A dynamic MEA absorption process model has been developed to study the operability of this process in a dynamic fashion and to develop a control strategy to maintain the operation of the MEA scrubbing CO2 capture process in the presence of the external perturbations that may arise from the transient operation of the power plant. The novelty in this work is that a mechanistic model based on the conservation laws of mass and energy have been developed for the complete MEA absorption process. The model developed in this work was implemented in gPROMS. The process response of the key output variables to changes in the key input process variables, i.e., the flue gas flow rate and the reboiler heat duty, are presented and discussed in this study. In order to represent the actual operation of a power plant, the dynamic response of the MEA absorption process to a sinusoidal change in the flue gas flow rate was also considered in the present analysis. The mechanistic dynamic model was applied to develop a basic feedback control strategy. The implementation of a control strategy was tested by changing the operating conditions for the flue gas flow rate. The controlled variables, i.e., the percentage of CO2 absorbed in the absorber column and the reboiler temperature, were maintained around their nominal set point values by manipulating the valve stem positions, which determine the lean solvent feed flow rate at the top of the absorber column, and the reboiler heat duty, respectively. For the sinusoidal test, the amplitude of the oscillations observed for the controlled variables was smaller than those observed for the open-loop tests. This is because the variability of the controlled variables was transferred to the manipulated variable in the closed loop. The mechanistic dynamic model developed in this process can be potentially used as a practical tool that can provide insight regarding the dynamic operation of MEA absorption process. The model developed in this work can also be used as a basis to develop other studies related to the operability, controllability and dynamic flexibility of this process.

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.

The present thesis proposes to explore the potential of Zeolitic Imidazolate Framework ZIFs for CO2 capture applications in the conditions required by the Pressure Swing Adsorption separations process. Molecular modelling methods, combining Monte Carlo, Density Functional Theory and ab-initio simulations, were employed to mimic pure and mixture gas adsorption in ZIF materials. A transferable Force Field specifically developed for ZIFs materials is used to characterize a large variety of frameworks. Theses studies enable us to better understand the phenomena acting during adsorption process. Thereby several innovative modifications are proposed to enhance the ZIFs properties for CO2 capture and a series of hypothetical ZIFs are designed, characterized and compared to existing materials. The results cumulated during this thesis were then summarized to propose a first correlative model able to predict ZIF properties from a set of solids descriptors. This study enables to guide the structure design to optimize the ZIF properties.

Microbial electrochemical technologies (MET) exploit the bioelectrocatalytic activity of microorganisms, with a main focus on waste-to-resource recovery. Electromethanogenesis, a type of MET, describes the process of CO2 reduction specifically to methane, catalyzed by methanogens that utilize the cathode directly as an electron donor or through H2 evolving from the cathode surface. Applications are mainly in the direction of bioelectrochemical power-to-gas, as well as biogas upgrading and carbon capture and utilization. As the cathode and its associated microbial consortia are key to the process, larger scale applications require improvements especially in terms of optimal operational parameters, cathode materials and the dynamics of the effect of electron transfer within the cathodic biofilm. The focus of this dissertation is to improve the understanding of the dynamics and function of methaneproducing biofilms grown on cathodes in electromethanogenic reactors in the presence of two different electron donors: the cathode and the H2 evolving from the cathode surface. The spatial homogeneity of the microbial communities across the area of the cathode was demonstrated, which is relevant for large scale applications where reproducibility is required for predictable engineered systems. Metagenomic and metatranscriptomic methods were applied to elucidate the short-term changes in the actively transcribed methanogenesis and central carbon assimilation pathways in response to varying the availability of electrons by changing the set cathode potential in a novel Methanobacterium species enriched from electromethanogenic biocathodes. Although changes in functional performance were evident with varying potential, no significant differential expression was observed and genes from the methanogenesis and carbon assimilation pathways were highly expressed throughout. Indium tin oxide (ITO) as a potentially hydrogen evolution reaction (HER) – inert cathode material was evaluated using the mixotrophic Methanosarcina barkeri in an attempt to develop a simplified material-science driven approach to future electron transfer studies. It was found to be electrochemically unstable under the tested conditions, losing its conductivity over time. Overall, the findings from these studies provide new knowledge on the effects of electron donor availability on the functional performance and the biocathode community dynamics. The understandings derived from the study are relevant to methanogenic processes and should aid in system scaleup design.

Carbon dioxide (CO2) has long been regarded as the major greenhouse gas, which leads to numerous negative effects on global environment. The capture and separation of CO2 by selective adsorption using porous materials proves to be an effective way to reduce the emission of CO2 to atmosphere. Porous organic polymers (POPs) are promising candidates for this application due to their readily tunable textual properties and surface functionalities. The objective of this thesis work is to develop new POPs with high CO2 adsorption capacities and CO2/N2 selectivities for post-combustion effluent (e.g. flue gas) treatment. We will also exploit the correlation between the CO2 capture performance of POPs and their textual properties/functionalities. Chapters Two focuses on the study of a group of porous phenolic-aldehyde polymers (PPAPs) synthesized by a catalyst-free method, the CO2 capture capacities of these PPAPs exceed 2.0 mmol/g at 298 K and 1 bar, while keeping CO2/N2 selectivity of more than 30 at the same time. Chapter Three reports the gas adsorption results of different hyper-cross-linked polymers (HCPs), which indicate that heterocyclo aromatic monomers can greatly enhance polymers’ CO2/N2 selectivities, and the N-H bond is proved to the active CO2 adsorption center in the N-contained (e.g. pyrrole) HCPs, which possess the highest selectivities of more than 40 at 273 K when compared with other HCPs. Chapter Four emphasizes on the chemical modification of a new designed polymer of intrinsic microporosity (PIM) with high CO2/N2 selectivity (50 at 273 K), whose experimental repeatability and chemical stability prove excellent. In Chapter Five, we demonstrate an improvement of both CO2 capture capacity and CO2/N2 selectivity by doping alkali metal ions into azo-polymers, which leads a promising method to the design of new porous organic polymers.

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Separation of CO2, the main global warming causing greenhouse gas, from other flue gases and from biogas has become of great interest due to the predicted effects of global warming that the world is already starting to experience. This research focuses on the separation of CO2 from CH4 and N2 gases using polymeric and mixed matrix membranes. Amine-based poly vinyl alcohol (PVA) polymeric membranes that had previously shown good gas separation results were adapted for use in this research. The physical aging of the adapted membrane was initially analyzed for 37 days and it was observed that the membrane stabilized after 21 days. The adapted membrane was then optimized using a 26 factorial design to improve the membranes’ performance with respect to CO2/N2 and CO2/CH4 selectivity when tested using single gas permeation experiments at near atmospheric conditions. This was done with the membrane components: PVA, formaldehyde, poly (allylamine hydroxide), potassium hydroxide, water and 2-aminoisobutyric acid. Zeolite 13X and ZIF-8 powdered adsorbents were incorporated in the optimized membranes to prepare mixed-matrix membranes with the goal of bettering the separation performance of the membranes. Membrane characterization was done on the best performing membranes through spectroscopy, microscopy, and contact angle measurements. This study concluded with feed pressure tests on the overall best performing membranes. The performance of the fabricated membranes was compared to other polymeric and mixed-matrix membranes and Robeson’s upper bound line. Overall, the polymeric optimized membranes seemed to perform better than the filled mixed matrix membranes due to the introduction of agglomerations and cracks with both the filler materials. Also, the separation performance of the membrane improved with a decrease in pressure. At 1.5 absolute pressure, the optimized membrane was able to achieve a CO2/N2 and CO2/CH4 selectivity of 5.94 and 2.13 respectively with a CO2 permeability of 15,813 Barrer.

The mass transfer area of nine structured packings was measured as a function of liquid load, surface tension, liquid viscosity, and gas rate in a 0.427 m (16.8 in) ID column via absorption of CO₂ from air into 0.1 mol/L NaOH. Surface tension was decreased from 72 to 30 mN/m via the addition of a surfactant (TERGITOL[trademark] NP-7). Viscosity was varied from 1 to 15 mPa·s using poly(ethylene oxide) (POLYOX[trademark] WSR N750). A wetted-wall column was used to verify the kinetics of these systems. Literature model predictions matched the wetted-wall column data within 10%. These models were applied in the interpretation of the packing results. The packing mass transfer area was most strongly dictated by geometric area (125 to 500 m²/m³) and liquid load (2.5 to 75 m³/m²·h or 1 to 30 gpm/ft²). A reduction in surface tension enhanced the effective area. The difference was more pronounced for the finer (higher surface area) packings (15 to 20%) than for the coarser ones (10%). Gas velocity (0.6 to 2.3 m/s), liquid viscosity, and channel configuration (45° vs. 60° or smoothed element interfaces) had no appreciable impact on the area. Surface texture (embossing) increased the area by 10% at most. The ratio of effective area to specific area (a[subscript e]/a[subscript p]) was correlated within limits of ±13% for the experimental database: [mathematical formula]. This area model is believed to offer better predictive accuracy than the alternatives in the literature, particularly under aqueous conditions. Supplementary hydraulic measurements were obtained. The channel configuration significantly impacted the pressure drop. For a 45°-to-60° inclination change, pressure drop decreased by more than a factor of two and capacity expanded by 20%. Upwards of a two-fold increase in hold-up was observed from 1 to 15 mPa·s. Liquid load strongly affected both pressure drop and hold-up, increasing them by several-fold over the operational range. An economic analysis of an absorber in a CO₂ capture process was performed. Mellapak[trademark] 250X yielded the most favorable economics of the investigated packings. The minimum cost for a 7 m MEA system was around $5-7/tonne CO₂ removed for capacities in the 100 to 800 MW range. / text