In this work the experimental results from the rapid screening and ranking of a wide range of novel adsorbents for carbon capture are presented. The samples were tested using the Zero Length Column (ZLC) method which has proved to be an essential tool for the rapid investigation of the equilibrium and kinetic properties of prototype adsorbents. The study was performed on different classes of nanoporous materials developed as part of the EPSRC-funded “Innovative Gas Separations for Carbon Capture” (IGSCC) project. More than 120 novel adsorbents with different key features for post-combustion carbon capture were tested. The classes of materials investigated were: • PIMs (Polymers of Intrinsic Microporosity) • MOFs (Metal - Organic Frameworks) • Mesoporous Silica • Zeolites • Carbons All the samples were tested at experimental conditions close to the ones of a typical flue gas of a fossil fuel power plant: 35 ºC and 0.1 bar of partial pressure of CO2. The results from the ranking of the CO2 capacity of the materials, at the conditions of interest, indicate the Mg and Ni-based MOF samples as the adsorbents with the highest uptake among all the candidates. The best sample shows a CO2 capacity almost double than the benchmark adsorbent, zeolite 13X (provided by UOP). The ranking also shows some of the zeolite adsorbents synthesised as promising materials for carbon capture: uptakes comparable or slightly higher than 13X were obtained for several samples of Rho and Chabazite zeolite. Water stability tests were also performed on the best MOFs and showed a deactivation rate considerably faster for the Mg-based MOFs, proving an expected higher resistance to degradation for the Ni based materials. A focused investigation was also carried out on the diffusion of CO2 in different ionexchanged zeolites Rho samples. The study of these samples, characterised by extremely slow kinetics, extended the use of the ZLC method to very slow diffusional time constants which are very difficult to extract from the traditional long time asymptotic analysis. The results show how the combination of the full saturation and partial loading experiment can provide un-ambiguous diffusional time constants. The diffusivity of CO2 in zeolite Rho samples shows to be strongly influenced by the framework structure as well as the nature and the position of the different cations in the framework. The kinetics of the Na-Cs Rho sample was also measured by the use of the Quantachrome Autosorb-iQ™ volumetric system. To correctly interpret the dynamic response of the instrument modifications were applied to the theoretical model developed by Brandani in 1998 for the analysis of the piezometric method. The analytical solution of the model introduces parameters which allow to account for the real experimental conditions. The results confirm the validity of the methodology in the analysis of slow diffusion processes. In conclusion the advantages offered by the small size of the column and the small amount of sample required proved the ZLC method to be a very useful tool for the rapid ranking of the CO2 capacity of prototype adsorbents. Equilibrium and kinetic measurements were performed on a very wide range of novel nanoporous materials. The most promising and interesting samples were further investigated through the use of the water stability test, the partial loading experiment and the volumetric system. The ZLC technique was also extended to the measurements of systems with very slow kinetics, for which is very difficult to extract reliable diffusional time constants. An improved model for the interpretation of dynamic response curves from a non-ideal piezometric system was developed.

Carbon Capture and Storage (CCS) is a legitimate technology option that should be part of a balanced portfolio of mitigation technologies available Post-Kyoto Protocol framework after Paris 2015 and beyond the 2020s or the cost achieving 2 degrees Celsius stabilisation scenario will significantly increase. Oxy-fuel combustion as a CCS technology option increases fuel flexibility. Additionally, oxy-biomass as a bio-energy with CCS (BECCS) technology can achieve negative carbon dioxide (CO2) emissions in sustainable biomass systems. Also, oxygen (O2) production in an air separation unit (ASU) gives potential for extra operational flexibility and energy storage. In this work, new designs of 20 litre spherical (R-20) and 30 litre non-spherical (R-30) ignition chambers have been built at the University of Edinburgh to carry-out dust ignition experiments with different ignition energies for evaluating pulverised fuel ignitability as a function of primary recycle (PR) O2 content for oxy-fuel PF milling safety. A set of coals and biomasses being used (at the time of submitting this work) in the utility pulverised fuel boilers in the UK have been employed. Coal and biomass dusts were ignited in air and oxy-fuel mixtures up to 30 % v/v O2 balance mixture CO2 where peak pressures (Pmax) from ignition were recorded. Pressure ratios (Pmax/Pinitial) were determined the key parameter for positive ignition identification with a value above 2.5 to be considered positive. Particle size effects in coal and biomass ignition were evaluated. Results on biomass were more variable than with coals, requiring a stronger ignition source (5,000 J) mainly due to larger particle sizes. Finer biomass particles behaved similarly to air ignition in 25 % v/v O2 in CO2. Larger particles of biomass did not ignite at all for most cases even reaching 30 % v/v O2 in CO2. A reference coal used, El Cerrejon, behaved as expected with 30 % v/v O2 balance CO2 matching air case; particles between 75-53 microns had lower ignitability than finer below 53 microns but were critical in devolatilisation. Most fuels did not ignite in 21 % v/v in CO2 below 200 g/m3 concentrations. The use of adequate ignition energy strength is needed for the PF mill safety case, with 5,000 J energy required for the biomasses tested. An indication of potential ignition chamber volume and geometry effect has also been observed when comparing results from R-20 and R-30 ignition chambers. Important implications include that oxy-biomass PR with 21 % v/v O2 content would give improved pulverised fuel (PF) milling safety when compared to air firing but reduced ignitability and a 25 % v/v O2 balance CO2 atmosphere would approach to oxy-biomass ignition behaviour in air in mills.

This thesis explores the international political dynamics of developing low carbon technology. Specifically, Carbon Capture and Storage (CCS) technology as a climate mitigation strategy in a developing country context is examined. CCS is a technological solution that allows for the continued use of fossil fuels without the large amounts of associated CO2 emissions. This entails capturing the CO2 emitted from large point sources, such as a coal-fired power station, and transporting the captured emissions to be injected and stored permanently into geological media. Consequently, CCS is a bridging technology that could provide more time for transitioning to a low-carbon economy. A case study of India is used, which is an emerging industrialising economy, and is also the third-largest coal producer in the world. India faces a dilemma: poverty alleviation and infrastructure development to support its billion plus population requires vast amounts of energy, which is predominantly based on fossil fuels. Therefore, it was envisioned that CCS would be a sustainable option, which could enable industrialisation at the rate required, whilst preventing the exacerbation of the negative effects of climate change. However, during the period of study (2007-2010), CCS was not embraced by India, despite there being a growing impetus to develop, demonstrate and transfer the technology. India was reluctant to consider CCS as part of a mitigation strategy, and this thesis focuses on the reasons why. An interdisciplinary approach is used, coupling perspectives from science, technology and innovation studies (STS) with concepts from International Relations (IR) scholarship. This sociotechnical conceptual framework is applied to gain a more holistic picture of the failed attempt to transfer CCS technology to India. Key technical challenges and blockages are identified within India’s existing energy system, which have restricted CCS technology implementation. In addition, the political challenges associated with the rejection of CCS by the Indian Government are explored. Empirical evidence is on the basis of elite interviews, an expert stakeholder survey and relevant documents. Another case study on the Cambay basin is used to further demonstrate the influence of political factors on CCS implementation, even in an area considered to have suitable technical conditions. The outcomes of this study have implications for policy addressing global challenges, especially by means of international cooperation and technological change.

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.

Anthropogenic CO₂ captured from a coal-fired power plant can be used for an enhanced oil recovery (EOR) operation while mitigating the atmospheric impact of CO₂ emissions. Concern about climate change caused by CO₂ emissions has increased the motivation to develop carbon capture and sequestration (CCS) projects to reduce the atmospheric impact of coal and other fossil fuel combustion. Enhanced oil recovery operations are typically constrained by the supply of CO₂, so there is interest from oil producers to use large-volume anthropogenic (LVA) CO₂ for tertiary oil production. The intermittency of LVA CO2 emissions creates an area of concern for both oil producers and electric utilities that may enter into a CO₂ supply contract for EOR. An oil producer wants to know if intermittency from a non-standard source of CO₂ will impact oil production from the large volume being captured. Since the electric utility must supply electricity on an as-needed basis, the CO₂ emissions are inherently intermittent on a daily and seasonal basis. The electric utility needs to know if the intermittent supply of CO₂ would reduce its value compared to CO₂ delivered to the oil field at a constant rate. This research creates an experimental test scenario where one coal-fired power plant captures 90% of its CO₂ emissions which is then delivered through a pipeline to an EOR operation. Using real emissions data from a coal-fired power plant and simplified data from an actual EOR reservoir, a series of reservoir simulations were done to address and analyze potential operational interference for an EOR operator injecting large-volume, intermittent CO₂ characteristic of emissions from a coal-fired power plant. The test case simulations in this study show no significant impact to oil production from CO₂ intermittency. Oil recovery, in terms of CO₂ injection, is observed to be a function of the total pore volumes injected. The more CO₂ that is injected, the more oil that is produced and the frequency or rate at which a given volume is injected does not impact net oil production. Anthropogenic CO₂ sources can eliminate CO₂ supply issues that constrain an EOR operation. By implementing this nearly unlimited supply of CO₂, oil production should increase compared to smaller-volume or water-alternating-gas (WAG) injection strategies used today. Mobility ratio and reservoir heterogeneity have a considerable impact on oil recovery. Prediction of CO₂ breakthrough at the production wells seems to be more accurate when derived from the mobility ratio between CO₂ and reservoir oil. The degree of heterogeneity within the reservoir has a more direct impact on oil recovery and sweep efficiency over time. The volume of CO₂ being injected can eventually invade lower permeability regions, reducing the impact of reservoir heterogeneity on oil recovery. This concept should mobilize a larger volume of oil than a conventional volume-limited or WAG injection strategy that may bypass or block these lower permeability regions. Besides oil recovery, a reservoir's performance in this study is defined by its CO₂ injectivity over time. Elevated injection pressures associated with the large-volume CO₂ source can substantially impact the ability for an oil reservoir to store LVA CO₂. As CO₂, a less viscous fluid, replaces produced oil and water, the average reservoir pressure slowly declines which improves injectivity. This gradual improvement in injectivity is mostly occupied by the increasing volume of recycled CO₂. Sweep efficiency is critical towards minimizing the impact of CO₂ recycling on reservoir storage potential. Deep, large, and permeable oil reservoirs are more capable of accepting LVA CO₂, with less risk of fracturing the reservoir or overlying confining unit. The depth of the reservoir will directly dictate the injection pressure threshold in the oil reservoir as the fracture pressure increases with depth. If EOR operations are designed to sequester all the CO₂ delivered to the field, additional injection capacity and design strategies are needed. / text

In this thesis, I present four research papers related by their focus on environmental and economic effects of low-carbon policies and technologies in electric power. The papers address a number of issues related to the operation and design of CCS-equipped plants with solvent storage and bypass, the effect of Renewable Portfolio Standards (RPS) on cycling of coal-fired power plants, and the EPA’s proposed CO2 emissions rule for existing power plants. In Chapter 2, I present results from a study of the design and operation of power plants equipped with CCS with flue gas bypass and solvent storage. I considered whether flue gas bypass and solvent storage could be used to increase the profitability of plants with CCS. Using a pricetaker profit maximization model, I evaluated the increase in NPV at a pulverized coal (PC) plant with an amine-based capture system, a PC plant with an ammonia-based capture system, and a natural gas combined-cycle plant with an amine-based capture system when these plants were equipped with an optimally sized solvent storage vessel and regenerator. I found that while flue gas bypass and solvent storage increased profitability at low CO2 prices, they ceased to do so at CO2 prices high enough for the overall plant to become NPV-positive. In Chapter 3, I present results from a Unit Commitment and Economic Dispatch model of the PJM West power system. I quantify the increase in cycling of coal-fired power plants that results when complying with a 20% RPS using wind power, accounting for cycling costs not usually included in power plant bids. I find that while additional cycling does increase cycling-related production costs and emissions of CO2, SO2, and NOX, these increases are small compared to the overall reductions in production costs and air emissions that occur with high levels of wind. In proposing its existing power plant CO2 emissions standard, the Environmental Protection Agency determined that significant energy efficiency would be available to aid in compliance. In Chapter 4, I use an expanded version of the model of Chapter 3 to evaluate compliance with the standard with and without this energy efficiency, as well as under several other scenarios. I find that emissions of CO2, SO2, and NOX are relatively insensitive to the amount of energy efficiency available, but that production costs increase significantly when complying without efficiency. In complying with the EPA’s proposed existing power plant CO2 emissions standard, states will have the choice of whether to comply individually or in cooperation with other states, as well as the choice of whether to comply with a rate-based standard or a mass-based standard. In Chapter 5, I present results from a linear dispatch model of the power system in the continental U.S. I find that cooperative compliance reduces total costs, but that certain states will prefer not to cooperate. I also find that compliance with a mass-based standard increases electricity prices by a larger margin than does compliance with a rate-based standard, with implications for the distribution of surplus changes between producers and consumers.

Carbon Capture and Storage (CCS) is an old technology matrix with new concept to mitigate climate change while utilizing fossil fuels by advancing the technology. The various level of advancement in technology has been successfully demonstrated in some part of the world. However the technology has inherent uncertainty of not having commercial CCS plant. Efforts to make CCS commercially viable unfold uncertainties in numerous aspects of CCS technology. Beside the uncertainties in technology many barriers restrain CCS to become a successful climate mitigation technology. However the growing energy demand and urgent need to mitigate climate change through emission reduction favours CSS as transition to clean energy production. FutureGen 2.0 is the only large commercial scale CCS project, initiated in 2003 to test the commercial viability of the technology and to meet the U.S energy demands besides emission reductions target. The project resurrection in 2010 as FutureGen 2.0 after FutureGen termination in 2008 provides an opportunity to understand and analyse numerous uncertainties. However through document analysis only major three uncertainties i.e. policy and regulatory, economic and financial and public acceptance uncertainties are identified and analysed. The interlinkages between these uncertainties are also analysed. The study results show that above uncertainties constrained the project engendering new uncertainties i.e. timeframe uncertainties. This study also provides an insight about the sustainability implication of CCS by evaluating economic, environmental and social impact of CCS technology. It is still early to term the CCS as Sustainable technological innovation however for many years CCS would upset and restrain investment in other clean energy technologies like Renewable technology system. This study gives an input in sustainability of CCS and technological assessment study. This study is helpful in managing uncertainties and planning new CCS projects.

A model for the evaluation of CO2-EOR projects has been developed. This model includes both reservoir simulation to handle reservoir properties, fluid flow and injection and production schedules, and a numerical economic model that generates a monthly cash flow stream from the outputs of the reservoir model. This model is general enough to be used with any project and provide a solid common basis to all of them. This model was used to evaluate CO2-EOR injection and production strategies and develop an optimization workflow. Producer constraints (maximum oil and gas production rates) should be optimized first to generate a reference case. Further improvements can then be obtained by optimizing the injection starting date and the injection plateau rate. Investigation of sensitivity of CO2-EOR to the presence of an aquifer showed that CO2 injection can limit water influx in the reservoir and is beneficial to recovery, even with a strong water drive. The influence of some key parameters was evaluated: the producer should be completed in the top part of the reservoir, while the injector should be completed over the entire thickness; it is recommended but not mandatory that the injection should start as early as possible to allow for lower water cut limit. Finally, the sensitivity of the economics of the projects to some key parameters was evaluated. The most influent parameter is by far the oil price, but other parameters such as the CO2 source to field distance, the pipeline cost scenario, the CO2 source type or the CO2 market price have roughly the same influence. It is therefore possible to offset an increase of one of them by reducing another.

I assess the potential of seismic and time-domain controlled-source electromagnetic (CSEM) methods to monitor carbon dioxide (CO2) migration through the application of a monitorability workflow. The monitorability workflow describes a numerical modelling approach to model variations in the synthetic time-lapse response due to CO2 migration. The workflow consists of fluid-flow modelling, rock-physics modelling and synthetic seismic or CSEM forward modelling. I model CO2 injected into a simple, homogeneous reservoir model before applying the workflow to a heterogeneous model of the Bunter Sandstone reservoir, a potential CO2 storage reservoir in the UK sector of the North Sea. The aim of this thesis is to model the ability of seismic and time-domain CSEM methods to detect CO2 plume growth, migration and evolution within a reservoir, as well as the ability to image a migrating front of CO2. The ability to image CO2 plume growth and migration within a reservoir has not been demonstrated in the field of CSEM monitoring. To address this, I conduct a feasibility study, simulating the time-lapse CSEM time-domain response of CO2 injected into a saline reservoir following the multi-transient electromagnetic (MTEM) method. The MTEM method measures the full bandwidth response. First, I model the response to a simple homogeneous 3D CO2 body, gradually increasing the width and depth of the CO2. This is an analogue to vertical and lateral CO2 migration in a reservoir. I then assess the ability of CSEM to detect CO2 plume growth and evolution within the heterogeneous Bunter Sandstone reservoir model. I demonstrate the potential to detect stored and migrating CO2 and present the synthetic results as time-lapse common-offset time sections. The CO2 plume is imaged clearly and in the right coordinates. The ability to image seismically a migrating front of CO2 remains challenging due to uncertainties regarding the pore-scale saturation distribution of fluids within the reservoir and, in turn, the most appropriate rock-physics model to simulate this: uniform or patchy saturation. I account for this by modelling both saturation models, to calculate the possible range of expected seismic velocities prior to generating and interpreting the seismic response. I demonstrate the ability of seismic methods to image CO2 plume growth and evolution in the Bunter Sandstone saline reservoir model and highlight clear differences between the two rock-physics models. I then modify the Bunter Sandstone reservoir to depict a depleted gas field by including 20% residual gas saturation. I assess the importance and implication of patchy saturation and present results which suggest that seismic techniques may be able to detect CO2 injected into depleted hydrocarbon fields.

Metal organic frameworks (MOFs) are a class of nanoporous materials composed through self-assembly of inorganic and organic structural building units (SBUs). MOFs show great promise for many applications due to their record-breaking internal surface areas and tunable pore chemistry. This thesis work focuses on gas separation applications of MOFs in the context of carbon capture and storage (CCS) technologies. CCS technologies are expected to play a key role in the mitigation of anthropogenic CO2 emissions in the near future. In the first part of the thesis, robust machine learning quantitative structure-property relationship (QSPR) models are developed to predict CO2 working capacity and CO2/H2 selectivity for pre-combustion carbon capture using the most topologically diverse database of hypothetical MOF structures constructed to date (358,400 MOFs, 1166 network topologies). The support vector regression (SVR) models are developed on a training set of 35,840 MOFs (10% of the database) and validated on the remaining 322,560 MOFs. The most accurate models for CO2 working capacities (R2 = 0.944) and CO2/H2 selectivities (R2 = 0.876) are built from a combination of six geometric descriptors and three novel y-range normalized atomic-property-weighted radial distribution function (AP-RDF) descriptors. 309 common MOFs are identified between the grand canonical Monte Carlo (GCMC) calculated and SVR-predicted top-1000 high-performing MOFs ranked according to a normalized adsorbent performance score. This work shows that SVR models can indeed account for the topological diversity exhibited by MOFs. In the second project of this thesis, computational simulations are performed on a MOF, CALF-20, to examine its chemical and physical properties which are linked to its exceptional water-resisting ability. We predict the atomic positions in the crystal structure of the bulk phase of CALF-20, for which only a powder X-ray diffraction pattern is available, from a single crystal X-ray diffraction pattern of a metastable phase of CALF-20. Using the predicted CALF-20 structure, we simulate adsorption isotherms of CO2 and N2 under dry and humid conditions which are in excellent agreement with experiment. Snapshots of the CALF-20 undergoing water sorption simulations reveal that water molecules in a given pore adsorb and desorb together due to hydrogen bonding. Binding sites and binding energies of CO2 and water in CALF-20 show that the preferential CO2 uptake at low relative humidities is driven by the stronger binding energy of CO2 in the MOF, and the sharp increase in water uptake at higher relative humidities is driven by the strong intermolecular interactions between water. In the third project of this thesis, we use computational simulations to investigate the effects of residual solvent on Ni-BPM’s CH4 and N2 adsorption properties. Single crystal X-ray diffraction data shows that there are two sets of positions (Set 1 and 2) that can be occupied by the 10 residual DMSO molecules in the Ni-BPM framework. GCMC simulations of CH4 and N2 uptake in Ni-BPM reveal that CH4 uptake is in closest agreement with experiment when the 10 DMSO’s are placed among the two sets of positions in equal ratio (Mixed Set). Severe under-prediction and over-prediction of CH4 uptake are observed when the DMSO’s are placed in Set1 and Set 2 positions, respectively. Through binding site analysis, the CH4 binding sites within the Ni-BPM framework are found to overlap with the Set 1 DMSO positions but not with the Set 2 DMSO positions which explains the deviations in CH4 uptake observed for these cases. Binding energy calculations reveal that CH4 molecules are most stabilized when the DMSO’s are in the Mixed Set of positions.