pris en compte. On suppose que tous les processus chimiques sont en équilibre thermodynamique. Les réactions de dissolution et de précipitation de la portlandite (CH) et de calcite (CC) sont décrites par des lois d'action de masse et des seuils de produit d'activité ioniques. Une cinétique de dissolution de CH est introduite pour faciliter la convergence numérique. La définition d'une variable principale permet de capturer la précipitation et la dissolution des phases solides à base de calcium. Une généralisation de la loi d'action de masse est développée et appliquée aux silicates de calcium hydratés (CSH) pour tenir compte de la variation continue (diminution) du rapport Ca/Si au cours de la dissolution des CSH. Les variations de porosité et de la microstructure induites par les réactions de précipitation et de dissolution sont également prises en compte. Le couplage entre le transport et la chimie est modélisé par cinq équations de bilan de masse écrites pour chaque atome (Ca, Si, C, K, Cl), ainsi que par une équation de conservation de la masse totale et celle de la charge électrique. Les lois de Darcy et de Nernst-Planck sont utilisées pour décrire le transport de masse et d'ions. Les propriétés de transport dépendent du degré de saturation et de la porosité. Le modèle est implémenté dans le code de volumes finis, Bil. Les principes de cette méthode et l'approche de modélisation sont discutés et illustrés sur un exemple simple. Ce modèle est en mesure de simuler les processus de carbonatation des matériaux à base de ciment, dans des conditions à la fois saturés et insaturés, dans une large plage de concentration de CO2, de température et de pression. Plusieurs expériences, rapportées dans la littérature, sont simulées en utilisant divers types de conditions aux limites: (i) solutions saturées ou non en CO2 et carbonate de calcium, (ii) gas supercritique de CO2. Les prédictions sont comparées avec les observations expérimentales. Certains phénomènes observés expérimentalement peuvent être également expliqués par le modèle / A reactive transport model is proposed to simulate the reactivity of cement based material in contact with CO2-saturated brine and supercritical CO2 (scCO2) under CO2 geological storage conditions. This code is developed to solve simultaneously transport and chemistry by a global coupled approach, considering the effect of temperature and pressure. The variability of scCO2 properties with pressure and temperature, such as solubility in water, density and viscosity are taken into account. It is assumed that all chemical processes are in thermodynamical equilibrium. Dissolution and precipitation reactions for portlandite (CH) and calcite (CC) are described by mass action laws and threshold of ion activity products in order to account for complete dissolved minerals. A chemical kinetics for the dissolution and precipitation of CH and CC is introduced to facilitate numerical convergence. One properly chosen variable is able to capture the precipitation and dissolution of the relevant phase. A generalization of the mass action law is developed and applied to calcium silicate hydrates (C-S-H) to take into account the continuous variation (decrease) of the Ca/Si ratio during the dissolution reaction of C-S-H. The changes in porosity and microstructure induced by the precipitation and dissolution reactions are also taken into account. Couplings between transport equations and chemical reactions are treated thanks to five mass balance equations written for each atom (Ca, Si, C, K, Cl) as well as one equation for charge balance and one for the total mass. Ion transport is described by using the Nernst-Plank equation as well as advection, while gas and liquid mass flows are governed by advection. Effect of the microstructure and saturation change during carbonation to transport properties is also considered. The model is implemented within a finite-volume code, Bil. Principles of this method and modeling approach are discussed and illustrated with the help of a simple example. This model, with all the efforts above, is able to simulate the carbonation processes for cement based materials, at both saturated and unsaturated conditions, in a wide CO2 concentration, temperature and pressure range. Several sets of experiments, including sandstone-like conditions, limestone-like conditions, supercritical CO2 boundary and unsaturated conditions reported in the literature are simulated. Good predictions are provided by the code when compared with experimental observations. Some experimental observed phenomena are also explained by the model in terms of calcite precipitation front, CH dissolution front, porosity profile, etc

Le stockage géologique du carbone dans les veines de charbon est une solution transitoire pour lutter contre le réchauffement climatique. La faisabilité de ce stockage à un coût abordable reste incertaine, en particulier parce que l'injection de dioxide de carbone dans les veines de charbon est lente. Les projets pilotes ont montré que la perméabilité du réservoir diminue lors de l'injection, suite au gonflement du charbon induit par l'adsorption préférentielle du dioxyde de carbone par rapport au méthane présent naturellement. Ce mémoire de thèse est consacré à l'étude de ce gonflement. Un premier travail théorique a consisté à étendre les équations constitutives de poromécanique classique dans les cas où l'adsorption sur des surfaces ou dans des micropores devient significative. Nous avons montré que le comportement poromécanique du solide ne peut être compris que si la dépendance de l'adsorption en fonction de la déformation du milieu poreux est connue. Le couplage entre adsorption et déformation est peu étudié dans la littérature et difficile à mesurer expérimentalement. Dans ce travail, nous avons utilisé la simulation moléculaire qui permet facilement de contrôler indépendamment la pression du fluide adsorbé et la déformation du milieu poreux. A l'aide de simulations moléculaires d'adsorption dans des systèmes modèles unidimensionnels, nous avons validé les nouvelles équations consitutives. Nous avons montré également que l'adsorption peut dépendre de la déformation de façon complexe et qu'elle est très sensible à la structure des micropores. Les résultats de simulations moléculaires d'adsorption dans un modèle moléculaire réaliste de la matrice organique du charbon nous ont permis de montrer que le gonflement du charbon en présence de fluide peut être expliqué par l'adsorption dans les micropores, mais pas dans les mésopores. Nous avons étudié numériquement le couplage entre adsorption et déformation dans le charbon. Le gonflement estimé en associant les simulations moléculaires d'adsorption aux nouvelles équations constitutives de poromécaniques est en bon accord avec les mesures expérimentales. De même, nous avons simulé l'adsorption de mélanges de dioxide de carbone et de méthane dans le charbon à des températures et pressions représentatives des conditions souterraines. Le résultat de ces simulations a permis d'estimer le gonflement différentiel durant l'injection de carbone pour des veines de charbon à différentes profondeurs. / Pas de résumé en anglais

Geologic storage of anthropogenic carbon dioxide (CO2) by injection into underground porous sandstone reservoirs has been proposed as a method for the reduction of anthropogenic greenhouse gas emissions. Upwards migration and leakage of injected fluids along natural fault and fracture networks is a key risk factor for potential injection locations. We examine exposed natural analogs to evaluate the impacts of faulting and fracturing on reservoir and top-seal pairs and to evaluate evidence for paleomigration of fluids along the fault zone. We examine the Iron Wash fault, a 25-km long normal fault which cuts Jurassic sedimentary rocks and has throws that range from 20-120 m, to examine how a fault may affect seal integrity. Field mapping, kinematic analysis, petrographic analysis, characterization of the fault zone facies and fault architecture, analysis of altered and mineralized rocks in and around the fault zone, and modeling of fault seal capacity was conducted to provide an understanding of the Iron Wash fault zone. Field data and observations were combined with well log and borehole data to produce three types of models for the Iron Wash fault: 1) geometric model of the fault in the subsurface, 2) predictive models of fault zone behavior and fault seal analysis, and 3) predictive geomechanical models of the response of the fault zone to an imposed stress field and increasing the effective stress on the fault. We conclude that the Iron Wash fault zone has low sealing capacity and will likely not behave as a seal for fluids against the fault zone due primarily to modest throw on the fault and high frequency of fractures associated with the fault zone. Analysis of fluid alteration and mineralization around the fault zone indicates that the fault zone was conduit for paleo-fluids. We conclude that the fault is not likely to develop a sealing membrane and therefore will most likely fail as a seal to fluids moving through the reservoirs modeled here. Modeling results indicate that a reduction in the effective normal stress on fault surfaces may induce failure of faults resulting in earthquakes or increased hydraulic conductivity of fractures.

Australia’s economy is heavily dependent on coal-based energy and greenhouse gas intensive natural resource extraction and processing industries. As part of an international climate change mitigation effort Australia will have to undergo a national transformation to a low emissions society by mid century. Federal and State Governments in Australia, like their counterparts in other major developed economies, have been persuaded that reliance on fossil fuels in stationary energy industries such as electricity generation and minerals processing will be able to continue with the deployment of a value chain of technologies fitted to these installations for capturing carbon dioxide, transporting it to a disposal site, and then injecting it into subsurface geological formations for permanent storage (carbon capture and storage, or CCS). Understanding the likely effectiveness of CCS for reducing greenhouse gas emissions from stationary energy industries is therefore critical to policy formulation for, and management of, Australia’s emissions mitigation effort and national transformation over the decades ahead. / This thesis aims to offer a clearer understanding of the practicalities, limitations and uncertainties surrounding future CCS use in Australia and of the contribution CCS can make to mitigating emissions from the Australian stationary energy sector in the period to 2050. It considers two central questions: Is CCS a realistic option for emissions mitigation in Australia? Are Australian climate policies formulated to facilitate CCS deployment and optimise its potential contribution? The criteria employed in this thesis for answering these questions are restricted to those having an ascertainable causal impact on the timing, pace and ultimate scale of CCS deployment within Australia. The methodology used for the research is grounded in critical approaches and integrated assessment within a holistic, trans-disciplinary paradigm. / This thesis finds that under Australia’s existing climate policy framework it is unrealistic to expect CCS can contribute more than 75 million tonnes of CO2 per annum to emissions mitigation by 2050. Australia does have sufficient potential geological storage resources to expect some environmentally safe CCS infrastructure could be engineered over time, but commencement of large scale build-out is not likely before 2025. When CCS will become a commercial mitigation option in Australia is unpredictable and dependent more on the political economy of climate change than on Australian research, development and demonstration activities. / The thesis also finds that the existing climate policy framework is increasing rather than decreasing the risks to timing and usefulness of CCS even to the level of 75 million tonnes of CO2 per annum by 2050. This thesis concludes that Australian Governments are not developing the institutional capability to oversee a holistic decarbonisation of the stationary energy sector. This capability is required not only to address the risks to CCS deployment but also to prevent market failures that foreclose an optimal contribution from all other potential mitigation technologies. The thesis proposes that an Australian national CCS company be created with responsibility for CCS integration, transport and storage services in order to develop Australian capability rather than that of international corporations.

Recently, carbon dioxide injection into deep sea sediments has become one of the carbon dioxide mitigation methods since carbon dioxide hydrates are stable at the prevailing pressure and temperature conditions. The Black Sea, which is one of the major identified natural methane hydrate regions of the world, can be a good candidate for carbon dioxide storage in hydrate form. Injected carbon dioxide under the methane hydrate stability region will be in contact with methane hydrate which should be analyzed thoroughly in order to increase our understanding on the gaseous carbon dioxide and methane hydrate interaction. For the storage of huge amounts of CO2, geological structure must contain an impermeable barrier. In general such a barrier may consist of clay or salt. In this study, sealing efficiency of methane hydrate and long term fate of the CO2 disposal under the methane hydrate zone is investigated. In order to determine the interaction of CO2 and CH4 hydrate and the sealing efficiency of CH4 hydrate, experimental setup is prepared and various tests are performed including the CH4 hydrate formation in both bulk conditions and within sand particles, measurement of the permeability of unconsolidated sand particles that includes 30% and 50% methane hydrate saturations and injection of CO2 into the CH4 hydrate. Results of the experiments indicate that, presence of hydrate sharply decreases the permeability of the unconsolidated sand system and systems with hydrate saturations greater than 50% may act as an impermeable layer. Also, CO2-CH4 swap within the hydrate cages is observed at different experimental conditions. As a result of this study, it can be concluded that methane hydrate stability region in deep sea sediments would be a good alternative for the safe storage of CO2. Therefore, methane hydrate stability region in the Black Sea sediments can be considered for the disposal of CO2.