Dissertations / Theses on the topic 'Carbon dioxide capture and storage'

Since 1996, super-critical CO$_2$ has been injected at a rate of $\sim$0.85~Mt~yr$^{-1}$ into a pristine, saline aquifer at the Sleipner carbon capture and storage project. A suite of time-lapse, three-dimensional seismic reflection surveys have been acquired over the injection site. This suite includes a pre-injection survey acquired in 1994 and seven post-injection surveys acquired between 1999 and 2010. Nine consistently bright reflections within the reservoir, mapped on all post-injection surveys, are interpreted to be thin layers of CO$_2$ trapped beneath mudstone horizons. The areal extents of these CO$_2$ layers are observed to either increase or remain constant with time. However, volume flux of CO$_2$ into these layers has proven difficult to measure accurately. In addition, the complex planform of the shallowest layer, Layer 9, has proven challenging to explain using reservoir simulations. In this dissertation, the spatial distribution of CO$_2$ in Layer~9 is measured in three dimensions using a combination of seismic reflection amplitudes and changes in two-way travel time between time-lapse seismic reflection surveys. The CO$_2$ volume in this layer is shown to be growing at an increasing rate through time. To investigate CO$_2$ flow within Layer~9, a numerical gravity current model that accounts for topographic gradients is developed. This vertically-integrated model is computationally efficient, allowing it to be inverted to find reservoir properties that minimise differences between measured and modelled CO$_2$ distributions. The best-fitting reservoir permeability agrees with measured values from nearby wells. Rapid northward migration of CO$_2$ in Layer~9 is explained by a high permeability channel, inferred from spectral decomposition of the seismic reflection surveys. This numerical model is found to be capable of forecasting CO$_2$ flow by comparing models calibrated on early seismic reflection surveys to observed CO$_2$ distributions from later surveys. Numerical and analytical models are then used to assess the effect of the proximity of an impermeable base on the flow of a buoyant fluid, motivated by the variable thickness of the uppermost reservoir. Spatial gradients in the confinement of the reservoir are found to direct the flow of CO$_2$ when the current is of comparable thickness to the reservoir. Finally, CO$_2$ volume in the second shallowest layer, Layer~8, is measured using structural analysis and numerical modelling. CO$_2$ in Layer~8 is estimated to have reached the spill point of its structural trap by 2010. CO$_2$ flux into the upper two layers is now $\sim$40\% of total CO$_2$ flux injected at the base of the reservoir, and is increasing with time. This estimate is supported by observations of decreasing areal growth rate of the lower layers. The uppermost layers are therefore expected to contribute significantly to the total reservoir storage capacity in the future. CO$_2$ flow within Layer~9 beyond 2010 is forecast to be predominantly directed towards a topographic dome located $\sim$3~km north of the injection point. This dissertation shows that advances in determining the spatial distribution and flow of CO$_2$ in the sub-surface can be made by a combination of careful seismic interpretation and numerical flow modelling.

Reducing carbon dioxide emissions is vital to reducing the effects of global warming. Numerous industrial methods exist, but developing alternative, greener and more energy-efficient methods is essential. Two pieces of work were investigated in this thesis towards developing alternative methods and are presented as two individual chapters, each with their own introduction, results, discussion, conclusion and future work sections. A general introduction to carbon dioxide and the vitality of decreasing carbon dioxide emissions acts as a preface to these chapters and is presented in Chapter 1. Chapter 2 examines promoting Carbon Dioxide Utilisation with new chromium(III) salophen complexes and Chapter 3 investigates a novel electrochemical carbon capture and mineralisation methodology. A range of chromium(III) salophen complexes were synthesised and were found to catalyse the synthesis of cyclic carbonates from carbon dioxide and terminal or internal epoxides at ambient conditions. The most active catalyst contained methoxy and tert-butyl groups on the salicylaldehyde and a bromide counterion, and is one of the most active catalysts in this field. Some of these catalysts were also used to catalyse the synthesis of the oxazolidinone diphenyloxazolidin-2-one from styrene oxide and phenyl isocyanate with successful results. A new electrochemical method was developed to perform carbon dioxide mineralisation, forming an amorphous aluminium hydroxycarbonate, at ambient conditions. The most energy efficient methods captured carbon with an energy requirement of 231-250 kJ mol-1 of carbon dioxide. This methodology worked with sustainable energy and materials, such as solar energy, seawater and “waste” aluminium. The carbon capture and energy efficiency of this methodology however could be improved to promote future developments and industrialisation, but nonetheless provides an interesting and alternative method to capture and mineralise carbon dioxide.

Carbon dioxide capture and storage by mineralisation (CCSM) is considered to be an alternative solution for reducing anthropogenic C0₂in some regions, where geological storage is not possible or considered uneconomically viable. However, low efficiency of mineral dissolution and use of unrecyclable additives are two key barriers for the development of CCSM. A novel CCSM process with recyclable ammonium salts is proposed to overcome these barriers in this study. This process integrates mineral carbonation with C0₂capture by employing NH₃, NH₄HSO₄and C0₂containing ammonium salts in the capture step, mineral dissolution and carbonation steps, respectively. The NH₄HSO₄ and NH₃can then be regenerated by thermal decomposition of (NH₄)₂SO₄, which is the by-product from the process. The use of C0₂ containing ammonium salts as the source of C0₂can avoid desorption and compression of C0₂, which account for 70 % of the total energy consumption in the whole CCS chain. In this work, a CCSM process route at low solid to liquid ratio (50 g/I) was experimentally investigated to validate the process concept. It was found that the dissolution efficiency of magnesium (Mg) can achieve 100 % by using NH₄HSO₄and the carbonation efficiency can reach 96.5 % by using CO₂containing ammonium salts from the capture step and addition of aqueous NH₃. Three products, including Si rich residue, Fe rich residue and pure hydromagnesite were obtained from the process. The TGA studies reported that the regeneration efficiency of NH₄HSO₄ and NH₃ in this process was 95 %. Both dissolution and carbonation efficiencies achieved in this work are higher than the values reported in previous work. In order to reduce the water usage, a CCSM process at high solid to liquid ratio (200-300 g/I) was developed. It was found that the dissolution efficiency of Mg was 64 and 72 % at 200 and 300 g/l, respectively. The increase of dissolution efficiency with a solid to liquid ratio could be explained by the removal of passive product layer caused by particle-particle interaction. At a solid to liquid ratio of 300 g/l, the highest carbonation efficiency achieved was 65.4 %. Magnesite instead of hydromagnesite was found after carbonation due to the CO₂ pressure caused by the decomposition of ammonium salts above 70 °C. Additionally, the carbonation efficiency was doubled by using (NH₄)₂CO₃compared to that using NH₄HCO₃. A preliminary evaluation was conducted to estimate the OPEX, including energy consumption, chemical costs and feedstock cost, based on the experimental results from the two process routes developed. In order to get low OPEX, the optimization process conditions, such as solid to liquid ratio and reaction time, were determined. Then, experiments at these optimized conditions were conducted. The dissolution efficiency of Mg from serpentine with particle size 75-150 pm using 2.8 M NH₄HSO₄at 100 g/l solid to liquid ratio for 1h was around 80 %. The carbonation efficiency was 96 % when the molar ratio of Mg: CO₂ containing NH⁴+ salts: NH₃was 1: 1.5: 2. Thus, the mass balance of the process showed that 3.0 t' of serpentine, 0.2 t of NH₄HSO₄and 0.1 t of NH₃ were required to sequester 1t of CO₂and produce 1.9 t of magnesite. Moreover, 1.7 t of high Si content (46.9 wt. %) and 0.3 t of high Fe content (60 wt. %) were produced. Finally, a cost evaluation study including CAPEX and OPEX was made using Aspen plus software to simulate the optimized CCSM process with recyclable ammonium salts for a 100 MW coal-fired power plant. For the input of 60 t/h CO₂, 93 % of them can be sequestered by the process with 29.5 % energy consumption and the total carbon capture and storage costs was 71.8 US$/t CO₂sequestered, excluding the product sale.

Thesis (S.M.)--Massachusetts Institute of Technology, System Design & Management Program, 2004.
Includes bibliographical references (p. 86-89).
Even as the acceptance of the fossil fuel greenhouse effect theory continues to grow amongst academics, statesmen and plebeians alike, the early adopters have already engaged in pre-emptive research activities aimed at mitigating the effects of such greenhouse gases. The focus of one such effort is on the capture and storage of CO₂ (carbon dioxide) from anthropogenic fixed source emissions. This effort can be broken down into a few broad categories such as terrestrial, ocean and geologic sequestration. Geologic sequestration refers to all activities geared towards the capture and storage of CO₂ under the surface of the earth in diverse 'reservoirs' such as deep saline formations, depleted oil and gas wells and unmineable coal seams to name a few. This investigation develops a systems perspective for assessing carbon dioxide capture and storage (CCS) opportunities within the realm of geologic sequestration. While multiple concurrent research activities continue to explore CCS opportunities from various perspectives, efforts at a systems analysis of the overall picture are just beginning. A systems view describing methodologies to integrate a variety of CCS data to assess potential sequestration opportunities is at the heart of this study. It is based on research being conducted at the Massachusetts Institute of Technology (MIT) under sponsorship of the United States Department of Energy (DOE). Using a Geographic Information System (GIS) and publicly available data, a detailed characterization of CO₂ sources and reservoirs are being developed. A source-reservoir matching process will be implemented which begins with quantifying the 'capturability' of a CO₂ source, a function of the purity, volume and several site specific considerations. Next, the potential
(cont.) proximate reservoirs are identified and then ranked based on transport options, type, capacity, cost, regulatory considerations and political sensitivity. All the above criteria will be spatially represented in the GIS and can be overlaid to produce a composite picture identifying the potential areas which would represent the maximum probability of success in sequestration efforts. A rigorous systems engineering approach will be adopted throughout the investigation. Novel tools such as the Object-Process CASE (OPCAT) tool will be used to model the complex and interdisciplinary system. A comprehensive systems modeling and engineering tool, it allows the representation of function, structure and behavior in a single model. Ultimately, the methodologies developed will be integrated and utilized in a case study to illustrate the methodology of evaluating CCS options for a given set of sources. A region in Mississippi has been identified for this model case-study. The methodology will be applied at a later time to evaluate CCS potential in the South East Regional Carbon Sequestration Partnership (SERCSP) and the West Coast Regional Carbon Sequestration Partnership (WCRCSP).
by Nisheeth Singh.
S.M.

To decrease carbon dioxide emissions into the atmosphere for climate change mitigation it is necessary to modify existing practices in processes where greenhouse gases are emitted. Due to the extremely large volumes of carbon dioxide produced globally, it is generally accepted that although carbon dioxide conversion and utilisation will contribute in the long term, in the short to medium term it will be necessary to capture and store carbon dioxide emissions to progress towards a low carbon future. Current industrial capture processes incur large energy and thus economic penalties. Storage in geological formations requires robust confidence in storage security to be publically accepted. Therefore the objective of this work was to study carbon dioxide capture and storage in processes directly confronting these two major challenges. Carbon dioxide adsorption on oxide materials for advanced carbon capture processes with lower energetic and economic penalties was investigated. Water was shown to play a crucial role in determining the presence of reactive sites, the speciation of carbonates formed and increased sorbent utilisation. A high surface area oxide with specifically exposed facets was prepared and the impact of these facets on carbon dioxide uptake performance was assessed. Volumetric gas adsorption and isotherm modelling supported the presence of two distinct adsorption sites. To enhance confidence in storage security it is necessary to understand storage processes that result in stable products. An apparatus capable of obtaining geological storage conditions was developed and carbonate formation and surface hydration at high pressure was investigated. By locating individual reactive cations on the surface of silica, silicate mineral analogues were prepared. It was shown that carbonate speciation was dependent on the reactive cation and the presence or absence of water.

Fossil fuels constitute a significant fraction of the world’s energy demand. The burning of fossil fuels emits huge amounts of carbon dioxide into the atmosphere. Therefore, the limited availability of fossil fuel resources and the environmental impact of their use require a change to alternative energy sources or carriers (such as hydrogen) in the foreseeable future. The development of methods to mitigate carbon dioxide emission into the atmosphere is equally important. Hence, extensive research has been carried out on the development of cost-effective technologies for carbon dioxide capture and techniques to establish hydrogen economy. Hydrogen is a clean energy fuel with a very high specific energy content of about 120MJ/kg and an energy density of 10Wh/kg. However, its potential is limited by the lack of environment-friendly production methods and a suitable storage medium. Conventional hydrogen production methods such as Steam-methane-reformation and Coal-gasification were modified by the inclusion of NaOH. The modified methods are thermodynamically more favorable and can be regarded as near-zero emission production routes. Further, suitable catalysts were employed to accelerate the proposed NaOH-assisted reactions and a relation between reaction yield and catalyst size has been established. A 1:1:1 molar mixture of LiAlH4, NaNH2 and MgH2 were investigated as a potential hydrogen storage medium. The hydrogen desorption mechanism was explored using in-situ XRD and Raman Spectroscopy. Mesoporous metal oxides were assessed for CO2 capture at both power and non-power sectors. A 96.96% of mesoporous MgO (325 mesh size, surface area = 95.08 ± 1.5 m2/g) was converted to MgCO3 at 350°C and 10 bars CO2. But the absorption capacity of 1h ball milled zinc oxide was low, 0.198 gCO2 /gZnO at 75°C and 10 bars CO2. Interestingly, 57% mass conversion of Fe and Fe3O4 mixture to FeCO3 was observed at 200°C and 10 bars CO2. MgO, ZnO and Fe3O4 could be completely regenerated at 550°C, 250°C and 350°C respectively. Furthermore, the possible retrofit of MgO and a mixture of Fe and Fe3O4 to a 300 MWe coal-fired power plant and iron making industry were also evaluated.

This Engineering Doctorate project aimed to study the effects of varying flowrates on the flow dynamics of carbon dioxide within a pipeline. The researched utilised the software gCCS to simulate three different transport system. The first system looked at the effects of transporting pure carbon dioxide in both the supercritical phase and the sub-cooled liquid phase. The outputs from the model showed that when the inlet flowrate is decreased, the outlet flowrate responds in three distinct phases. The second system compared the effects of three different impurities; hydrogen, nitrogen and oxygen, on the flow response when the inlet flowrate is decreased. It was found that all three impurities caused an increase in the offset between the inlet and outlet flowrate. The third system looked at how multiple sources of carbon dioxide effect the flowrate within the main trunk pipeline. It was found that multiple sources of carbon dioxide do not affect the flow of CO2 within the pipeline beyond that of the base case. The final part of the research compared data from the Shell QUEST pipeline to the model. This showed the model was able to predict the flowrate and pressure of the carbon dioxide with good accuracy.

Sverige har som ambition att uppnå nettonollutsläpp av fossilt CO2 till år 2045. För att lyckas med detta ska landet minska sina utsläpp med 85%, samtidigt som så kallade kompletterande åtgärder kommer vidtas för att kompensera för resterande 15%. Denna studie utreder Sveriges arbete med negativa utsläpp som kompletterande åtgärd med fokus på teknikerna bio-energy for carbon capture and storage (Bio-CCS på svenska), Direct air capture for carbon capture and storage (DACCS) och biokol. Även carbon capture and storage (CCS), som kan bidra till att göra anläggningar CO2-neutrala, har studerats. Under arbetets gång har en litteraturstudie samt intervjuer med forskare, politiker, bransch- och företagsrepresentanter samt myndigheter genomförts.  För CCS och Bio-CCS, som innefattar avskiljning av CO2 från punktutsläpp, finns fyra olika avskiljningsstrategier som kallas post-, pre-, och oxyfuel combustion samt chemical looping. I fallet med DACCS tillämpas antingen absorption eller adsorption för att avskilja koldioxiden från atmosfären. Biokol produceras genom förbränning av biomassa i en pyrolysanläggning och kan sedan användas som jordförbättringsmedel och kolsänka. Det finns idag en inhemsk biokolsproduktion på kommersiell skala vilket gör att biokol skiljer sig från de övriga tre teknikerna som inte kommit lika långt i sin utveckling. Däremot finns det ett flertal pilotprojekt inom CCS och Bio-CCS i Sverige.  Sveriges väletablerade bioekonomi gör att det finns goda förutsättningar för biokol och Bio- CCS att bidra till negativa utsläpp ur ett 2045-perspektiv. DACCS anses däremot inte aktuellt som kompletterande åtgärd till år 2045. Efter intervjuer framgår att det råder en god samstämmighet mellan olika aktörer kring vilka faktorer som behöver behandlas för att implementera teknikerna. Gemensamt för alla tekniker är att det krävs ekonomiska incitament för att möjliggöra storskalig implementering. För CCS-teknikerna krävs även regulatoriska förändringar för att underlätta transporten av CO2.
Sweden's ambition is to achieve net zero emissions of fossil CO2 by the year 2045. To reach this target, Sweden aims to reduce its emissions by 85%, while so-called supplementary measures will be taken to compensate for the remaining 15%. This study investigates Sweden's work with negative emissions as a complementary measure with a focus on the technologies bio-energy for carbon capture and storage (Bio-CCS in Swedish), Direct air capture for carbon capture and storage (DACCS) and biochar. Carbon capture and storage (CCS), which can help make industrial plants CO2-neutral, has also been studied. During the project, a literature study and interviews with researchers, politicians, industry and company representatives as well as authorities were carried out, which formed the basis of the report.  For CCS and Bio-CCS, which include separation of CO2 from point source emissions, there are four different separation strategies called post-, pre-, and oxyfuel combustion as well as chemical looping. Among these, post combustion is highlighted as the most developed. In the case of DACCS, either absorption or adsorption is applied to separate CO2 from the atmosphere. CCS, Bio-CCS and DACCS all have in common that the captured CO2 must be stored in deep geological formations once it has been separated. Biochar is produced by heating biomass in a pyrolysis plant and can be used as a soil improver and carbon sink. Today Sweden has a domestic biochar production on a commercial scale, which means that biochar differs from the other three technologies that have yet to reach that stage of development. However, there are several pilot projects within Bio-CCS and CCS in Sweden.  Sweden's well-established bioeconomy means that the conditions are good for biochar and Bio-CCS to contribute to negative emissions in relation to the 2045 target. DACCS, on the other hand, is not considered relevant as a supplementary measure to the year 2045 due to its technical immaturity and high cost. From interviews with researchers, authorities, companies, industry organizations and politicians, it is clear that there is a consensus between the different actors on which factors need to be addressed in order to enable large-scale implementation of the technologies. Common to all technologies is that financial incentives are required to enable large-scale implementation. The CCS technologies also require regulatory changes to facilitate the transport of CO2.

Carbon dioxide (CO2) capture and geological storage (CCS) is recognised as one of themain options in the portfolio of greenhouse gas (GHG) mitigation technologies beingdeveloped worldwide. The CO2 capture and storage technologies require significantamounts of energy during their implementation and also change the environmentalprofile of power generation. The holistic perspective offered by Life Cycle Assessment(LCA) enables decision makers to quantify the trade-offs inherent in any change to thepower production systems and helps to ensure that a reduction in GHG emissions doesnot result in significant increases in other environmental impacts. Early LCA studies ofpower generation with CCS report a wide range of results, as they focus on specific CO2capture cases only. Furthermore, previous work and commercial LCA software have arigid approach to system boundaries and do not recognise the importance of the level ofdetail that should be included in the Life Cycle Inventory (LCI) data. This research developed a complete LCA framework for the ?cradle-to-grave?assessment of alternative CCS technologies in carbon-containing fuel power generation. A comprehensive and quantitative Life Cycle Inventory (LCI) database, which modelsinputs/outputs of processes at high level of detail, accounts for technical and geographicdifferences, generates LCI data in a consistent and transparent manner was developedand arranged and flexible structure. The developed LCI models were successfully applied to power plants with alternativepost-combustion chemical absorption capture and oxy-fuel combustion capture. Theresults demonstrate that most environmental impacts come from power generation withCCS and the upstream process of coal production at a life-cycle perspective. LCAresults are sensitive to the type of coal used and the CO2 capture options chosen. Moreover, the models developed successfully trace the fate of elements (including tracemetals) of concern throughout the power generation, CO2 capture, transport andinjection chain. Monte Carlo simulation method combined with the LCI models wasapplied to quantify the uncertainty of emissions of concern. A novel analytical framework for the LCA of CO2 storage was also developed andapplied to a saline aquifer storage field case. The potential CO2 leakage rates werequantified and the operational and geological parameters that determine the ratio of CO2leakage total volume of CO2 injected were identified.

In an effort to reduce atmospheric carbon dioxide (CO2) emissions and mitigate climate change, it has been proposed to sequester supercritical CO2 in underground saline aquifers. Geological storage of CO2 involves different trapping mechanisms which are not yet fully understood. In order to improve the understanding of the effect of chemical reaction on the flow and transport of CO2, these storage mechanisms are modelled experimentally and numerically in this work. In particular, the destabilising interaction between the fluid hydrodynamics and a density-increasing second-order chemical reaction is considered. It is shown that after nondimensional scaling, the flow in a given physicochemical system is governed by two dimensionless groups, Da/Ra2, which measures the timescale for convection compared to those for reaction and diffusion, and CBo', which reflects the excess of the environmental reactant species relative to the diffusing solute. The destabilising reactive scenario is modelled experimentally under standard laboratory conditions using an immiscible two-layer system with acetic acid acting as the solute. A novel colorimetric technique is developed to infer the concentrations of chemical species from the pH of the solution making it possible to measure the flux of solute into the aqueous domain. The validity of this experimental system as a suitable analogue for the dissolution of CO2 is tested against previous work and the destabilising effect of reaction is investigated by adding ammonia to the lower aqueous layer. The system is also modelled numerically and it is shown that the aqueous phase reaction between acetic acid and ammonia can be considered to be instantaneous, meaning that Da/Ra2 tends to infinity and the flow is therefore governed only by the initial dimensionless concentration of reactant in the aqueous phase. The results from the experiments and numerical simulations are in good agreement, showing that an increase in the initial concentration of reactant increases the destabilising effect of reaction, accelerates the onset of convection and enhances the rate of dissolution of solute. The numerical model is then applied to a real world aquifer in the Sleipner gas field and it is demonstrated how the storage capacity of a potential CO2 reservoir could be enhanced by chemical reaction.

This thesis reports an investigation into carbon dioxide capture and catalysis in several target metal-organic frameworks (MOFs) and porous organic polymers (POPs). In chapter 2, a series of Zr-MOFs were synthesised for potential applications in carbon capture and storage. In the first instance, a novel Zr-based MOF was constructed exclusively from the monocarboxylate ligand formate. Despite the low surface area, the new material exhibited a high affinity for CO2 over nitrogen at room temperature. In addition, the water-stable Zr–tricarboxylate series of frameworks, exhibited tunable porosity by virtue of systematic modulation of the chain length of the monocarboxylate ligand. Last but not least, defect concentrations and their compensating groups have been systematically tuned within UiO-66 frameworks by using modified microwave-assisted solvothermal methods. Both of these factors have a pronounce effect on CO2 and H2O adsorption at low and high pressure. Chapter 3 focuses on the development of a rapid and efficient microwave-assisted solvothermal method for a series of zirconium oxide based MOFs known as MIL-140s. Combined experimental and computational studies have revealed the interplay between the framework pore size and functionality on the CO2 adsorption performance of MIL-140 frameworks. The potential for CO2 photocatalysis in POPs was also explored in chapter 4. A POP with free 2,2’-bipyridyl sites was prepared via Sonogashira-Hagihara coupling and catalytically active moieties ([(α-diimine)Re(CO)3Cl]) were introduced using a post-synthesis metalation method. Thereafter, the Re-containing porous organic polymer was tested for the photocatalytic reduction of CO2. After an induction period, Re-POP produced CO at a stable rate, unless soluble [(bpy)Re(CO)3Cl] (bpy = 2,2´-bipyridine) was added. This provides some of most convincing evidence to date that [(α-diimine)Re(CO)3Cl] catalysts for photocatalytic CO2 reduction decompose via a bimetallic pathway.

Carbon capture, utilization and storage (CCUS) in confined saline aquifers in sedimentary formations has the potential to reduce the impact of fossil fuel combustion on climate change by storing CO2 in geologic formations in perpetuity. At PT conditions relevant to CCUS, CO2 is less dense than the pre-existing brine in the formation, and the more buoyant CO2 will migrate to the top of the formation where it will be in contact with cap rock. A typical cap rock is clay-rich shale, and interactions between shales and CO2 are poorly understood at PT conditions appropriate for CCUS in saline formations. In this study, the interaction of CO2 with clay minerals in the cap rock overlying a saline formation has been examined, using Na-rich montmorillonite as an analog for clay-rich shale. Attenuated Total Reflectance -- Fourier Transform Infrared Spectroscopy (ATR -FTIR) was used to identify potential crystallographic sites (AlAlOH, AlMgOH and interlayer space) where CO2 could interact with montmorillonite at 35"C and 50"C and from 0-1200 psi.  Analysis of the data indicates that CO2 that is preferentially incorporated into the interlayer space, with dehydrated montmorillonite capable of incorporating more CO2 than hydrated montmorillonite. No evidence of chemical interactions between CO2 and montmorillonite were identified, and no spectroscopic evidence for carbonate mineral formation was observed.  Further work is needed to determine if reservoir seal quality is more likely to be degraded or enhanced by CO2 - montmorillonite interactions.
Master of Science

This work explores the use of computational methods to aid in the design of Metal Organic Frameworks (MOFs) for use as CO2 scrubbers in carbon capture and storage applications. One of the main challenges in this field is in identifying important MOF design characteristics which optimize the complex interactions governing surface adsorption. We approach this in a high-throughput manner, determining properties important to CO2 adsorption from generating and sampling a large materials search space. The utilization of MOFs as potential carbon scrubbing agents is a recent phenomenon, as such, many of the computational tools necessary to perform high-throughput screening of MOFs and subsequent analysis are either underdeveloped or non-existent. A large portion of this work therefore involved the development of novel tools designed specifically for this task. The chapters in this work are contiguous with the goal of designing MOFs for CO¬2 capture, and somewhat chronological in order and complexity, meaning as time and expertise progressed, more advanced tools were developed and utilized for the purposes of computational MOF discovery. Initial work towards MOF design involved the detailed analysis of two experimental structures; CALF-15 and CALF-16 using classical molecular dynamics, grand canonical Monte Carlo simulations, and DFT to determine the structural features which promote CO2 adsorption. An unprecedented level of agreement was found between theory and experiment, as we are able to capture, with simulation, the X-ray resolved binding sites of CO2 in the confined pores of CALF-15. Molecular simulation was then used to provide a detailed breakdown of the energy contributions from nearby functional groups in both CALF-15 and CALF-16. A large database of hypothetical MOF structures is constructed for the purposes of screening for CO2 adsorption. The database contains 1.3 million hypothetical structures, generated with an algorithm which snaps together rigid molecular building blocks extracted from existing MOF crystal structures. The algorithm for constructing the hypothetical MOFs and the building blocks themselves were all developed in-house to form the resulting database. The topological, chemical, and physical features of these MOFs are compared to recently developed materials databases to demonstrate the larger structural and chemical space sampled by our database. In order to rapidly and accurately describe the electrostatic interactions of CO2 in the hypothetical database of MOFs, parameters were developed for use with the charge equilibration method. This method assigns partial charges on the framework atoms based on a set of parameters assigned to each atom type. An evolutionary algorithm was used to optimize the charge equilibration parameters on a set of 543 hypothetical MOFs such that the partial charges generated would reproduce each MOFs DFT-derived electrostatic potential. Validation of these parameters was performed by comparing the CO2 adsorption from the charge equilibration method vs DFT-derived charges on a separate set of 693 MOFs. Our parameter set were found to reproduce DFT-derived CO2 adsorption extremely well using only a fraction of the time, making this method ideal for rapid and accurate high-throughput MOF screening. A database of 325,000 MOFs was then screened for CO2 capture and storage applications. From this study we identify important binding pockets for CO2 in MOFs using a binding site analysis tool. This tool uses a pattern recognition method to compare the 3-D configurations of thousands of pore structures surrounding strong CO2 adsorption sites, and present common features found amongst them. For the purposes of developing larger databases which sample a more diverse materials space, a novel MOF construction tool is devloped which builds MOFs based on abstract graphs. The graph theoretical foundations of this method are discussed and several examples of MOF construction are presented to demonstrate its use. Notably, not only can it build existing MOFs with complicated geometries, but it can sample a wide range of unique structures not yet discovered by experimental means.

Carbon Capture and Storage is a nascent technology developed with the intention of collecting carbon dioxide emissions from the flue gasses of point source producers, such as power stations or cement works. The carbon dioxide is then stored in underground geological reservoirs so that it does not reach the atmosphere, reducing the rate at which greenhouse gasses accumulate and influence climate change. However, as with all nascent technologies, the benefits of these developments and concepts must be weighed against the risks of serious and long-term environmental impact should an accidental release occur. The aim of this thesis is to study the potential for environmental damage caused by a release of carbon dioxide into the marine environment from a sub-seabed carbon dioxide reservoir generated through carbon capture and storage development. The quantification of the rate of change caused by such an accidental release of carbon dioxide will be studied, as will the rate at which natural conditions are re-established upon cessation of the release.

The present study presents a draft national CCT (Clean Coal Technologies) and CCS (Carbon Capture and Storage) technology roadmap to policy makers. Various technical and non-technical (economic and social) challenges that currently prevent CCT and CCS from being a widely used commercial technology are discussed and the goals for each research pathway are defined. The process of creating the roadmap started with a review and assessment of the existing national and international technology roadmaps which represent a global picture of the state of the art and national and international plans for future on CCT and CCS research development, demonstration and deployment (R&
D&
D). Following this step, the national situation, capacities and priorities were examined. Finally, R&
D&
D actions discussed in the existing roadmaps and/or new actions were carefully selected and suggested as a draft Turkish CCT and CCS Roadmap that needs further development and discussion by the input of interdisciplinary national stakeholders. As a conclusion a number of technical and non-technical suggestions are delivered.

Dispatchable low carbon electricity has been identified as a key requirement for low carbon electricity systems because these systems must provide reliable electricity services to an increasing portion of the world’s population while utilising an increasing share of nondispatchable assets such as renewable and nuclear generators. Fossil fuel generators can provide dispatchable low carbon electricity by leveraging post-combustion carbon capture technologies assuming post-combustion capture (PCC) plants can operate in a flexible and efficient manner. This thesis explores the connection between solvent analysis techniques and the optimal operation of PCC plants with a particular focus on process optimisation and control under flexible and transient conditions. The connection between solvent analysis measurements and PCC plant process control and optimisation strategies is established. An ideal set of analysis technique criteria is established for flexible post-combustion capture plants. Currently available solvent analysis techniques are surveyed and evaluated against the ideal set of criteria. Specific weaknesses of current techniques are highlighted and two novel solvent analysis techniques are introduced to address these weaknesses. The first provides continuous amine concentration and CO2 loading measurements at process flow conditions by inferring solvent chemical composition from physical properties. This method was evaluated by deploying an instrument prototype to a post-combustion pilot plant to continuously analyse solvent during a test campaign which simulated flexible plant operation. The measurement results were compared against industry standard solvent analysis techniques and the inferential technique was found to produce sufficient measurement accuracy and sensitivity while providing a faster, lower cost and more robust measurement technique. The second technique combines the strengths of several currently available CO2 loading techniques to measure CO2 gas evolved from an acidified solvent under vacuum conditions. The technique was found to provide superior measurement accuracy and sensitivity compared to currently available methods when measuring lab standard solutions. The integration of these novel analysis techniques into advanced process control systems is proposed and future method improvements are suggested.

Carbon dioxide enhanced oil recovery (CO2EOR) is a proven and available technology used to produce incremental oil from depleted fields. Although this technology has been used successfully onshore in North America and Europe, projects have maximised oil recovery and not CO2 storage. While the majority of onshore CO2EOR projects to date have used CO2 from natural sources, CO2EOR is now more and more being considered as a storage option for captured anthropogenic CO2. In the North Sea the lack of low cost CO2, in large volumes, has meant that no EOR projects have utilised CO2 as an injection fluid. However CO2EOR has the highest potential of all EOR techniques to maximise recovery from depleted UK oil fields. With the prospect of Carbon Capture and Storage (CCS) capturing large tonnages of CO2 from point source emission sites, the feasibility of CO2EOR deployment in the North Sea is high. This thesis primarily aims to address a number of discrete issues which assess the effectiveness of CO2EOR to both produce oil and store CO2. Given the fundamental shift in approach proposed in North Sea CO2EOR projects, the carbon balance of such projects is examined. Using a life cycle accounting approach on a theoretical North Sea field, we examine whether offshore CO2EOR can store more CO2 than onshore projects traditionally have, and whether CO2 storage can offset additional emissions produced through offshore operations and incremental oil production. Using two design scenarios which optimise oil production and CO2 storage, we find that that net GHG emissions were negative in both ‘oil optimised’ and ‘CO2 storage optimised’. However when emissions from transporting, refining and combusting the produced crude oil are incorporated into the life cycle calculations the ‘oil optimised scenario’ became a net emitter of GHG and highlights the importance of continuing CO2 import and injection after oil production has been maximised at a field. This is something that has not traditionally occurred. After assessing rates of flaring and venting of produced associated gas at UK oil fields it is found that the flaring or venting of reproduced CH4 and CO2 has a large control on emissions. Much like currently operating UK oil fields the rates of flaring and venting has a control on the carbon intensity of oil produced. Here values for the carbon intensity of oil produced through CO2EOR are presented. Carbon intensity values are found to be similar to levels of current UK oil production and significantly lower than other unconventional sources. As well as assessing the climate benefits of CO2EOR, a new assessment of CO2EOR potential in Residual Oil Zones (ROZ) is also made. ROZ resource, which is thought to add significant potential to both the oil reserves and CO2 storage potential in some US basins, is here identified in the North Sea for the first time. Based on the foundation of North Sea hydrodynamics study, this thesis identifies the Pierce field as a candidate ROZ field where hydrodynamic tilting of the oil water contact has naturally occurred leaving a zone of residual oil. To test the feasibility of CO2EOR in such a zone a methodology is presented and applied. Notably the study highlights that in this case study recoverable reserves from the ROZ may approach 20% of total field recoverable reserves and have the capability to store up to 11Mt of CO2. While highlighting the CO2EOR potential in the ROZ the thesis discusses the importance in expanding the analysis to quantify its importance on a basin scale. Discussion is also made on whether new resource identification is necessary in a mature basin like the North Sea. With CO2EOR being considered as a feasible option for storing captured anthropogenic CO2, it is important to assess the security of storage in CO2EOR. Using real geochemical and production data from a pilot CO2EOR development in Western Canada two approaches are used to assess the partitioning of CO2 between reservoir fluids through time. Using a number of correlations it is found that CO2 dissolution in oil is up to 7 times greater than in reservoir brine when saturations between the two fluids are equal. It is found that after two years of CO2 injection solubility trapping accounts for 26% of injected CO2. The finding that significantly more dissolution occurs in oil rather than brine indicates that CO2 storage in EOR is safer than in brine storage. However a number of factors such as the increase in oil/CO2 mobility due to CO2 injection is also discussed. The overall conclusion from the work is that CO2EOR in the North Sea has the potential to be an effective way of producing oil and storing CO2 in the North Sea. A number of design, operational and accounting factors are however essential to operate an exemplar CO2EOR project where low carbon intensity oil can be produced from a mature basin while storing large tonnages of captured anthropogenic CO2.

Le reazioni di carbonatazione di specifiche tipologie di minerali e materiali di diversa origine, come ad esempio malte cementizie o calce, costituiscono un ben noto processo naturale che produce una serie di significativi effetti sugli stessi materiali alcalini, ed in particolare: lo stoccaggio di CO2 mediante la formazione di una fase carbonatica solida e termodinamicamente stabile, la riduzione del pH e modifiche del comportamento alla lisciviazione del materiale, oltre alla variazione di alcune proprietà fisiche e meccaniche. Dato che le cinetiche di reazione sono in genere molto lente in condizioni naturali, per sfruttare alcuni dei sopradetti effetti dell’invecchiamento chimico, come la stabilizzazione chimica di alcune tipologie di residui e lo stoccaggio minerale di CO2, sono stati investigati e sviluppati specifici processi di carbonatazione accelerata selezionando e controllando le condizioni operative in modo tale da incrementare significativamente le cinetiche di reazione. In funzione dell’applicazione del processo e della tipologia di materiale selezionato, sono state sperimentate diverse condizioni operative e differenti tipologie di trattamento (gas-solido, ad umido, ecc.). Il principale obiettivo della presente tesi di dottorato è stato quello di studiare sperimentalmente i processi di carbonatazione accelerata applicati sia a minerali che a residui industriali, così da ottenere nuove indicazioni relative ai meccanismi fondamentali influenzanti il processo per ogni tipologia di materiale analizzato. Lo studio del processo di carbonatazione accelerata di minerali ha riguardato in particolare gli effetti della presenza di CO2 ad alta pressione (fino a 100 bar) e di alcuni sali sulla cinetica di dissoluzione dell’olivina a 120 °C in un reattore agitato a flusso continuo per analizzare se queste sostanze esercitino un effetto positivo o al contrario limitante nei confronti della cinetica di dissoluzione del Mg. Esperimenti di carbonatazione in modalità batch su materiale umidificato (con rapporti liquido/solido <1 l/kg) sono stati eseguiti in condizioni operative blande (temperatura di 30-50 °C e pressione di CO2 pari a 1-10 bar) su residui di incenerimento di rifiuti solidi, in particolare scorie di fondo e ceneri volanti, e su scorie della produzione di acciaio inossidabile. Gli obiettivi di questo lavoro sono stati essenzialmente: la stima della capacità di sequestro ottenibile per ogni tipologia di residuo industriale correlata alla dimensione granulometrica e alla composizione chimica del campione; lo studio dell’influenza dei principali parametri operativi (temperatura, pressione e rapporto liquido solido) sulla cinetica di reazione; e ad ultimo l’analisi degli effetti della carbonatazione sulla mineralogia ed il comportamento alla lisciviazione dei residui. Lo studio della cinetica di dissoluzione dell’olivina ha mostrato che, per tutte le condizioni operative esaminate (pH variabile tra 3 e 8), l’unico fattore controllante il tasso specifico di dissoluzione è risultato essere il pH della soluzione. Dunque la pressione parziale dell’anidride carbonica e la salinità hanno mostrato di influenzare la cinetica di dissoluzione solo indirettamente, variando il valore finale del pH della soluzione. Questo risultato appare significativo, poiché implica che la precipitazione dei carbonati, che ha luogo in presenza di CO2 ad elevata pressione e valori di pH maggiori di 6, e la dissoluzione dell’olivina potrebbero essere teoricamente essere eseguiti nello stesso reattore, senza effetti di inibizione sulla cinetica di dissoluzione del magnesio. Per quanto concerne gli effetti della carbonatazione accelerata sul comportamento alla lisciviazione dei residui alcalini esaminati, significativi risultati sono stati ottenuti in particolare per i residui di incenerimento; per entrambi i materiali, la carbonatazione accelerata ha mostrato di esercitare un importante effetto di immobilizzazione nei confronti di Pb, Zn e Cu, i quali sono risultati essere elementi critici in termini di rilascio per entrambe le tipologie di residui tal quali. Per le ceneri volanti, i risultati ottenuti dalla modellazione geochimica dei dati ricavati dai test di lisciviazione condotti a pH variabile hanno mostrato una variazione nelle fasi minerali controllanti la solubilità di vari elementi tra campioni tal quali e campioni carbonatati. Per le ceneri trattate con CO2, il rilascio di metalli è risultato chiaramente controllato da una varietà di fasi carbonatiche, indicando la potenzialità di questo processo di convertire le iniziali fasi minerali contenenti i metalli in fasi carbonatiche meno solubili, con positive implicazioni per il comportamento ambientale di questa tipologia di residui. Significativi sequestri di CO2 sono stati ottenuti in particolare per le ceneri volanti (250 g/kg residuo); comunque, data l’esiguità dei quantitativi di questo materiale rispetto alle emissioni complessive di CO2 generate tipicamente negli impianti di incenerimento, il processo di carbonatazione su questa tipologia di residui, come sulle scorie di fondo, non risulta essere un processo efficace per lo stoccaggio di CO2. La carbonatazione accelerata di scorie di acciaieria è risultata invece una tecnica potenzialmente molto interessante per il sequestro minerale dell’anidride carbonica generata dallo stesso impianto industriale, per quanto condizioni operative più severe rispetto a quelle adottate nel presente studio dovrebbero essere applicate per incrementare il sequestro di CO2.
Carbonation of specific types of minerals and anthropogenically derived products, such as cement or lime binders, is a well known naturally occurring process which exerts several significant effects on alkaline materials, including specifically: CO2 uptake by formation of a solid and thermodynamically stable carbonate phase, pH decrease and modifications of the leaching behaviour of the material, besides variations of some of its physical and mechanical properties. Since the kinetics of this reaction is very slow at ambient conditions, to exploit some of the above mentioned effects of chemical weathering for developing specific engineered processes, such as waste chemical stabilization and CO2 mineral storage, carbonation processes carried out under selected and controlled operational conditions have been developed, in order to significantly increase the kinetics of the reactions involved. Depending on the application of the process and the selected material, different operating conditions have been employed and several process routes have been tested. The main objective of this doctoral thesis was to investigate the accelerated carbonation process applied both to minerals and industrial residues in order to gain new insight on the key reaction mechanisms for each type of material. Regarding accelerated carbonation of minerals, the effects of the presence of high pressure CO2 (up to 100 bar) and salinity on olivine dissolution kinetics at 120 °C in a stirred flow-through reactor were specifically investigated, in order to assess whether these parameters may exert an enhancing or inhibiting effect on the kinetics of Mg dissolution. Batch carbonation experiments on humidified material (with liquid to solid ratios < 1 l/kg) at mild operating conditions (temperature of 30-50 °C and CO2 pressure of 1-10 bar) were specifically carried out on waste incineration residues such as bottom ash (BA) and air pollution control (APC) residues, as well as on stainless steel slag. The objectives of this study were essentially threefold: to assess the CO2 storage capacity achievable for each type of industrial residue correlating it to the particle size and to the chemical composition of the samples; to study the influence of the main operational parameters (temperature, pressure and liquid to solid ratio) on reaction kinetics; and finally to investigate the effects of carbonation on the mineralogy and leaching behaviour of the residues. The study on olivine dissolution kinetics showed that, under all the examined operating conditions (pH range 3-8), the only factor governing the specific dissolution rate was the pH of the solution. Hence CO2 pressure and salinity appeared to influence olivine dissolution kinetics only indirectly, by affecting the final pH of the solution. This is a significant finding, since it implies that carbonate precipitation, which occurs in presence of high pressure CO2 at pH values above 6, and olivine dissolution could theoretically be carried out in the same reactor without inhibition effects on Mg dissolution kinetics. As for the effects of accelerated carbonation on the leaching behaviour of the studied alkaline residues, significant results were obtained in particular for the BA and APC residues; for both types of materials, accelerated carbonation showed to exert a strong immobilization effect on Pb, Zn and Cu, which were among the critical elements in terms of heavy metal leaching for both types of untreated residues. For APC ash, chemical speciation modelling indicated a change in the solubility-controlling minerals from the untreated to the carbonated ash. For the latter, metal release was found to be clearly controlled by a number of carbonate minerals, indicating the potential of the carbonation process to convert the initial metal-containing minerals into generally less soluble carbonate forms, with positive implications on the environmental behaviour of the ash. Significant CO2 uptakes were achieved in particular for the APC ash (250 g/kg residue); however, owing due to the meagre quantities of this material generated in incineration plants compared to CO2 emissions, accelerated carbonation of this type of industrial residues, as well as of bottom ash, does not appear to be a feasible process for CO2 storage. Accelerated carbonation of stainless steel slag instead, appears to be an interesting technique for carrying out mineral storage of carbon dioxide in industrial facilities using part of the waste streams generated in the same plant, although more severe operating conditions than those used in this work should be applied in order to increase the CO2 uptake of the slag.

Flexible carbon capture and storage (CCS) has the potential to play a significant part in the decarbonisation of electricity generation portfolios which have significant penetration from intermittent renewable sources. Post-combustion capture (PCC) with amine solvents is a mature technology and is currently the state-of-the-art for CO2 emissions reduction from power stations. However, knowledge of the dynamic capture process is currently limited due to a dearth of dynamic datasets which reflect real plant operation, lack of a robust in-situ solvent analysis method for plant control and uncertainty about how changing plant design affects the response to dynamic operations. In addition, the nature of interfacial gas-liquid dynamics inside the absorber column are not well known and rely on correlations for effective mass transfer area and liquid holdup which may have uncertainties of up to +/- 13%. This could result in absorption columns being improperly sized for CCS operations. Two pilot-scale test campaigns are implemented in order to gain an understanding of how the capture plant responds to dynamic operations, the first on natural gas combined cycle (NGCC)-equivalent flue gas, the second on pulverised coal (PC)-equivalent. Changes in flue gas flow rates and steam supply which are designed to be representative of PCC operation on real NGCC and PC plant are implemented, using 30%wt monoethanolamine (MEA) as absorbent in both cases. Dynamic datasets are obtained for 5 scenarios with NGCC and 8 with PC flue gas. The test campaigns are carried out using two separate pilot-scale facilities and highlight the effect of plant design on hydrodynamics and hence, the response of the capture plant to dynamic operations. Finally, a novel solvent sensor is used to demonstrate, for the first time, control of the capture facility using in-situ measurements of solvent composition, combined with knowledge of test facility hydrodynamics and response times. Results from the pilot-scale test campaign are then used along with a mathematical NGCC capture plant scale up to investigate the potential effects of dynamic operations on total yearly CO2 emissions and the associated environmental penalties, depending on CO2 price. Manufacturers of column internals for CCS often rely on computational fluid dynamic (CFD) software tools for design, but existing commercial codes are unable to handle complex two-phase flows such as those encountered in the absorber column of a CO2 capture plant. An open-source direct numerical simulation (DNS) tool which will be capable of rigorously modelling two-phase flow with turbulence and mass transfer has been developed and could eventually replace the empirical methods currently used in packing design. The DNS code requires validation by experiment. For the purpose of validation a dual-purpose wetted-wall column is constructed, which in addition to mass transfer measurements can be used to determine liquid film thickness using an optical method. Measurements of average film thickness, wave amplitude, frequency, velocity and growth rate are provided for three liquid flow rates of fresh 30%wt MEA solution. Wave measurements are made with quiescent, laminar and turbulent gas flow, with and without mass transfer. These measurements can be used to validate the DNS code at its existing level of complexity, and in the future when turbulence and mass transfer are added.

Carbon dioxide capture and storage (CCS) is an essential part of the portfolio of technologies to achieve climate mitigation targets. Cost efficient and large scale deployment of CCS necessitates that all three elements of the supply chain (capture, transportation and storage) are coordinated and planned in an optimum manner both spatially and across time. However, there is relatively little experience in combining CO2 capture, transport and storage into a fully integrated CCS system and the existing research and system planning tools are limited. In particular, earlier research has focused on one component of the chain or they are deterministic steady-state supply chain optimisation models. The very few multi-period models are unable to simultaneously make design and operational decisions for the three components of the chain. The major contribution of this thesis is the development for the first time of a multi-period spatially explicit least cost optimization model of an integrated CO2 capture, transportation and storage infrastructure under both a deterministic and a stochastic modelling framework. The model can be used to design an optimum CCS system and model its long term evolution subject to realistic constraints and uncertainties. The model and its different variations are validated through a number of case studies analysing the evolution of the CCS system in the UK. These case studies indicate that significant cost savings can be achieved through a multi-period and integrated system planning approach. Moreover, the stochastic formulation of the model allows analysing the impact of a number of uncertainties, such as carbon pricing or plant decommissioning schedule, on the evolution of the CSS system. In conclusion, the model and the results presented in this thesis can be used for system planning purposes as well as for policy analysis and commercial appraisal of individual elements of the CCS network.

Concerns about climate change have rejuvenated global efforts in reducing carbon dioxide (CO2) emissions. Tactics include capture and sequestration of CO2 from point sources and the promotion of hydrogen (H2) as a “transport fuel”. Current H2 vehicles use high pressure H2 tanks which lack the convenience of their fossil fuel counterparts and present potential safety hazards. Development of adsorbent materials that reduce the energetic costs of H2 and CO2 capture, facilitating reversible storage under safer conditions, are hoped to increase the viability of these technologies for industrial application. This thesis is the first to utilise magnetron sputtering, a technique allowing fine control over nano-material synthesis, for the design of novel solid adsorbents and deposition of novel dopants for H2 storage and CO2 capture. Work includes an in-depth study of the influence of nitrogen as a sputter gas on the growth of carbonaceous films, and is the first to explore these films performance as H2 and CO2 adsorbents. Several conflicting nitrogen effects were identified, their influence on the films growth dependent upon the nitrogen fraction of the sputter gas. Performance of the deposited films as adsorbents was also dependent on the growth conditions. The H2 storage capacity at 77 K and 20 bar of an optimised adsorbent, synthesised by magnetron sputtering, was 4.7 wt.%, comparable in performance to alternatives from the literature. Further work provides the first evidence that cerium, deposited by magnetron sputtering, can function as an adsorbent catalyst and identified that sputtering is a worthwhile, yet slow process for adsorbent doping as it facilitates intimate binding between the adsorbent and the dopant. The novel synthesis of graphene by magnetron sputtering was also attempted. Whilst tests failed, results collected could provide guidance for more successful attempts in the future.

The Earth gets warmer primarily as a result of human activity, which results in the release of greenhouse gases into the atmosphere, most notably carbon dioxide, CO2. Increasing carbon dioxide concentration brings many problems with itself such as climate change, global warming, freshwater issues, reduced soil productivity, increasing acid rains, human health issues, extinction of species and more. And developing countries have a huge share in this increase in carbon dioxide emissions. To tackle with undesirable change, new missions and technologies are needed. In the coming decades, a carbon capture, utilisation, and storage appears to be a viable problem-solving technology. Developed countries started to use these technologies, demonstrating that although zero-emission is currently unlikely, reducing pollution is entirely feasible. This paper mainly focus on this relationship and provide information for developing countries to shift from linear economy to circular economy. The idea of a "circular economy" (CE) is quickly gaining traction as a new model for sustainable development. A circular economy is one in which goods, gases and materials are removed, recycled, repaired, and reused rather than discarded, and waste from one manufacturing process is turned into a valuable input. The research development scenario aims to increase the number of CCUS plants which result with decreasing of carbon dioxide emissions. The scenario says that, four factories should come together and construct one carbon capture, utilisation and storage plant. One of the main part of this idea is capturing process begins where the greenhouse gas emit to the atmosphere. Those gases absorbed by special adsorbers and transported to main pipeline by polyethylene pipelines. The main pipeline takes all the absorbed gases to the CCUS plants. By using this system, emitted carbon dioxide will be captured before mixing to air or atmosphere.

Porous organic polymers containing nitrogen-rich building units are among the most promising materials for selective CO2 capture and separation applications that impact the environment and the quality of methane and hydrogen fuels. The work described herein describes post-synthesis modification of Nanoporous Organic Frameworks (NPOFs) and its impact on gas storage and selective CO2 capture. The synthesis of NPOF-4 was accomplished via a catalysed cyclotrimerization reaction of 1,3,5,7-tetrakis(4-acetylphenyl)adamantane in Ethanol/Xylenes mixture using SiCl4 as a catalyst. NPOF-4 is microporous and has high surface area (SABET = 1249 m2 g-1). Post-synthesis modification of NPOF-4 by nitration afforded (NPOF-4-NO2) and subsequent reduction resulted in an amine-functionalized framework (NPOF-4-NH2) that exhibits improved gas storage capacities and high CO2/N2 (139) and CO2/CH4 (15) selectivities compared to NPOF-4 under ambient conditions. These results demonstrate the impact of nitro- and amine- pore decoration on the function of porous organic materials in gas storage and separation application.

Activated carbons as emerging classes of porous materials have gained tremendous attention because of their versatile applications such as gas storage/separations sorbents, oxygen reduction reaction (ORR) catalysts and supercapacitor electrodes. This diversity originates from fascinating features such as low-cost, lightweight, thermal, chemical and physical stability as well as adjustable textural properties. More interestingly, sole heteroatom or combinations of various elements can be doped into their framework to modify the surface chemistry. Among all dopants, nitrogen as the most frequently used element, induces basicity and charge delocalization into the carbon network and enhances selective adsorption of CO2. Transformation of a task-specific and single source precursor to heteroatom-doped carbon through a one-step activation process is considered a novel and efficient strategy. With these considerations in mind, we developed multiple series of heteroatom doped porous carbons by using nitrogen containing carbon precursors. Benzimidazole-linked polymers (BILP-5), benzimidazole monomer (BI) and azo-linked polymers (ALP-6) were successfully transformed into heteroatom-doped carbons through chemical activation by potassium hydroxide. Alternative activation by zinc chloride and direct heating was also applied to ALP-6. The controlled activation/carbonization process afforded diverse textural properties, adjustable heteroatom doping levels and remarkable gas sorption properties. Nitrogen isotherms at 77 K revealed that micropores dominate the porous structure of carbons. The highest Brunauer-Emett-Teller (BET) surface area (4171 m2 g-1) and pore volume (2.3 cm3 g-1) were obtained for carbon synthesized by KOH activation of BI at 700 °C. In light of the synergistic effect of basic heteroatoms and fine micropores, all carbons exhibit remarkable gas capture and selectivity. Particularly, BI and BIPL-5 derived carbons feature unprecedented CO2 uptakes of 6.2 mmol g-1 (1 bar) and 2.1 mmol g-1 (0.15 bar) at 298 K, respectively. The ALP-6 derived carbons retained considerable amount of nitrogen dopants (up to 14.4 wt%) after heat treatment owing to the presence of more stable nitrogen-nitrogen bonds compared to nitrogen-carbon bonds in BILP-5 and BI precursors. Subsequently, the highest selectivity of 62 for CO2/N2 and 11 for CO2/CH4 were obtained at 298 K for a carbon prepared by KOH activation of ALP-6 at 500 °C.

Thesis (MScEng)--Stellenbosch University.
ENGLISH ABSTRACT: Carbon dioxide (CO2) is classified as the main greenhouse gas (GHG) contributing to global warming. Estimates by the Intergovernmental Panel on Climate Change (IPCC) suggest that CO2 emissions must be reduced by between 50 to 85% by 2050 to avoid irreversible impacts. Carbon capture and storage (CCS) strategies can be applied to de-carbonize the emissions from fossil-fueled power plants. Compared to other CCS techniques, post-combustion capture (PCC) is most likely to be implemented effectively as a retrofit option to existing power plants. At present however CCS is not yet commercially viable. The main challenge with CCS is to reduce the inherent energy penalty of the CO2 separation stage on the host plant. Seventy-five to eighty percent of the total cost of CCS is associated with the separation stage. There are several technologies available for separating CO2 from power plant flue gas streams. Reactive absorption with aqueous amine solutions has the ability to treat low concentration, low pressure and large flux flue gas streams in industrial-scale applications. It is most likely to be the first technology employed commercially in the implementation of CCS. The energy required for solvent regeneration however, is high for the standard solvent used in reactive absorption processes, i.e. MEA. This leads to a reduction in thermal efficiency of the host plant of up to 15%. Alternative solvent formulations are being evaluated in an attempt to reduce the energy intensity of the regeneration process. The main objective of this study was to establish a novel, simplified thermodynamic method for solvent screening. Partial solubility parameters (PSPs) were identified as the potential basis for such a method. The major limitation of this approach is that the model doesn’t account for effects from chemical reaction(s) between materials, e.g. CO2 reacting with aqueous alkanolamine solutions; considering only the effects from dissolution. The EquiSolv software system was developed based on PSP theory. The Hansen 3-set PSP approach was used to describe the equilibrium behaviour of CO2 absorbing in task specific solvents. The Hansen theory was expanded to a 4-set approach to account for contributions from electrostatic interactions between materials. The EquiSolv program was used successfully to screen large sets of solvent data (up to 400 million formulations) in the search for suitable alternative solvent formulations for CO2 absorption. The secondary objective of this study was to evaluate the ability of the proposed PSP model to accurately predict suitable alternative solvents for CO2 absorption through preliminary experimental work. A series of CO2 absorption experiments were conducted to evaluate the absorption performance of predicted alternative solvent formulations. The predicted alternative solvent formulations exhibited a significant improvement in absorption performance (up to a 97% increase in the measured absorption capacity) compared to conventional solvent formulations. Statistical analysis of the experimental results has shown that there is a statistically significant concordant relationship between the predicted and measured rankings for the absorption performance of the predicted solvent formulations. Based on this it was concluded that PSP theory can be used to accurately predict the equilibrium behaviour of CO2 absorbing in task specific solvents. Recently ionic liquids (ILs) have been identified as potential alternatives to alkanolamine solutions conventionally used for CO2 absorption. Absorption experiments were conducted as a preliminary assessment of the absorption performance of ILs. Results have shown ILs to have significantly improved performance compared to conventional alkanolamine solvents; up to a 96% increase in the measured absorption capacity compared to conventional solvents. Future work should focus on developing task specific ionic liquids (TSILs) in an attempt to reduce the energy intensity of solvent regeneration in CO2 absorption processes.
AFRIKAANSE OPSOMMING: Koolsuurgas (CO2) word geklassifiseer as die vernaamste kweekhuis gas (GHG) wat bydra to globale verwarming. Beramings deur die Interregeringspaneel oor Klimaatsverandering (IPKV) toon aan dat CO2 emissies teen 2050 verminder moet word met tussen 50 en 85% om onomkeerbare invloede te vermy. Verskeie koolstof opvangs en bergings (KOB) strategieë kan toegepas word ten einde die koolstof dioksied konsentrasie in die emissies van kragstasies wat fossielbrandstowwe gebruik, te verminder. Naverbranding opvangs (NVO) is die mees aangewese KOB tegniek wat effektief toegepas kan word op bestaande kragstasies. Tans is KOB egter nog nie kommersieël lewensvatbaarvatbaar nie. Die hoof uitdaging wat KOB in die gesig staar is om die energie boete inherent aan die CO2 skeidingstap te verminder. Tussen vyf-en-sewentig en tagtig persent van die totale koste van KOB is gekoppel aan die skeidingstap. Daar is verskeie metodes beskikbaar vir die skeiding van CO2 uit die uitlaatgasse van kragstasies. Reaktiewe absorpsie met waterige oplossings van amiene kan gebruik word om lae konsentrasie, lae druk en hoë vloei uitlaatgasstrome in industriële toepassings te behandel. Dit is hoogs waarskynlik die eerste tegnologie wat kommersieël aangewend sal word in die toepassing van KOB. Die oplosmiddel wat normalweg vir reaktiewe absorpsie gebruik word (d.w.s. MEA) benodig egter ‘n groot hoeveelheid energie vir regenerasie. Dit lei tot ‘n afname in die termiese doeltreffendheid van die voeder aanleg van tot 15%. Alternatiewe oplosmiddelstelsels word tans ondersoek in ‘n poging om the energie intensiteit van die regenerasieproses te verminder. Die hoof doelwit van hierdie studie was om ‘n nuwe, ongekompliseerde termodinamiese metode te vestig vir die keuring van alternatiewe oplosmiddels. Parsiële oplosbaarheidsparameters (POPs) is geïdentifiseer as ‘n moontlike grondslag vir so ‘n metode. Die model beskryf egter slegs die ontbindings gedrag van materiale. Die effekte van chemise reaksie(s) tussen materiale, bv. die tussen CO2 en waterige oplossings van alkanolamiene, word nie in ag geneem nie. Die POP teorie het gedien as grondslag vir die ontwerp van die EquiSolv sagteware stelsel. Die Hansen stel van drie POPs is gebruik om die ewewigsgedrag te beskryf van CO2 wat absorbeer in doelgerig-ontwerpte oplosmiddels. Die Hansen teorie is verder uitgebrei na ‘n stel van vier POPs om die bydrae van elektrostatiese wisselwerking tussen materiale in ag te neem. Die EquiSolv program is verskeie kere met groot sukses gebruik vir die sifting van groot stelle data (soveel as 400 miljoen formulasies) in die soektog na alternatiewe oplosmiddels vir CO2 absorpsie. Die sekondêre doelwit van die studie was om die vermoë van die voorgestelde POP model om geskikte alternatiewe oplosmiddels vir CO2 absorpsie akkuraat te voorspel, te ondersoek deur voorlopige eksperimentele werk. ‘n Reeks CO2 absorpsie eksperimente is gedoen ten einde die absorpsie werkverrigting van die voorspelde alternatiewe oplosmidels te ondersoek. ‘n Verbetering in absorpsie werkverrigting van tot 97% is gevind vir die voorspelde oplosmiddels vergeleke met die van oplosmiddels wat tipies in die industrie gebruik word. Statistiese ontleding van die eksperimentele resultate het getoon dat daar ‘n beduidende ooreenstemming tussen die voorspelde en gemete rangskikking van die voorspelde oplosmiddels se werkverrigting bestaan. Dus kan POP teorie gebruik word om die absorpsie van CO2 in doelgerig-ontwerpte oplosmiddels akkuraat te beskryf. Ioniese vloeistowwe (IVs) is onlangs geïdentifiseer as moontlike alternatiewe oplosmidels vir die alkanolamien oplossings wat normaalweg gebruik word vir CO2 absorpsie. Absorpsie eksperimente is gedoen ten einde ‘n voorlopige raming van die absorpsie werkverrigting van IVs te bekom. Daar is bevind dat IVs ‘n beduidende verbetering in werkverrigting toon in vergelyking met die alkanolamien oplosmiddels wat normaalweg gebruik word. ‘n Verbetering in absorpsie werkverrigting van tot 96% is gevind vir die voorspelde IV-bevattende oplosmiddels vergeleke met die van oplosmiddels wat tipies in die industrie gebruik word. Die fokus van toekomstige navorsing moet val op die ontwikkeling van doelgemaakte ioniese vloeistowwe (DGIVs) in ‘n poging om die energie intensiteit van oplosmiddel regenerasie in CO2 absorpsie prosesse te verminder.

This research investigates the existence of and potential challenges to the development of a transdisciplinary approach to the climate change mitigation technology research focusing on carbon dioxide capture, utilization, and storage (CCUS) in North America. The unprecedented challenge of global climate change is one that invites a transdisciplinary approach. The challenge of climate change mitigation requires an understanding of multiple disciplines, as well as the role that complexity, post-normal or post-modern science, and uncertainty play in combining these various disciplines.

This research followed the general discourse of transdisciplinarity as described by Klein (2014) and Augsburg (2016) which describe it as using transcendence, problem solving, and transgression to address wicked, complex societal problems, and as taught by California School of Transdisciplinarity, where the research focuses on sustainability in the age of post-normal science (Funtowicz & Ravetz, 1993).

Through the use of electronic surveys and semi-structured interviews, members of the North American climate change mitigation research community shared their views and understanding of transdisciplinarity (Kvale & Brinkmann, 2009). The data indicate that much of the research currently being conducted by members of the North American CCUS research community is in fact transdisciplinary. What is most intriguing is the manner in which researchers arrived at their current understanding of transdisciplinarity, which is in many cases without any foreknowledge or use of the term transdisciplinary.

The data reveals that in many cases the researchers now understand that this transdisciplinary approach is borne out of personal beliefs or emotion, social or societal aspects, their educational process, the way in which they communicate, and in most cases, the CCUS research itself, that require this transdisciplinary approach, but had never thought about giving it a name or understanding its origin or dimensions. Much of this new knowledge has come from the analysis and understanding of the Tier 1, Tier 2 and Emergent traits of the transdisciplinarian.

Orientador: Arnaldo Cesar da Silva Walter
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica
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Resumo: Atualmente o setor de refino de petróleo é responsável por cerca de 5% do total das emissões de CO2 relacionadas ao uso de energia no Brasil. O objetivo principal desta tese é avaliar as opções de mitigação de CO2 e seus respectivos custos para a REPLAN, que é a maior refinaria nacional. A revisão bibliográfica, a obtenção de informações adicionais na refinaria e a análise crítica das informações obtidas possibilitaram realizar uma prospecção de tecnologias de mitigação de emissões de CO2 para a indústria de refino. Através da utilização do conceito de Custo Marginal de Abatimento foi possível realizar a análise econômica das opções de mitigação de CO2 existentes na REPLAN. Os resultados mostram que melhorias de eficiência energética e substituição de combustível representam as estratégias mais promissoras para a redução das emissões de CO2 no curto prazo. Os custos de abatimento estimados são negativos (média de -130 US$/t CO2), o que significa que as medidas já são atrativas e poderiam ser implementadas imediatamente. Entretanto, o potencial global de redução é relativamente baixo (0,23 milhão de t CO2/ano, ou 6% do total das emissões). É mostrado ainda que a técnica de captura e armazenamento de carbono (CCS) oferece potencial para reduções mais significativas de emissões no longo prazo (até 1,62 milhão de t CO2/ano, ou 43% do total das emissões), mas os custos são bem maiores e, no cenário considerado, se situam na faixa de 64-162 US$/t de CO2, dependendo da fonte de emissão de CO2 (regeneradores de unidades de craqueamento catalítico ou unidades de geração de hidrogênio) e da tecnologia considerada para a captura de CO2 (oxi-combustão ou pós-combustão). Nesta tese é mostrado que as oportunidades remanescentes de melhoria de eficiência energética são limitadas na REPLAN. Dessa forma, CCS seria tecnicamente viável para reduzir as emissões de CO2, mas há uma série de questões políticas, legais, financeiras e técnicas que precisam ser superadas. Em caso de um cenário de restrição de emissões de gases de efeito estufa no Brasil, uma opção é considerar uma estratégia de mitigação de CO2 em duas etapas. A implementação de CCS poderia ser adiada para um período após 2020 até que a tecnologia se torne economicamente viável. Finalmente, o estudo de caso da REPLAN pode ser considerado como um plano de ação replicável para outras refinarias brasileiras
Abstract: Currently the oil refining sector is responsible for approximately 5% of Brazilian energy related CO2 emissions. The main objective of this thesis is to evaluate the CO2 mitigation options and their costs to REPLAN, which is the largest national refinery. The literature review, the achievement of additional information at the refinery and the critical analysis of information enabled to conduct a survey of CO2 emissions mitigation technologies for the refining industry. By using the concept of Marginal Abatement Cost it was possible to conduct an economic analysis of existing CO2 mitigation options at REPLAN. The results show that energy efficiency improvements and fuel substitution represent the most promising strategies for reducing CO2 emissions in the short term. The estimated abatement costs are negative (on average, about -130 US$/t CO2), meaning that the measures are already cost-effective and could be implemented immediately. However, the overall abatement potential is relatively low (0.23 million t CO2/year, or 6% of the total emissions). It is further shown that the technique of carbon capture and storage (CCS) offers the potential for more significant emission reductions in the long term (up to 1.62 million t CO2/year, or 43% of the total emissions), but costs are much higher and, in the considered scenario, are in the range of US$ 65-164/t CO2, depending on the CO2 emission source (regenerators of catalytic cracking units or hydrogen production units) and the CO2 capture technology considered (oxyfuel combustion or post-combustion). In this thesis it is shown that remaining opportunities of energy efficiency improvement are limited at REPLAN. Thus, CCS would be technically feasible to reduce CO2 emissions, but there are a number of political, legal, financial and technical issues that must be overcome. In case of a scenario with restriction of greenhouse gas emissions in Brazil, one option is to consider a two-step CO2 mitigation strategy. CCS implementation could be postponed for a period after 2020 until the technology becomes economically viable. Finally, the case study of REPLAN can be considered as a replicable action plan to other Brazilian refineries
Doutorado
Planejamento de Sistemas Energeticos
Doutor em Planejamento de Sistemas Energéticos

La problématique de cette thèse porte sur les conditions technico-économiques et sociales d’émergence des techniques de Captage, transport et Stockage géologique du Carbone (CSC) dans le secteur électrique. Il existe effectivement un hiatus entre le niveau actuel de déploiement du CSC et son rôle dans les scénarii climatique de long terme. Les travaux s’appuient sur deux approches complémentaires ; l’approche positive met en exergue les déterminants économiques et sociaux nécessaires à l’émergence du CSC et répond à deux interrogations : pour quel prix du CO2 devient-il intéressant d’investir dans des centrales CSC ? Quand l’usage du CSC est-il socialement optimal ? Sur le plan normatif, diverses recommandations relatives au déploiement optimal du CSC sont apportées. Elles concernent notamment le portefeuille optimal d’instruments de soutien au CSC. Cette thèse s’articule en quatre chapitres. Dans l’optique de minimiser les coûts de la transition énergétique, les deux premiers chapitres embrassent la vision investisseur et mettent en évidence les déterminants économiques indispensables au déploiement commercial du CSC. Les deux derniers chapitres adoptent la vision de la puissance publique. Bien que compétitive, une technologie peut ne pas se développer du fait de problèmes d’acceptabilité sociale ; c’est l’objet du modèle du Chapitre 3. Le Chapitre 4 élargit le propos et intègre la problématique de décision dans le CSC en univers ambigu, en s’appuyant sur des simulations numériques
This thesis analyses the techno-economic and social conditions required for the emergence of Carbon Capture and Storage (CCS) techniques in the power sector, in compliance with CCS role in long-term mitigation scenarios. The research combines two complementary approaches: the positive one deals with the economic and social determinants necessary to trigger CCS investments, and addresses two significant issues: (1) for which CO2 price is it worth investing in CCS plants, and (2) when is CCS use socially optimal? The normative approach gives recommendations on how CCS can best be deployed as part of a least cost approach to climate change mitigation. Notably, recommendations are provided about the optimal combination of CCS policy supports that should be implemented. This Ph.D. dissertation is composed of four chapters. The first two chapters embrace the investor’s vision and highlight the determinants necessary for CCS commercial emergence. The last two chapters embrace the public decision-makers’ vision. Based on the fact that, although cost-effective, one technology may not be deployed because of social acceptance issues, Chapter 3 deals with CCS public acceptance and optimal pollution. Chapter 4 goes further and addresses the optimal CCS investment under ambiguity by providing a decision criterion with simulations on the European Union’s 2050 Energy Roadmap

This article deals with main aspects of a novel technique for carbon dioxide capture and storage released by large combustion plants. Since this novel technique has become essential for reducing greenhouse gas emissions, it has been regulated by the European Union through the Directive number 2009/31. Therefore, acknowledging relevant legal aspects for regulation, suchas: mandatory, exploration permits, storage among others, the focus has been pointed out on responsibilities and guarantees regime.
El presente artículo desarrolla las principales aristas de la captura y almacenamiento del dióxido de carbono emanado de las grandes instalaciones de combustión, novedosa técnica que al tornarse imprescindible para la reducción de emisión de gases de efecto invernadero ha sido regulada porla Unión Europea (UE) a través de la directiva 2009/31. Así, tras reconocerlos aspectos jurídicos relevantes de su regulación —obligatoriedad, permisos de exploración y almacenamiento, entre otros— se incide en el régimen de responsabilidad y garantías.

Jordens befolkning behöver kraftigt reducera koldioxidutsläppen till atmosfären för att förhindra klimatförändringar. Klimatmål har sats upp av unioner och länder där de bland annat vill förhindra en global temperaturökning över 1.5 grader. För att uppnå dessa klimatmål menar forskare och institutioner på att stora mängder koldioxid kommer att behöva avskiljas vid utsläppskällor och lagras geologiskt (eng. carbon capture storage, förkortad CCS). I Sverige har ett fåtal CCS-projekt tagit fart men CCS är fortfarande inte kommersiellt tillgängligt. Frågeställningen för det här arbetet var därför: vilka är de mest relevanta utmaningar som kommersiellt tillgänglig CCS står inför idag i Sverige?Metoderna som användes var en litteraturstudie och tre\newline intervjuer. Personerna som intervjuades var en forskare från Chalmers Tekniska högskola, en chef från företaget Stockholm Exergi och en civilingenjör från projektet Northern lights. Utmaningarna delades in i kategorierna: tekniska-, politiska-, ekonomiska- och övriga utmaningar, för att enklare identifieras och jämföras. Resultaten visade att det fanns utmaningar i samtliga kategorier. Den tekniska utmaningen låg framförallt i att bygga upp och anpassa den tillgängliga CCS-tekniken till olika tillämpningsbara industrier. Politiskt var utmaningen främst att övertyga politiker att satsa på CCS, men också att införskaffa tillräckligt stora ekonomiska styrmedel, incitament och investeringar. Detta eftersom de som existerar idag antingen saknades helt eller ansågs vara för små. De ekonomiska utmaningarna var att stimulera investerare samt att bygga upp en fungerande och hållbar ekonomisk plan för CCS. I kategorin övriga utmaningar var den främsta utmaningen att övertyga befolkningen och att sprida kunskap kring CCS och dess potential. Avgränsningar i det här arbetet var framförallt bristen på resurser och tid. Fler intervjuer och en djupare litteraturstudie hade varit önskvärd för att fördjupa studien men begränsades av tid och möjligheter för kursens omfattning.
The world population need to reduce its carbon dioxide emissions to the atmosphere in order to prevent a climate change. Climate targets have been set by unions and countries to reduce carbon dioxide emissions before the average temperature rise exceeds 1.5 degrees Celsius. To achieve these climate goals, researchers and institutions believe large amounts of carbon dioxide needs to be stored below ground (carbon capture storage, abbreviated CCS). In Sweden have a small number of projects taken off, but CCS is still not commercially available. The question for this work was therefore: what are the most relevant challenges that commercially CCS currently faces in Sweden?The methods used were a literature study and three interviews.The persons interviewed were a researcher from Chalmers Tekniska university, a manager from the company Stockholm Exergi and an engineer from the Northern Lights project. The challenges were divided into four categories: technical-, political-, economic-, and other challenges, to make it easier to identify and compare. Results showed that there were challenges in all four categories. The technical challenge was mainly to build and adapt the available CCS technology to different types of industries. Politically, the challenge was primarily to increase their interest and support towards CCS. This along with the challenge of acquiring financial instruments, incentives and investments that was currently lacking or was too small. The economic challenges were to stimulate investors from both private and political quarters and to organize and operate a functioning and sustainable financial plan. In the category other challenges, the most mentioned challenge was convincing the population and to spread knowledge about CCS and its potential. Delimitations in this work was above all the lack of resources and time. More interviews anda deeper literature study would have been desirable to deepen the study but was limited by time and opportunities for the scope of the course.

BECCS (Bioenergy Carbon Capture and Storage) is an important part of measures to achieve zero net emissions globally by 2050, as the technology can create carbon sinks. However, the technology is very energy-intensive and expensive, and affects the existing systems at implementation. The purpose of this study is to investigate the possibility of implementing BECCS at Karlstad Energy's biofuel-fired CHP-plant, Heden 3. The goal is, by simulation in CHEMCAD, to generate energy consumption key figures for two different separation technologies (MEA-MonoEthanolAmine and HPC-HotPotassiumCarbonate) with 90 % separation rate in three different operating cases. In addition, the systemic impact on Heden 3 will be determined by analyzing three different scenarios. In the first scenario fuel consumption is kept unchanged and steam to the carbon capture system is extracted before the turbine. In the second scenario fuel supply increases to meet the district heating needs of the existing system and steam to the carbon capture system is extracted before the turbine. In the third scenario fuel supply is kept unchanged and steam is extracted from the turbine. In addition, the study investigates various transport options for storage of carbon dioxide and finally calculate the total carbon sink Karlstad Energy can contribute to. The results show that production of electricity is reduced by 65-87 % after implementation of MEA and 151-238 % for HPC in the first scenario. Without heat utilization in the carbon capture system, heat production is reduced by 66-86 % with MEA and 54-76% for HPC. In the second scenario, a fuel supply increase by 134 % is required to meet the needs, which corresponds to more than twice the boiler capacity and results in a reduced production of electricity by 247 %. In the third scenario, production of electricity is reduced by 104 % at maximum load with HPC. The HPC system has high-quality heat to utilize, probably enough to meet the district heating needs without increasing the boiler power. But heat optimization opportunities need to be further explored in order to be able to express something to a greater extent. The MEA process does not offer the same opportunities for heat utilization. As the CHP-plant have heat as the main product, HPC would be a more suitable alternative despite the high load on the electricity production. The performance of the carbon dioxide plant seems to vary between different operating cases and it can be concluded that the variation is related to the flue gas composition rather than being load dependent. Transport of carbon dioxide by train has the lowest carbon dioxide emissions and requires the least number of cargoes for transport from Karlstad to storage in Norway. However, this is not relevant at present because of the lack of rail connection to the plant. Total carbon sink is approximately 127 000 tonnes per year if the boiler capacity is assumed to be unchanged.
BECCS (Bioenergy Carbon Capture and Storage) är en viktig del av åtgärder i målet om att nå nollnetto utsläpp år 2050 globalt, då tekniken kan skapa kolsänkor. Tekniken är dock mycket energikrävande och dyr, och påverkar de befintliga systemen vid implementering. Syftet med den här studien är att undersöka möjligheten att implementera BECCS på Karlstad Energis biobränsleeldade kraftvärmeverk, Heden 3. Målet är att, genom simulering i CHEMCAD, ta fram förbrukningsnyckeltal för två olika avskiljningstekniker (MEA-MonoEtanolAmin och HPC-HotPotassiumCarbonate) med 90 % avskiljningsgrad vid tre olika driftfall. Dessutom ska systempåverkan på Heden 3 fastställas genom analys av tre olika scenarier. I första scenariot hålls bränsleförbrukningen oförändrad och ånga till koldioxidavskiljningssystemet tappas av innan turbinen. I det andra scenariot ökar bränsletillförseln för att tillgodose fjärrvärmebehovet i det befintliga systemet och ånga till koldioxidavskiljningssystemet tappas av innan turbinen. I det tredje scenariot hålls bränsletillförseln oförändrad och ånga extraheras från turbinen. Därtill undersöks i studien olika transportmöjligheter till lagringsplats av koldioxiden och slutligen beräknas den totala kolsänkan Karlstad Energi kan bidra med. Resultaten visar att elproduktionen i det första scenariot reduceras med 65-87 % för MEA och för HPC 151-238 %. Utan värmeutnyttjande från koldioxidavskiljningssystemen reduceras värmeproduktionen med 66-86 % med MEA och 54-76 % med HPC. I det andra scenariot krävs att bränsletillförseln ökar med 134 % för att tillgodose behoven vilket motsvarar mer än dubbla panneffekten och innebär en reducerad elproduktion på 247 %. I det tredje scenariot reduceras elproduktionen med 104 % vid maximal last med HPC.  I HPC-systemet finns högvärdig värme att utnyttja, sannolikt tillräckligt mycket för att kunna uppfylla fjärrvärmebehovet utan att öka panneffekten. Men värmeoptimeringsmöjligheter behöver undersökas ytterligare för att kunna uttrycka något i större omfattning. I MEA-processen finns inte samma möjligheter till värmeutnyttjande. Eftersom kraftvärmeverket har värme som främsta produkt skulle således HPC vara ett lämpligare alternativ trots den höga belastningen på elproduktionen. Koldioxidanläggningens prestanda förefaller variera mellan olika driftfall och med en enklare undersökning kunde slutsatsen dras att variationen har ett samband med rökgassammansättningen snarare än att det är ett lastberoende. Transport av koldioxid med tåg har lägst koldioxidutsläpp och kräver minst antal laster för transport från Karlstad till lagring i Norge. Detta är dock inte aktuellt i dagsläget på grund av avsaknaden av räls in till verket. Den totala kolsänkan är cirka 127 000 ton per år om pannan antas köras oförändrat.

La séparation du CO2 d'un mélange de gaz par cristallisation d'hydrates de gaz est un procédé qui pourrait à terme présenter une alternative intéressante aux techniques conventionnelles de capture du CO2. L'objectif de cette thèse était d'évaluer le potentiel de ce procédé "hydrates" pour séparer le CO2 d'un mélange CO2-CH4 riche en CO2. Nous avons étudié en particulier la sélectivité de la séparation vis-à-vis du CO2 et la cinétique de cristallisation des hydrates, ainsi que l'effet d'additifs thermodynamiques et cinétiques (et de certaines de leurs combinaisons) sur ces deux paramètres pour différentes conditions opératoires (pression, température, concentrations). Les expériences de formation/décomposition d’hydrates ont été réalisées en mode "batch" dans un réacteur haute pression faisant partie d'un pilote expérimental conçu et construit entièrement pendant cette thèse. Un modèle semi-empirique a été également développé pour estimer le taux de conversion de l’eau en hydrate et la composition des différentes phases en présence (hydrates, liquide et vapeur) à l'équilibre. Les résultats obtenus montrent que l'association du sodium dodécyl sulfate (SDS), utilisé en tant que promoteur cinétique, avec du tétrahydrofurane (THF), utilisé en tant que promoteur thermodynamique, permet d'obtenir des résultats intéressants en terme de quantité d'hydrates formés et de cinétique de formation. La sélectivité de la séparation vis-à-vis du CO2 reste cependant trop faible (en moyenne quatre molécules de CO2 piégées dans la structure de l'hydrate pour une de CH4) pour envisager d’utiliser ce procédé "hydrates" à plus grande échelle afin de séparer le CO2 de ce type de mélange de gaz
The separation of CO2 from a gas mixture by crystallization of gas hydrates is a process that could eventually provide an attractive alternative to the conventional techniques used for CO2 capture. The aim of this thesis was to evaluate the potential of this "hydrate" process to separate CO2 from a CO2-CH4 gas mixture, rich in CO2. We have studied in particular the selectivity of the separation toward CO2 and the hydrate crystallization kinetics. The effects of thermodynamic and kinetic additives (and some additive combinations) on these two parameters for different operating conditions (pressure, temperature, concentrations) were evaluated. Hydrate formation and dissociation experiments were performed in "batch mode” in a high pressure reactor, and with an experimental pilot rig designed and built entirely during this thesis. A semi-empirical model was also developed to estimate the water to hydrate conversion and the composition of the different phases (hydrates, liquid and vapor) at equilibrium. The results show that the combination of sodium dodecyl sulfate (SDS) used as a kinetic promoter, with tetrahydrofuran (THF) used as a thermodynamic promoter, provides interesting results in terms of both the amount of hydrates formed and the hydrate formation kinetics. The selectivity of the separation toward CO2 remains too low (an average of four CO2 molecules trapped in the hydrate structure for one of CH4) to consider using this "hydrate" process on a larger scale to separate CO2 from such a gas mixture

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Conforme reconhecido pelo Protocolo de Kyoto, planejar um futuro energético ecologicamente correto é o grande desafio do Século XXI. Os padrões atuais de recursos energéticos e de uso de energia se mostram prejudiciais para o bem-estar da humanidade ao longo prazo. A integridade dos sistemas naturais essenciais já está em risco devido às mudanças climáticas causadas pelas intensas emissões dos Gases de Efeito Estufa na atmosfera. Neste contexto, o Sequestro Geológico de Carbono (ou Carbon Capture and Storage – CCS) é uma atividade promissora que visa contribuir para a redução da emissão dos gases causadores do efeito estufa e a mitigação das alterações climáticas, por meio da captura, transporte e armazenamento de CO2 em formações geológicas adequadas (aquíferos salinos, reservatórios de hidrocarbonetos e reservatórios de carvão). Portanto, inserida neste cenário, esta Dissertação teve como objetivo analisar o potencial técnico do sequestro geológico de CO2 na Bacia do Espírito Santo onshore e offshore abordando os ambientes geológicos propícios para a aplicação de projetos de CCS, as fases que compõem estes projetos, seus investimentos e custos operacionais. Além disso, foi realizada a modelagem matemática da potencialidade de armazenamento assim como a estimativa de rentabilidade financeira com a execução do projeto de armazenamento por meio da venda do óleo extra produzido pela técnica de recuperação avançada de petróleo e pela comercialização dos Créditos de Carbono. Para isso, este projeto teve como estratégia metodológica: a xviii pesquisa exploratória e a revisão da literatura relacionada com o tema, a coleta de dados secundários, via análise de documentos, e a coleta de dados primários, via entrevistas com experts e participações em congressos nacionais e internacionais voltados para o tema. Sendo assim, conclui-se que os projetos de CCS são possíveis de implantação no estado do Espírito Santo, isto porque além da estrutura geológica dos reservatórios de petróleo e gás da bacia capixaba contribuir para bons resultados (pois, na maioria dos casos, são reservatórios areníticos com presença de rocha selante), o potencial dos aquíferos salinos capixabas e o potencial dos campos de hidrocarbonetos estudados nesta dissertação (Campo de Golfinho, Inhambú, Fazenda Alegre, Cação, Canapu, Cangoá, Peroá e Camarupim) merecem destaque nacional; entretanto, a falta de maturidade dos setores privado e público, com relação ao gerenciamento dos projetos desta natureza e ao seu uso em larga escala, impede o avanço de tais tecnologias no estado do Espírito Santo e, por consequência, no Brasil.
According to the Kyoto Protocol, planning an ecologically sustainable future is the greatest challenge of the 21st Century. Current patterns of energy resources and energy use are shown detrimental to the welfare of mankind in the long run. The integrity of essential natural systems is already at risk because of the climate change caused by the intense emission of greenhouse gases into the atmosphere. In this context, the Carbon Capture and Storage (CCS) technology is a promising activity that aims to reduce the emission of gases responsible by the greenhouse effect and climate change mitigation through CO2 capture, transport and storage in suitable geological formations (saline aquifers, coal reservoirs, oil and gas reservoirs). Therefore, inserted in this context, this dissertation has how objective analysis of the technical potential for carbon capture and geological sequestration of Espírito Santo onshore and offshore basin addressing amenable geologic environments to the application of CCS projects, phases that make up these projects, their investments and operational costs and the development of mathematical modeling for the calculations regarding the storage capability and calculation of estimated financial profitability along with its execution through the sale of extra oil produced by the advanced recovery technique of oil and the sale of carbon credits. For that, this project had how methodological strategy: the exploratory research and review of the literature on the subject, the collection of secondary data, via document analysis, and xx collecting primary data via interviews with experts and participation in national and international congress geared for the theme. Therefore, it is concluded that CCS projects are possible deployment in the state of Espírito Santo, this is because in addition to the geological structure of oil and gas reservoirs in the Espírito Santo basin contribute to good results (as, in most cases, are sandstone reservoirs with presence of seal rock), the potential of saline aquifers and the potential of hydrocarbon fields studied in this dissertation (Golfinho, Inhambú, Fazenda Alegre, Cação, Canapu, Cangoá, Peroá and Camarupim) deserve national recognition; however, the lack of maturity of the private and public sectors, with respect to the management of projects of this nature and their widespread use, prevents the advancement of such technologies in the state of Espírito Santo and therefore in Brazil.

Carbon dioxide from biogas production is currently considered to be without value and isbecause of this released into the atmosphere in the biogas upgrading process. The residualgas is a potential carbon source and can create value in the biogas manufacturing process.By finding a suitable value-creating process that utilizes carbon dioxide, it can be possibleto provide both economic and environmental incentives for companies to develop theiroperations. This project explored the possibility to create value from this CO2. Through anevaluation of the technical maturity of CCU technologies, a recommendation could be givenat the end of the project. An analysis of technical barriers, such as pollutants in the gas, aswell as barriers in the form of competence and corporate culture were examined in orderto provide a reasoned recommendation. The project mapped which value-creating systemswould be suitable for biogas producers in a Swedish context. This included established methaneand carbon dioxide upgrading techniques currently in use and suitable CCU techniquesthat can interact with the selected upgrading processes and serve as value creators. Based onthis survey, it was then possible to identify common, critical variables for these systems. Thereafter,a recommendation of an appropriate CCU technology could be given depending onthe CO2 composition produced. One conclusion from the study was that carbon dioxide concentrationsfrom the residual gas was often high (approx. 97-98 %) and did not contain anycorrosive or toxic components, and that this largely depends on how the digestion reactor ishandled in the production process. Thus, questions were raised about what the actual limitationsof the CCU are, as they did not seem to be technical. CCU techniques that proved to beof particular interest were pH regulation of sewage plants, CO2 as a nutrient substrate for thecultivation of microalgae, and manufacturing of dry-ice for refrigerated transports. All of thesetechnologies currently have a sufficiently high degree of technical maturity to be installedalready today. Other CCU techniques, such as "’Power to gas”, require a high CO2 concentrationand were discarded as the literature review did not suggest the economic potential forthem as they require additional CO2 upgrading steps. Instead, CCU techniques were chosenthat could be implemented directly with the existing CO2 quality. Furthermore, it was concludedthat one reason why CCU technologies have not been widely implemented is internalbarriers between distributors and manufacturers (or users) of CCU technologies. Thus, theuse of carbon dioxide from biogas production and implementation of CCU technologies canbe promoted by eliminating barriers in companies, such as a lack of both knowledge andfinancial incentives.
Koldioxid från biogasproduktion betraktas i dagsläget som utan värde och släpps ut i atmosfärenvid uppgradering av biogas. Restgasen är en potentiell kolkälla och kan vara värdeskapandeför biogasprocessen. Genom att finna en lämplig värdeskapande process som utnyttjarkoldioxid går det att ge både ekonomiska och miljömässiga incitament till företag att utvecklasin verksamhet. I detta projekt undersöktes möjligheten att skapa värde av denna CO2.Genom en utvärdering av den tekniska mognadsgraden hos CCU-tekniker kunde en rekommendationges vid projektets slut. En analys av tekniska hinder, såsom föroreningar i gassammansättningen,såväl som hinder i form av kompetens och företagskultur undersöktes för attkunna ge en motiverad rekommendation. I projektet kartlades vilka värdeskapande systemsom skulle passa för biogasproducenter i en svensk kontext. Detta inkluderade etableradeuppgraderingstekniker för metan- och koldioxid som används i dagsläget. I projektet undersöktesäven lämpliga CCU-tekniker som kan samverka med de valda uppgraderingsprocessernaoch och agera värdeskapande. Utifrån denna kartläggning kunde det sedan anges vilkagemensamma, kritiska variabler som finns för dessa system. Därefter kunde en rekommendationav lämplig CCU-teknik ges beroende på den producerade CO2 sammansättningen. Enslutsats i projektet var att koldioxid från restgasen ofta var av hög koncentration (ca. 97-98 %)och ej innehöll några korrosiva eller toxiska komponenter, och att detta till stor del beror påhur rötkammaren är hanterad i produktionsprocessen. Således väcktes frågor kring vilka defaktiska begränsningarna för CCU är, då de inte torde vara tekniska. CCU-tekniker som visadesig vara av särskilt intresse var pH-reglering av avloppsverk, CO2 som näringssubstratför odling av mikroalger, samt tillverkning av kolsyreis för kyltransporter. Samtliga dessatekniker har tillräckligt hög teknisk mognadsgrad för att kunna installeras i dagsläget. AndraCCU-tekniker, såsom ”Power to gas”, kräver en hög CO2-koncentration och avfärdades dålitteraturstudien inte talade för den ekonomiska potentialen i dessa eftersom de kräver ytterligareuppgraderingssteg för CO2. Således valdes istället CCU-tekniker som skulle gå attimplementera direkt med den befintliga CO2 kvalitén. Vidare drogs slutsatsen att en anledningtill att CCU-tekniker inte har blivit vida implementerade till stor del är interna hindermellan distributörer och tillverkare (eller utnyttjare) av CCU-tekniker. Således kan användandetav koldioxid från biogasproduktion och implementering av CCU-tekniker främjasgenom att eliminera hinder hos företag. I projektet yttrade sig detta som bristande ekonomiskaincitament och okunskap. Ett ökat användande av CCU-tekniker kan också uppnås genomatt införa lagar och regler som begränsar användandet av föråldrade tekniker som drivs avfossila bränslen, och som kan ersättas av klimatvänliga CCU-tekniker.

A necessidade atual do mercado brasileiro para aumentar a oferta de gás incentiva a comunidade científica nacional no desafio de desenvolvimento de novas rotas tecnológicas, visando aumentar o aproveitamento do gás natural. Tal desafio é acompanhado por uma demanda mundial dos países signatários do Protocolo de Quioto (ratificado em 2005) para a redução das emissões de gases de efeito estufa. Apesar de o Brasil não apresentar nenhuma meta de redução, no primeiro período deste Protocolo (2008 a 2012), o setor do petróleo (atividade de E&P), através de suas companhias operadoras, que atuam no país, já estabeleceram metas corporativas para emissão evitada de gases de efeito estufa, em suas instalações de produção (maior predominância das unidades marítimas de produção). O presente trabalho aborda a análise técnica e econômica de um processo proposto de separação e captura de dióxido de carbono (CO2), através de estudo de caso (Primeira e Segunda Proposição) de simulação de processo, em uma instalação marítima de produção de petróleo, comparativamente a sua ausência (Caso Base). A Primeira Proposição considera a separação e a captura do CO2 oriundo tanto do gás natural produzido, quanto do gás de queima de uma turbina a gás. A Segunda Proposição considera a separação e a captura do CO2 oriundo somente do gás natural produzido. Até o momento, no Brasil, ainda não foram desenvolvidas tecnologias adequadas para a captura do CO2, em instalações marítimas de produção de petróleo. Adicionalmente a regulação atual (Portaria nº104/2002 da ANP) limita o potencial de utilização do CO2 que existe na composição do gás natural comercializado no país, pelo fato de não diferenciar em sua especificação técnica, os usos deste importante combustível. Os resultados obtidos nesta tese, com a utilização de simulador de processo de uso comercial mostraram emissões evitadas de CO2 para atmosfera de 55 % (caso Segunda Proposição que apresentou maior viabilidade econômica), em relação ao resultado obtido para o Caso Base. Este relevante resultado equivale a uma emissão evitada de aproximadamente 241 x 103 t/ano, para uma única unidade piloto proposta. De acordo com o estudo de análise econômica apresentado, a Segunda Proposição (VPL US$ 15,3 x 106) foi melhor do que a da Primeira Proposição (VPL: US$ 13,9 x 106) ambos usando o Caso Base como referência. Dentre os ganhos esperados com o uso desta nova tecnologia destacam-se: redução do consumo interno e das perdas de gás natural, emissão evitada de CO2 e hidrocarbonetos para a atmosfera, além do aumento das práticas de armazenamento de gás e CO2, em reservatórios geológicos depletados de petróleo. Estima-se que num cenário futuro, com a implantação deste novo processo proposto, em instalações marítimas de produção de petróleo, uma relevante contribuição de emissões evitadas de gases de efeito estufa possa ocorrer na área de E&P de petróleo no Brasil.
The current Brazilian market needs to increase the natural gas supply to incentive the national scientific community to the challenge of developing new technologies routes aiming increase the utilization of the produced natural gas. Such challenge is followed by a world demand from signatory countries of the Kyoto Agreement (ratified in 2005) to reduce the greenhouse gas emissions. In spite of, the Brazil does not have any reduction goal, in the first period (2008 to 2012) the oil sector (E&P activity), by their oil operators companies that works in our country, has already established corporative goals to avoided greenhouse gas emissions in their production facilities (bigger predominance of offshore production unities). The present work approaches the economic and technical evaluation of a carbon dioxide (CO2) separation and capture proposal process (First and Second Proposal Case) comparatively your absence (Base Case). The First Case consider the CO2 separation and capture both the produced gas and exhausted gases of one turbine driven by gas. The Second Case consider only the CO2 separation and capture from the produced gas. At the present, in Brazil, it has not been developed yet suitable technologies, for such use, and the CO2 is normally disposal to the atmosphere. Moreover, the present Regulation (104/2002 ANP Decree) limit the potential of CO2 use existing in the gas composition that is marketed in the country, due to not differentiate the uses of this important fuel. The results obtained of this thesis, by using a process simulator of commercially use showed CO2 avoided emissions of 55 % to the atmosphere (Second Proposal Case that shows the best economic evaluation) related to the result obtained from the Base Case. This relevant result is equivalent in mass flow, to the avoidance emission of roughly 241 x 103 tons per year, for a single pilot unity proposal. According the economic evaluation study, the Second Proposal Case (VPL:US$ 15,3 x 106) was better than the First Case (VPL: US$ 13,9 x 106), using the Case Base as reference. Within the benefits expected with the use of this new technology are the following: reduction both the internal gas consumption and natural gas losses (atmospheric disposal), emissions avoided of CO2 and hydrocarbons, beyond the increase of CO2 and gas storage practices in offshore depleted oil fields. It is estimated, in future scenery, with the implantation of this new proposal process in offshore production unities, relevant contribution of avoided greenhouse gases emissions can occur in oil E&P tasks in Brazil.

L'atténuation du changement climatique est l'un des défis majeurs de notre époque. Les émissions anthropiques de gaz à effet de serre ont augmenté de façon continue depuis la révolution industrielle, provoquant le réchauffement climatique. Un ensemble de technologies très diverses doivent être mises en œuvre pour respecter les accords internationaux relatifs aux émissions de gaz à effet de serre. Certaines d'entre elles ont recours au sous-sol pour le stockage de diverses substances. Cette thèse traite plus particulièrement de la dynamique du stockage souterrain du dioxyde de carbone (CO2) et de l'hydrogène (H2). Des modèles numériques de transport réactif et multiphasiques ont été élaborés pour mieux comprendre la migration et les interactions des fluides dans des milieux poreux de stockage souterrain. Ils fournissent des recommandations pour améliorer l'efficacité, la surveillance et la sécurité du stockage. Trois modèles sont présentés dans ce document, dont deux dans le domaine du captage et du stockage du CO2 (CCS pour Carbon Capture and Storage), et le troisième s'appliquant au stockage souterrain de l'hydrogène (UHS pour Underground Hydrogen Storage). Chacun d'entre eux traite plus spécifiquement un aspect de la recherche : Modèle multiphasique appliqué au CCS L'efficacité et la sécurité à long terme du stockage du CO2 dépend de la migration et du piégeage du panache de CO2 flottant. Les grandes différences d'échelles temporelles et spatiales concernées posent de gros problèmes pour évaluer les mécanismes de piégeage et leurs interactions. Dans cet article, un modèle numérique dynamique diphasique a été appliqué à une structure aquifère synclinale-anticlinale. Ce modèle est capable de rendre compte des effets de capillarité, de dissolution et de mélange convectif sur la migration du panache. Dans les aquifères anticlinaux, la pente de l'aquifère et la distance de l'injection à la crête de l'anticlinal déterminent la migration du courant gravitaire et, donc, les mécanismes de piégeage affectant le CO2. La structure anticlinale arrête le courant gravitaire et facilite l'accumulation du CO2 en phase libre, en dessous de la crête de l'anticlinal, ce qui stimule la mise en place d'une convection et accélère donc la dissolution du CO2. Les variations de vitesse du courant gravitaire en raison de la pente de l'anticlinal peuvent provoquer la division du panache et une durée différente de résorption du panache en phase libre, qui dépend de l'endroit de l'injection
Climate change mitigation is one of the major challenges of our time. The anthropogenic greenhouse gases emissions have continuously increased since industrial revolution leading to global warming. A broad portfolio of mitigation technologies has to be implemented to fulfill international greenhouse gas emissions agreements. Some of them comprises the use of the underground as a storage of various substances. In particular, this thesis addresses the dynamics of carbon dioxide (CO2) and hydrogen (H2) underground storage. Numerical models are a very useful tool to estimate the processes taking place at the subsurface. During this thesis, a solute transport in porous media module and various multiphase flow formulations have been implemented in COMSOL Multiphysics (Comsol, 2016). These numerical tools help to progress in the understanding of the migration and interaction of fluids in porous underground storages. Three models that provide recommendations to improve the efficiency, monitoring and safety of the storages are presented in this manuscript: two in the context of carbon capture and storage (CCS) and one applied to underground hydrogen storage (UHS). Each model focus on a specific research question: Multiphase model on CCS. The efficiency and long-term safety of underground CO2 storage depend on the migration and trapping of the buoyant CO2 plume. The wide range of temporal and spatial scales involved poses challenges in the assessment of the trapping mechanisms and the interaction between them. In this chapter a two-phase dynamic numerical model able to capture the effects of capillarity, dissolution and convective mixing on the plume migration is applied to a syncline-anticline aquifer structure. In anticline aquifers, the slope of the aquifer and the distance of injection to anticline crest determine the gravity current migration and, thus, the trapping mechanisms affecting the CO2. The anticline structure halts the gravity current and promotes free-phase CO2 accumulation beneath the anticline crest, stimulating the onset of convection and, thus, accelerating CO2 dissolution. Variations on the gravity current velocity due to the anticline slope can lead to plume splitting and different free-phase plume depletion time is observed depending on the injection location. Injection at short distances from the anticline crest minimizes the plume extent but retards CO2 immobilization. On the contrary, injection at large distances from anticline crest leads to large plume footprints and the splitting of the free-phase plume. The larger extension yields higher leakage risk than injection close to aquifer tip; however, capillary trapping is greatly enhanced, leading to faster free-phase CO2 immobilization. Reactive transport model on convective mixing in CCS. Dissolution of carbon-dioxide into formation fluids during carbon capture and storage (CCS) can generate an instability with a denser CO2-rich fluid located above the less dense native aquifer fluid. This instability promotes convective mixing, enhancing CO2 dissolution and favouring the storage safety

The objective of this thesis is to provide an extensive description of the correlations in some of the most crucial sub-processes for hard coal fired IGCC with carbon capture (CC-IGCC). For this purpose, process simulation models are developed for four industrial gasification processes, the CO-shift cycle, the acid gas removal unit, the sulfur recovery process, the gas turbine, the water-/steam cycle and the air separation unit (ASU). Process simulations clarify the influence of certain boundary conditions on plant operation, performance and economics. Based on that, a comparative benchmark of CC-IGCC concepts is conducted. Furthermore, the influence of integration between the gas turbine and the ASU is analyzed in detail. The generated findings are used to develop an advanced plant configuration with improved economics. Nevertheless, IGCC power plants with carbon capture are not found to be an economically efficient power generation technology at present day boundary conditions.

Dans un contexte de croissance effrénée de la demande mondiale d'énergie et de pression environnementale pour lutter contre le réchauffement climatique, cette thèse étudie une des technologies envisagées pour réduire les émissions de dioxyde de carbone (CO2) : la capture et le stockage géologique du carbone (CSC). Nous étudions principalement l’application de cette technologie à la production des bioénergies (BCSC) car ce procédé permet d’épurer l’atmosphère tout en fournissant un substitut énergétique non polluant aux énergies fossiles. La première partie de ce travail analyse le potentiel économique et environnemental de la technologie de BCSC. Tout d'abord, une évaluation économique et environnementale de la BCSC dans le secteur de la production de bioéthanol en France est conduite.Ensuite, grâce à un modèle bottom-up d’optimisation TIAM-FR, nous étudions le potentiel global et régional de cette technologie dans le secteur de l'électricité. Enfin, les incitations économiques à mettre en place pour assurer son développement sont mises en évidences. Dans la deuxième partie, un modèle d'équilibre général calculable est utilisé pour évaluer les politiques environnementales. Nous construisons le modèle théorique en introduisant les technologies de CSC et de BCSC ainsi qu’une large variété d’instruments économiques. Le modèle est ensuite calibré pour comparer l’efficacité économique des instruments de politique environnementale à un niveau mondial et à un niveau français
In a context of unbridled growth of global energy demand and environmental pressure in the fight againstglobal warming, this thesis studies one of the proposed technologies to reduce carbon dioxide (CO2)emissions: carbon capture and geological storage (CCS). We therefore consider the application of thistechnology to the production of bioenergies (BCCS) because this technology allows purifying theatmosphere while providing a clean energy alternative to fossil fuels. The first part of this work analyzesthe economic and environmental potential of BCCS. First, an economic and environmental assessment ofBCCS in the bioethanol production in France is conducted. Then, using the bottom-up optimization modelTIAM-FR, we study the global and regional potential of this technology in the electricity sector. Finally,the economic incentives that need to be provided to ensure BCCS deployment are highlighted. In thesecond part, a general equilibrium model is used to evaluate environmental policies. We construct thetheoretical model by introducing the CCS and BCCS as well as a wide range of economic instruments.The model is then calibrated to compare the effectiveness of environmental policy instruments at a globallevel and at a French level

This thesis analyses two strategies for decreasing anthropogenic carbon dioxide (CO2) emissions: to capture and store CO2, and to increase the use of biomass. First, two concepts for CO2 capture with low capture penalties are evaluated. The concepts are an integrated gasification combined cycle where the oxygen is supplied by a membrane reactor, and a hybrid cycle where the CO2 is captured at elevated pressure. Although the cycles have comparatively high efficiencies and low penalties, they illustrate the inevitable fact that capturing CO2 will always induce significant efficiency penalties. Other strategies are also needed if CO2 emissions are to be forcefully decreased. An alternative is increased use of biomass, which partially could be used for production of motor fuels (biofuels). This work examines arguments for directing biomass to the transport sector, analyses how biofuels (and also some other means) may be used to reduce CO2 emissions and increase security of motor fuel supply. The thesis also explores the possibility of reducing CO2 emissions by comparatively easy and cost-efficient CO2 capture from concentrated CO2 streams available in some types of biofuel plants. Many conclusions of the thesis could be associated with either of three meanings of the word sense: First, there is reason in biofuel production – since it e.g. reduces oil dependence. From a climate change mitigation perspective, however, motor fuel production is often a CO2-inefficient use of biomass, but the thesis explores how biofuels’ climate change mitigation effects may be increased by introducing low-cost CO2 capture. Second, the Swedish promotion of biofuels appears to have been governed more by a feeling for attaining other goals than striving for curbing climate change. Third, it seems to have been the prevalent opinion among politicians that the advantages of biofuels – among them their climate change mitigation benefits – are far greater than the disadvantages and that they should be promoted. Another conclusion of the thesis is that biofuels alone are not enough to drastically decrease transport CO2 emissions; a variety of measures are needed such as fuels from renewable electricity and improvements of vehicle fuel economy.
QC 20100823

En vue de réduire à moyen terme les émissions de gaz à effet de serre d'origine anthropique, le captage-transport-stockage du dioxyde de carbone (CO2) est considéré comme une technologie prometteuse. Plusieurs sites pilotes existent déjà dans le monde. Cependant, avant de développer la technique de façon industrielle, des recherches expérimentales et numériques doivent être menées afin de garantir le succès et la pérennité d'un projet de stockage. Sur un site de stockage, les discontinuités naturelles ainsi que le(s) puits d'injection constituent des chemins préférentiels pour des fuites éventuelles. Ce travail de doctorat s'attache à l'étude des effets de la présence de dioxyde de carbone sur les géomatériaux en présence et, plus particulièrement, sur le ciment du puits d'injection. L'intégrité du puits et donc la garantie de son étanchéité est critique au niveau de la roche de couverture. Après injection et remontée du panache de dioxyde de carbone vers la roche de couverture, le ciment du puits au niveau de la zone triple (puits/réservoir/couverture) est en contact avec un fluide saturé en CO2 dissous. Un tel fluide, au pH acide, est amené à réagir avec les géomatériaux et entraîne diverses réactions de dissolution des minéraux de la matrice cimentaire ainsi que des réactions de précipitation pouvant altérer le matériau. Ce couplage fort existant entre réactions chimiques et comportement poro-mécanique du ciment du puits peut en effet induire un endommagement de la matrice cimentaire, lié aux modifications de la porosité et des caractéristiques de transport, à la dégradation des modules mécaniques, ou encore à la création de surpressions interstitielles localisées. Un modèle constitutif entièrement couplé a été développé pour simuler le comportement chimio-poromécanique du ciment en présence d'un fluide chargé de CO2. Ce modèle a été implémenté dans deux codes numériques, à savoir, un code aux volumes finis d'une part, et un code aux éléments finis, BIL, développé au Laboratoire Navier, d'autre part. La première implémentation se révèle être bien adaptée aux problèmes de transport réactif à front raide, et est utilisée dans ce mémoire pour modéliser une géométrie unidimensionnelle alliant ciment du puits et roche de couverture. La seconde méthode d'implémentation est quant à elle mieux adaptée à la modélisation du comportement poro-mécanique du ciment, mais, comme nous le verrons, nécessite des adaptations numériques a fin d'être convenable pour la modélisation de phénomènes chimiques impliquant des discontinuités. L'endommagement mécanique lié aux phénomènes chimiques est évalué d'une part via une approche micro-mécanique simplifiée, et d'autre part par une théorie de l'endommagement isotrope. En fin, en ce qui concerne la seconde approche, les résultats sont comparés à des tests expérimentaux issus de la littérature scientifique dans le contexte du stockage géologique du CO2
In order to reduce in medium-term the anthropogenic original greenhouse gas, the processes of capture-transport-storage of carbon dioxide (CO2) is considered as a promising technology. Several pilot sites already exist in the world. However, before developing the technology on an industrial scale, experimental and numerical researches have to be performed in order to ensure the success and the sustainability of a storage project. In a storage site, the natural discontinuities of the rocks and of the injection wells are normally the preferential leak paths of CO2. In this context, the present PhD research focuses particularly on the cement injection wells. The problems of the integrity of the well and thus ensuring its sealing are the critical points of the caprock.After the injection and the ascent of the CO2 plume to the caprock, the cement paste of well at the triple zone (well/ reservoir/caprock) is contacted with a fluid saturated with dissolved CO2. Because of its acidity, such a fluid is reacted with geomaterials and causes diverse reactions of dissolution of the minerals in the cementitious matrix and precipitation reactions that may affect the material. This strong coupling existing between the chemical reactions and poro-mechanical behavior of the cement well can indeed induce damage to the cementitious matrix related to the modifications of the porosity and the transport characteristics, to the degradation of mechanical modulus, or to the development of localized pore pressure.A constitutive model fully coupled has been developed to simulate the chemo-poro-mechanical behaviour of the hard cement paste of the well with the presence of a CO2-rich fluid. This model has been implemented in two numerical codes: on the one hand, a finite volume code, and on the other hand, a finite element code, BIL, developed at the Navier Laboratory. The first implementation was found to be well adapted to the problems of reactive transport with sharp front, and is used in this thesis to modeling an one-dimensional geometry by combining the cement well and the caprock. The second implementation method is best suited to modeling the poro-mechanical behavior of cement, but, as we shall see, requires numerical adaptations in order to be suitable for modeling chemical phenomenon involving discontinuities. The mechanical damage related to chemical phenomena is evaluated firstly via a simplified micro-mechanical approach, and secondly a theory of isotropic damage. Finally, the results are compared to experimental tests from the scientific literature in the context of the CO2 geosequestration

La conversion de la biomasse en énergie génère des flux de gaz carbonique qui peuvent être captés,transportés puis stockés dans des strates géologiques. Ce procédé, nommé BCCS (Biomass Carbon Captureand Storage), réduit drastiquement les émissions carbonées et dans certaines conditions le puits artificiel peutstocker plus de carbone que le système de conversion n’en aura produit (émissions négatives). Ainsi, le BCCSrend plus envisageable l’obtention de certains plafonds de concentrations de CO2 atmosphériques inférieurs ouégaux à 450ppm. Des incitations économiques sont nécessaires pour déclencher l’investissement dans leBCCS de la part d’acteurs du secteur privé. Ceux-ci sont confrontés à une incertitude de grande ampleurconcernant le prix du carbone. Nous étudions dans cette thèse le comportement d’un décideur ayant le choixd’investir dans une variante du BCCS, à savoir la production de bioéthanol à partir de betteraves sucrières.Après une analyse déterministe sur un cas réel, nous étudions l’influence de différentes incertitudes sur le profild’investissement via une approche par options réelles. Nous analysons notamment l’influence de l’incertitudedu progrès technique via une loi de Poisson et montrons que l’investisseur tend à attendre l’innovation. Nousdistinguons ensuite progrès de court terme et de long terme. Puis, nous nous intéressons à l’incertitude derégulation climatique. Le marché du carbone est alors modélisé par un mouvement de retour à la moyenneavec des sauts de prix à dates fixes
Using biomass to produce energy emits carbon dioxide. These emissions can be captured, transported andstored into geological formations. This process is named BCCS (Biomass Carbon Capture and Storage). Itleads to massive reductions and the whole system carbon balance system could be negative given specificassumptions, which is called ‘negative emissions’. BCCS may help to achieve low CO2 concentration target,even below the 450ppm threshold. Providing suitable incentives is necessary to trigger private investment.Private investors are facing considerable uncertainty, about the carbon market. We study in this dissertation thebehavior of decision makers who can invest in a specific variant of BCCS, which is the production ofbioethanol coming from sugar beets. After a deterministic analysis based on a real case study, we consider theinfluence of different kinds of uncertainties on the investment profile through a real option approach. Thetechnical progress uncertainty has been modeled with Poisson jumps. We show that investors tend to wait forinnovations. We distinguish two cases depending on the progress rate: early or delayed technical progressrate. First allowance price is driven by geometric Brownian motion. Second, the price follows a mean revertingprocess with jumps at specific fixed dates, to take into account the international round of negotiations aboutclimatic change, as a kind of climate regulation uncertainty

To curb greenhouse gases and mitigate climate change is one of the biggest challenges human society face today. Carbon dioxide (CO2) has accumulated rapidly in the atmosphere as a consequence of burning of fossil fuels and deforestation. The aim of this study is to explore two methods to store carbon dioxide in geological formations and biological sinks. The aim is also to discuss the two mitigation options from a sustainable perspective and whether it can lead to a better environment and benefits for local and global societies. The research questions are: Which method to store carbon dioxide, geological or biological, is the most effective? Which method to store carbon dioxide, geological or biological, has the greatest potential to promote sustainable development for local communities? The method used is a comparative case study and presents four case studies that explore the potential for CO2 storage offshore in Norway and Brazil; and in tropical forests in Mexico and Brazil. The mitigation options are discussed from two different theoretical perspectives. The principle of the theory of ecological modernisation is that innovation and environmentally friendly technology can solve the environmental problems human societies face today, whereas the theory of common pool resources promotes local communities to govern limited resources in order to manage them sustainably. The findings suggest that ecological modernisation legitimize environmental destruction as carbon dioxide storage in geological formations (CCS) use the technology as a mean to extract more oil and gas; which results in a rebound-effect. Therefore, carbon dioxide capture in geological formations is not a realistic method unless it can prevent further emissions. Protected forest resources can be seen as biological insurance, which safeguard ecosystem services, biodiversity, and the forest potential to hold carbon. Carbon sequestration in tropical forest has the potential to store carbon dioxide given that the forests are protected and local communities have tenure rights, knowledge, and the means to protect the forest and manage them sustainably.

Im Rahmen dieser Arbeit werden Konzepte für Gasaufbereitung in Kombikraftwerken mit integrierter Wirbelschichtvergasung und CO2-Abtrennung untersucht (IGCC-CCS). Dabei stehen die Konvertierung von Kohlenmonoxid (CO-Shift) und die Einbindung dieses Prozeß-schrittes in ein IGCC-CCS-Kraftwerk im Mittelpunkt. Ziel der Arbeit ist die energetische und wirtschaftliche Bewertung von Konzepten zur CO2-Abtrennung für ein ab 2015 baubares, grundlastfähiges IGCC-CCS-Kraftwerk der 800-MW-Klasse. Dazu werden neben den bekannten konventionellen, mehrstufigen Konzepten der Rohgas- und Reingas-Shift weitere alternative Ansätze zur Steigerung des Anlagenwirkungsgrades sowie zur Senkung der spezifischen CO2-Emission verfolgt. Die Ergebnisse der mit Hilfe von ASPEN Plus und EBSILON Professional durchgeführten Prozesssimulationen werden im Vergleich zu Dampfkraftwerken neuester Bauart wirtschaftlich bewertet.

Les technologies de captage, transport et stockage du CO2 ont pour finalité de capter le CO2 issu des industries afin de le stocker géologiquement et ainsi, réduire l impact de ces activités sur le réchauffement climatique. L Axe-Seine (Paris Le Havre) est un territoire très industrialisé et fortement émetteur de CO2. Dans ce territoire, les décideurs locaux envisagent l utilisation des technologies de CTSC afin de réduire les émissions de gaz à effet de serre. L objectif de notre recherche est de comprendre les futurs possibles de ces technologies dans l Axe-Seine. Dans cette perspective, cette thèse analyse tout d'abord le fonctionnement des technologies de CTSC dans une approche de sociologie des sciences et des techniques et les promesses technoscientifiques initiales associées à ce dispositif technique. Ensuite, cette recherche examine les dynamiques socio-spatiales de la vallée de la Seine concernant l'environnement. Enfin, cette thèse par une exploration des récits relatifs aux technologies de CTSC par les promoteurs de ce dispositif technique et des parties prenantes locales, identifie les hybridations potentielles entre ce dispositif technique et les dynamiques socio-spatiales de l'Axe-Seine. Ainsi est-il possible de décrire les futurs possibles des technologies dans l'Axe-Seine. Par ailleurs, dans cette recherche nous questionnons également la place des sciences sociales au côté des sciences de la vie et de la matière dans la dynamique de l'innovation technologique
Carbon Capture and Storage enables industrial facilities to capture their CO2 emissions in order to geologically store it and then reduce their impact on global warming. The Seine Waterway Axis (from Paris to Le Havre) counts a lot of industrial facilities emitting huge quantities of CO2. From 2006 local stakeholders of this territory are willing to develop CCS to a commercial scale in order to reduce CO2 emissions.In our research we aim to understand potential futures of CCS technology in the Seine Waterway Axis. In this Phd thesis we first analyse initial technoscientific promises related to Carbon Capture and Storage in using Science and Technology Studies theoretical framework. Then we focus on the Seine Waterway Axis territorial dynamics regarding sustainable development. Finnaly, we focus on narratives related to Carbon Capture and Storage in the Seine Waterway Axis in order to identify hybridations between CCS implementations and territorial dynamics. These cross analysis will enable us to describe potential future of CCS establishment in the Seine Waterway Axis

Carbon dioxide is released by natural and anthropogenic processes, such as the production and combustion of fossil fuels. Production of biogas also generates carbon dioxide, but of biogenic origin. The global, yearly emissions of greenhouse gases are regularly increasing, although agreements such as the Paris Agreement is signed by parties globally. Sweden has the goal to reach net-zero emissions by 2045, and thereafter to only obtain negative emission levels. To reach these goals the biogenic version of Carbon Capture and Storage (CCS) called Bioenergy with Carbon Capture and Storage (BECCS) is considered to be an essential strategy. Using carbon dioxide, through Carbon Capture and Utilization (CCU), in for example products, can complement BECCS since the strategy can increase the value of carbon dioxide. These strategies make it possible to reduce the climate impact of biogas production.  This master thesis aimed to chart different techniques in CCS and CCU to examine how they can be used to utilize or store carbon dioxide from biogas plants. What technical demands different solutions create was explored. The different techniques were assessed through a multi criteria analysis by a technological, environmental, marketable and economical standpoint to investigate which ones were the most suitable for a specific, studied case – Tekniska verken’s biogas plant. One suitable technique within CCU was analyzed through a screening of actors in the region. An environmental assessment of one technique in CCS and one in CCU were compared with the reference case Business as usual, to explore how a simulated biogas plant’s climate impact can change through the implementation of CCS and CCU.  The charting of literature gave findings of 42 different techniques, which were sifted down to 7; algae farming for wastewater treatment, BECCS in saltwater aquifers, carbon dioxide curing of concrete, bulk solutions, production of methanol, production of methane through Power To Gas and crop yield boosting in greenhouses. The multi criteria analysis pointed out carbon dioxide curing of concrete and BECCS in saltwater aquifers as suitable solutions for the studied case. The implementation of these techniques requires a liquefaction plant, infrastructure for transportation as well as business partners.  A life cycle assessment of the studied cases climate impact was given through modelling and simulation of a model plant of the studied case, with the functional unit 1 Nm3 biomethane. The reference case Business as usual had a climate impact of 0,38 kg CO2 eq, which corresponds to approximately one eighth of the climate impact of fossil fuels such as gasoline or diesel. By storing the carbon dioxide through BECCS in saltwater aquifers the climate impact decreased to - 0,42 kg CO2 eq. By utilizing the carbon dioxide through curing of concrete the biomethane’s climate impact decreased to -0,72 kg CO2 eq. The results thereby evince that Swedish biogas producers can improve their climate performance through CCS and CCU.
Koldioxid släpps ut av såväl naturliga som antropogena processer, exempelvis vid produktion och förbränning av fossila bränslen. Även vid biogasproduktion uppkommer koldioxid, men av biogent ursprung. Årliga globala utsläpp av växthusgaser ökar regelbundet, trots överenskommelser som Parisavtalet som syftar till att begränsa klimatförändringarna. Sverige ska nå nettonollutsläpp senast 2045 och därefter ha negativa utsläppsnivåer. För att uppnå detta mål anses en biogen version av Carbon Capture and Storage (CCS), det vill säga avskiljning och lagring av koldioxid, kallad Bioenergy with Carbon Capture and Storage (BECCS) vara en essentiell strategi. Tillvaratagande av koldioxid, genom Carbon Capture and Utilization (CCU), kan ge ett bra komplement till BECCS eftersom det nyttiggör koldioxid i produkter och kan öka värdet av koldioxid. Tekniker inom CCS och CCU möjliggör minskad klimatpåverkan inom biogasproduktion.  Detta examensarbete syftade till att kartlägga olika alternativ inom teknikerna CCS och CCU för att undersöka hur dessa kan användas för att nyttiggöra eller lagra koldioxid från biogasanläggningar, samt att undersöka vilka tekniska krav som ges av lösningarna. Utifrån en multikriterieanalys bedömdes vilka lösningar som var tekniskt, miljömässigt, marknadsmässigt och ekonomiskt motiverade för tillvaratagande av koldioxid. Bedömningen genomfördes genom att studera specifikt fall som var Tekniska verken i Linköpings biogasanläggning. Den lösning som valdes ut som lämplig inom CCU analyserades ur ett marknadsmässigt perspektiv genom en översiktlig kartläggning av aktörer i regionen. Därefter studerades klimatpåverkan från en förenklad modell av Tekniska verkens biogasanläggning för att undersöka hur denna förändras vid implementering av en lämplig lösning inom CCS respektive CCU.  Genom en screening av lösningsförslag identifierades 42 lösningsförslag inom CCS och CCU som sållades ner till sju stycken; algodling vid vattenrening, BECCS i saltvattenakviferer, betong härdad av koldioxid, bulklösning, metanoltillverkning, tillverkning av metan genom Power To Gas samt växthusodling. Multikriterieanalysen visade att koldioxidhärdad betong inom CCU och BECCS i saltvattenakviferer inom CCS var lämpliga lösningar för det studerade fallet. För implementering av förslagen krävdes bland annat en förvätskningsanläggning, infrastruktur för transport och samarbetspartners.  De studerade scenariernas klimatmässiga livscykel erhölls genom modellering och simulering av en modellanläggning av det studerade fallets biogasanläggning i programvaran SimaPro med användning av den funktionella enheten 1 Nm3 fordonsgas. Resultatet visade att fordonsgasen i referensfallet har en klimatpåverkan på 0,38 kg koldioxidekvivalenter. Fordonsgasens klimatpåverkan var cirka en åttondel av fossila bränslen såsom bensin och diesels klimatpåverkan. Vid lagring av koldioxid genom BECCS i saltvattenakviferer förändrades klimatpåverkan till - 0,42 kg koldioxidekvivalenter. När koldioxid användes till härdning av betong förändrades fordonsgasens klimatpåverkan till -0,72 kg koldioxidekvivalenter. Detta innebär att svenska producenter av biogas kan förbättra sin klimatpåverkan genom såväl lösningar inom CCS som CCU.

The Petronas C02 project aimed to design an ionic liquid-based technology for the removal of C02 from natural gas. Current technology using amine-based system is not economical. It is envisioned that an ionic liquid method has the potential to be superior to current technology, due to their unique characteristics, such as high thermal stability, negligible vapour pressure and the possibility to fine-tune their properties, by combining appropriate cations and anions. This project involved the development of a "simple" synthetic method for ionic liquids, utilising Group 2 metal hydroxides (especially, strontium hydroxide octahydrate). This gave a wide array of carboxylate ionic liquids, via an intermediate hydroxide solution. It is a very simple, straightforward procedure which uses starting materials which are commercially available in bulk. The classes of carboxylate ionic liquids that have been synthesised and fully characterised are those based on the cations: l-ethyl-3-methylimidazolium, tributylmethylammonium, tetraalkylphosphonium and l -al kyl -l-methylpyrrolidinium. The Hunig's based derivatives of l -alkyl•3•methylimidazolium bistriflamides, as well as phosphonium and ammonium caboxylates were tested for their ability ty to absorb C02. In the anhydrous us system, initial screening showed that the most promising anions for C02 solubility are the methanoate and ethanoate. In parallel, it was observed that the C02 solubility in ionic liquids was not greaby the alkyl chain length on cation. The most noticeable effect on C02 capture was the addition of 1 mole of water to the carboxylate ionic liquids. This greatly enhanced the solubility of C02 by an order of magnitude, which is due to a different mechanism of C02 absorption; chemisorption on in the presence of water, instead of physisorption. A mechanism via the formation of hydrogencarbonate has been proposed due to this remarkable ability for C02 capture, which was later proven by other team members. All in all, the system that has been put forward for consideration as a potential C02 absorber in industrial processes within Petronas is the equimolar system of [4441][CH3C02] and water .

The research described in this thesis relates to the development and optimisation of a novel polymerisation reaction and its subsequent use in the generation of novel ‘Polymers of Intrinsic Microporosity’ (PIMs). The polymerisation reaction takes monomers containing two or more aromatic amines and fuses them together by the synthesis of a bridged bicyclic heterocyclic link called Tröger’s base (TB). This link not only strongly holds the polymer chain together, but also provides a site of contortion, which is necessary for a PIM to exhibit microporosity. The first part of this work introduces the background to the research, detailing the reasons behind the development of a new class of PIM and the competitor materials. Following this is detailed the optimisation of the TB forming condensation reaction and the synthesis of a variety of amine functionalised monomers. Also described in this section is the optimisation of a second condensation reaction used for the synthesis of a family of compounds based around a coumaron framework, all of which lack amine functionality. This precedes discussion of X-ray crystal structure analysis of several TB model compounds, amine functionalised monomers and coumaron-based compounds. After this is a description of the development of the novel TB polymerisation reaction, the results of the TB polymerisation of the amine functionalised monomers, characterisation of the successful polymers and the attempted polymerisation of two coumaron-based monomers. The final part of this work reports the experimental procedure for each compound together with full characterisation. In closing, the TB polymerisation reaction has successfully used for the production of highly stable and soluble PIMs exhibiting a wide range of microporosity, with BET surface areas ranging from 0 m2/g to 1035 m2/g. A few of these PIMs have been found to have excellent molecular weight, capable of forming strong membranes, suitable for gas separation, most notably for the purification of oxygen, hydrogen and carbon dioxide from nitrogen. Conversely, the synthesis of coumaron-based PIMs proved unsuccessful, but nevertheless this research should allow the future synthesis of a coumaron-based PIM. The research on TB polymerisation detailed in this thesis has contributed towards an International Patent122 and a paper in Science123so can be deemed to have been successful by that measure.

Carbon dioxide capture is an urgently needed pathway to mitigation of climate change, yet the amine-based solvents currently considered the leading industrial technologies suffer from many shortcomings; namely their high operating cost, poor stability and potentially damaging environmental impact from emission of degradation products. This work is a study of possible routes to improved CO2 capture technologies from a fundamental chemistry perspective. Initial work focused on the development of a straightforward and adaptable protocol for studying the species formed by CO2 capture into amine solvents, using 1H NMR spectroscopy for its combination of speed and accuracy. The applicability of this approach to diverse blended-amine solvents was demonstrated. This method was then applied to the study of phenoxide as a novel possible capture agent in conjunction with amines. Blends of potassium phenoxide with monoethanolamine were found to have an excellent capture capacity and favourable speciation that suggests a low energy consumption in practical use. This demonstrates the feasibility of blended solvents with a reduced amine component. Finally, a possible amine-free route to CO2 capture, exploiting the high susceptibility of carboxylate acidity to solvation, was explored. The first systematic study of the pKa of CO2 in mixtures of organic solvent and water was carried out, finding that this value is relatively insensitive to the makeup of the solvent and therefore in organic-rich solutions, carboxylate salts can be used as a CO2-absorbing base. CO2 capture using a system developed along these principles was demonstrated, and the possible basis for the observed insensitivity was discussed with particular emphasis given to the thermodynamics of the process.

In this work two research topics are presented: investigation of carbonation reactions of high – calcium waste materials and CO2 storage in coal. Firstly, sorption capacity of CO2 and CH4 of hard coal and associated sorption-induced expansion of the material was measured. This investigation was maintained in isothermal and non-isothermal conditions. Experiments were done on purpose-design apparatus allowing simultaneous measurement of sorption kinetics and sorption-induced swelling/contraction of coal. Chosen coal sample had higher sorption capacity for CO2 when compare to capacity for CH4.. Next to CO2 storage, the topic of CO2 utilization has been investigated. Carbonation of European high-calcium fly ashes is assessed. The experiments have been done on different fly ashes with content of 5-36% CaO. Complementary, characterization and analysis of fly ash samples has been performed. Acceleration of carbonation has been explored. Experiments has been done in temperature range between 25 and 290°C, 1-12 bar of CO2, CO2 + H2O and simulated flue gas over reaction times between 2 and 72 hours. Major conclusions of this work is that increasing the temperature and pressure strongly enhances the process of carbonation. Also, addition of water vapor substantially accelerates the process and increase its kinetics. This thesis reports that maintaining the carbonation process without steam addition leads to effective carbonation conversion. Chemical fixation of CO2 molecules with solid material of fly ash with high content of CaO to produce calcium carbonate is possible. The highest sequestration capacity achieved is 117.7 g CO2/kg fly ash and highest carbonation efficiency obtained is 48%. The microstructural analysis of fly ash samples showed the evolution of the cenosphere surface according to the carbonation experiments conditions. Different shapes and sizes of calcium carbonate has been detected after carbonation experiments. The compositional constraints of fly ashes that control reaction with CO2 has been described. It was found that not the bulk content of CaO is the factor controlling the carbonation reaction, but the content of free lime. Impact on carbonation of two pressure flow systems was assessed: batch and continuous flow, with and without addition of steam. Using he batch treatment with addition of steam gave the highest carbonation efficiency. Another set of carbonation experiments which has been done was with using simulated flue gas (84% N2, 15% CO2, 1 % H2O) instead of pure CO2 stream, in conditions: 160°C, 6 bar of gas and 2 hours of reaction time. It was concluded that using flue gas instead of pure stream of carbon dioxide lowers the carbonation rate of about 9%. Final part of this research was to determine the change of free lime content in fly ash samples before and after carbonation. Carbonation reactions lead to substantial decrease of free lime contents in fly ashes. In most cases, the amount of free lime in fly ash after carbonation was compatible with the current EU legislations regarding fly ash incorporation to cement as admixture.
En este trabajo se presentan dos temas de investigación: almacenamiento de CO2 en carbón y carbonatación de residuos industriales con un alto contenido en calcio. En primer lugar, se midió la capacidad de sorción de CO2 y CH4 de la hulla y su asociada expansión. Esta investigación se mantuvo en condiciones isotérmicas y no isotérmicas. Los experimentos se realizaron en un aparato diseñado específicamente, el cual permite la medición simultánea de la cinética de sorción y su asociada expansión y contracción. La muestra de carbón elegido tenía una mayor capacidad de absorción de CO2 comparado a CH4. Además, la absorción de CO2 indujo una expansión de volumen en el carbón, duplicando la obtenida tras la absorción de CH4. La cinética de deformación lineal muestra que la expansión del carbón inducida por ambos gases es anisotrópica, y es mayor en la dirección perpendicular al plano de estratificación que en paralelo a este. El análisis dilatométrico hace referencia a la deformación del material en presencia de CH4 es casi dos veces más baja que la obtenida en presencia de CO2, en el mismo rango de presión. El aumento de temperatura da como resultado una expansión adicional del carbón cuando se expone a CH4. La absorción de CO2 en el carbón en condiciones iso-térmicas conduce a la contracción de la muestra. Esto podría estar asociado con la composición petrográfica del carbón. Los datos obtenidos de la cinética de absorción y expansión de carbón se ajustaron en una ecuación cinética. El modelo utilizado fue: ‘Ecuación Exponencial Estirada’. El modelado de la cinética de absorción y expansión es importante para determinar la respuesta del carbón como posible almacenamiento de gas y permite predecir los cambios en la absorción-transporte de carbón. Junto al almacenamiento de CO2, la utilización de este también ha sido investigado. Se evalúa la carbonatación de las cenizas volante de origen europeo con alto contenido en calcio. Los experimentos se han realizado en diferentes cenizas volantes con un contenido entre 5-36% de CaO. Un estudio detallado de la carbonatación acelerada de las cenizas volantes has sido llevado a cabo Los experimentos se han realizado en un rango de temperatura entre 25 y 290°C, 1 - 12 bares de CO2, CO2 + H2O y gases de combustión simulados durante tiempos de reacción entre 2 y 72 horas. La principal conclusión de este trabajo es: el aumento de temperatura, presión y la adición de vapor de agua acelera considerablemente el proceso de carbonatación en estos materiales. Evidencias experimentales sugieren que una carbonatación efectiva se puede obtener sin la adición de vapor de agua. La mayor capacidad de CO2 secuestrado es de 117.7 g CO2/kg de cenizas volantes y la mayor eficiencia de carbonatación obtenida equivale a 48%. El análisis microestructural de las cenizas volantes mostró una evolución de la superficie de la cenosferas según las condiciones de los experimentos de carbonatación. Se han detectado diferentes formas y tamaños de carbonato de calcio después de los experimentos de carbonatación Se han descrito las restricciones referidas a la composición de las cenizas volantes que controlan su reacción con CO2. Se encontró que el factor dominante que controla la reacción de carbonatación es el contenido mineralógico de cal libre, en lugar del contenido total de CaO. Se evaluó el impacto en la carbonatación de dos sistemas presurizados: batch y flujo continuo, con y sin adición de vapor. Las reacciones llevadas a cabo en sistemas tipo batch con la adición de vapor produjeron la mayor eficiencia de carbonatación. Otra serie de experimentos de carbonatación realizados consistieron en el uso de gas de combustión simulado (84% N2, 15% CO2, 1% H2O) en lugar de CO2 puro. Las condiciones experimentales fueron: 160°C, 6 bares de presión total y 2 horas de tiempo de reacción. Se concluyó que el uso de gas de combustión en lugar de dióxido de carbono puro reduce la tasa de carbonatación de aproximadamente el 9%. Finalizando, el contenido de cal libre ha sido determinado para cada muestra antes y después de las reacciones de carbonatación en una variedad de cenizas volantes. Las reacciones de carbonatación produjeron una disminución sustancial del contenido de cal libre en las cenizas volantes. En la mayoría de los casos, el contenido de cal libre después de la carbonatación fue compatible con las legislaciones actuales de la UE con respecto a la incorporación de cenizas volantes al cemento como aditivo.
W niniejszej przedstawiono dwa tematy badawcze: badanie reakcji karbonatyzacji odpadów wysoko wapniowych i składowania CO2 w węglu. W pierwszej części badawczej dokonano analizy pojemności sorpcyjnej CO2 i CH4 węgla kamiennego oraz zmiany wolumetryczne węgla spowodowane procesem sorpcji. Eksperymenty prowadzono w warunkach izotermicznych i nieizotermicznych. Do pomiarów użyto specjalistycznego aparatu do jednoczesnego pomiaru sorpcji oraz ekspansji próbek wywołanej sorpcją. Wybrana próbka węgla charakteryzowała się większą pojemnością sorpcyjną dla CO2 niż dla CH4. Odkształcenia próbki węgla spowodowane sorpcją CO2 były dwa razy większe niż odkształcenia próbki wzbudzone sorpcją metanu. Ekspansja próbki jest anizotropowa w wyniku sorpcji obu gazów i większa w kierunku prostopadłym niż równoległym. Analiza dylatometryczna wskazuje, że ekspansja węgla w obecności CH4 jest prawie dwukrotnie mniejsza niż ekspasnsja węgla podczas sorpcji CO2, w tym samym zakresie ciśnień. Prowadzenie eksperymentów sorpcji w warunkach nieizotermicznych powoduje dodatkową ekspansję węgla podczaj reakcji z CH4. Sorpcja CO2 na węglu w tych warunkach prowadzi do kontrakcji próbki. Przedstawione różnice wolumetryczne mogą być związane ze składem petrograficznym węgla. Dane kinetyk sorpcji i rozszerzalności próbki węgla kamiennego zostały dopasowane do równania kinetycznego. Zastosowanym modelem było równanie ’Stretched Exponential Equation’. Modelowanie kinetyki sorpcji i rozszerzalności węgla jest ważne w celu określenia potencjalu zmagazynowania CO2 w węglu oraz pozwala przewidzieć zmiany wolumetryczne pokładów węglowych. W drugiej części niniejszej pracy zbadano temat utylizacji ditlenku węgla. Przedstawiono oraz zbadano temat karbonatyzacji europejskich popiołów lotnych o wysokiej zawartościści tlenku wapnia. Doświadczenia przeprowadzono na różnych popiołach lotnych o całkowitej zawartości CaO w przedziale 5-36%. Dokonano również charakteryzacji oraz analizy wybranych próbek popiołów lotnych. Przeprowadzono próby akceleracji kinetyki procesu karbonatyzacji. Eksperymenty wykonano w zakresie temperatur od 25 do 290°C, ciśnienia 1-12 barów CO2, CO2 + H2O lub mieszaniny gazów. Czas reakcji eskerymentów mieścił się w przedziale 2 a 72 godzin. Podwyższenie temperatury oraz ciśnienia CO2 zwiększa konwersję gazu i CaO do węglanu wapnia. Ponadto, dodanie pary wodnej do strumienia CO2 przyśpiesza proces karbonatyzacji. Uzyskane wyniki eskerymentów pozwalają wnioskować, że karbonatyzacja w warunkach gaz – ciało stałe, bez dostępu wody jest możliwa do przeprowadzenia. Opisane warunki doświadczeń pozwoliły na interakcję cząsteczek CO2 z tlenkiem wapnia zawartym w popiele lotnym i wytworzenie kalcytu. Najwyższa uzyskana pojemność sekwestracyjna CO2 wyniosła 117,7 g CO2/kg popiołu lotnego, a najwyższa uzyskana wydajność karbonatyzacji wyniosła 48%. Analiza mikrostrukturalna próbek popiołów lotnych ukazała ewolucję powierzchni cenosfer podczas zmieniających się warunków eskerymentalnych procesu karbonatyzacji. Podczas analizy próbek popiołu po karbonatyzacji wykryto w materiale różne kształty i rozmiary węglanu wapnia. Zdeterminowano wpływ składu chemicznego popiołów lotnych na reakcję z ditlenkiem węgla. Stwierdzono, że zawartość wolnego wapna jest czynnikiem kontrolującym reakcję, a nie całkowita zawartość CaO. Oceniono wpływ na reakcję karbonatyzacji dwóch układów przepływu ciśnieniowego: reaktor zamknięty oraz reaktor z ciągłym przepływem gazu, z dodatkiem pary wodnej lub bez. Zastosowanie reaktora zamkniętego z dodatkiem pary dało najwyższą wydajność karbonatyzacji. W finalnej partii eskerymentów karbonatyzacji użyto symulowanego gazu spalinowego (84% N2, 15% CO2, 1% H2O) zamiast czystego strumienia CO2, w warunkach: 160°C, 6 barów ciśnienia i 2 godzin czasu reakcji. Stwierdzono, że stosowanie gazu spalinowego zamiast czystego strumienia dwutlenku węgla obniża wydajność karbonatyzacji o około 9%. Końcową częścią badań procesu karbonatyzacji było określenie zmiany zawartości wolnego wapna w próbkach popiołu lotnego przed i po nasyceniu ditlenkiem węgla. Reakcje karbonatyzacji prowadzą do znacznego zmniejszenia zawartości wolnego wapna w popiele lotnym. W większości przypadków ilość wolnego wapna w popiele lotnym po nasycaniu ditlenkiem węgla była zgodna z obowiązującymi przepisami UE dotyczącymi utylizacji popiołów lotnych w cemencie, jako domieszki.