Surfactant templating provides for the synthesis of ordered mesoporous silica and the opportunity to tailor the pore size, pore structure, particle morphology and surface functionality of the silica through the selection of synthesis conditions and surfactant template. This work extends the synthesis of nanostructured silica using fluorinated surfactant templates to the synthesis of organic/inorganic composites. The effect of fluorinated surfactant templates (C6F13C2H4NC5H5Cl, C8F17C2H4NC5H5Cl and C10F21C2H4NC5H5Cl), which have highly hydrophobic fluorocarbon tails, on functional group incorporation, accessibility, and silica textural properties is examined and compared to properties of hydrocarbon surfactant (C16H33N(CH3)3Br, CTAB) templated silica. Hydrocarbon (vinyl, n-decyl and 3-aminopropyl) and fluorocarbon (perfluoro-octyl, perfluorodecyl) functional group incorporation by direct synthesis is demonstrated, and its effects on silica properties are interpreted based on the aggregation behavior with the surfactant templates. Silica materials synthesized with CTAB possess greater pore order than materials synthesized with the fluorocarbon surfactants. The incorporation of the short vinyl chain substantially reduces silica pore size and pore order. However, pore order increases with functionalization for materials synthesized with the fluorinated surfactant having the longest hydrophobic chain. The incorporation of longer chain functional groups (n-decyl, perfluorodecyl, perfluoro-octyl) by direct synthesis results in hexagonal pore structured silica for combinations of hydrocarbon/fluorocarbon surfactant and functional groups. The long chain of these silica precursors, which can be incorporated in the surfactant micelle core, affect the pore size less than vinyl incorporation. Synthesis using the longer chain fluoro-surfactant (C8F17C2H4NC5H5Cl) template in ethanol/water solution results in highest incorporation of both n-decyl and the fluorocarbon functional groups, with a corresponding loss of material order in the fluorinated material. Matching the fluorocarbon surfactant (C6F13C2H4NC5H5Cl) to the perfluoro-octyl precursor did not show improved functional group incorporation. Higher incorporation of the perfluoro-octyl functional group was observed for all surfactant templates, but the perfluoro-decyl silica is a better adsorbent for the separation of hydrocarbon and fluorocarbon tagged anthraquinones. Incorporating a reactive hydrophilic functional group (3-aminopropyl) suggests further applications of the resulting nanoporous silica. Greater amine incorporation is achieved in the CTAB templated silica, which has hexagonal pore structure; the order and surface area decreases for the fluorinated surfactant templated material.

Membrane gas absorption technology is considered as one of the promising alternatives to conventional techniques for CO2 separation from the flue gas of fossil fuels combustion. As a hybrid approach of chemical absorption and membrane separation, it may offer a number of important features, including operational flexibility, compact structure, linear scale up and predictable performance. The main challenge is the additional membrane mass transfer resistance, especially when this resistance increases due to the absorbent intruding into the membrane pores. In this thesis, the experimental was set up to investigate how the operating parameters affect the absorption performance when using absorbent in hollow fiber contactor, and to obtain the optimal range of operation parameters for the designated membrane gas absorption system . During 20 days’ continuous experiment, we observed that the CO2 mass transfer rate decreases significantly following the operating time, which is attributed to the increase of membrane mass transfer resistance resulting from partial membrane wetting. To better understand the wetting evolution mechanism, the immersion experiments were carried out to assume that the membrane fibers immersed in the absorbents would undergo similar exposure as those used in the membrane contactor. Various membrane characterization methods were used to illustrate the wetting process before and after the membrane fibers were exposed to the absorbents. The characterization results showed that the absorbent molecules diffuse into the polypropylene (PP) polymer during the contact with the membrane, resulting in the swelling of the membrane. In addition, the effects of operating parameters such as immersion time, CO2 loading, as well as absorbent type on the membrane wetting were investigated in detail. Finally, based on the analysis results, methods to smooth the membrane wetting were discussed. It was suggested that improving the hydrophobicity of PP membrane by surface modification may be an effective way to improve the membrane long-term performance. Modification of the polypropylene membrane by depositing a rough layer of PP was carried out in order to improve the non-wettability of membrane. The comparison of long-term CO2 absorption performance by PP membranes before and after modification proves that the modified polypropylene membranes retained higher hydrophobicity than the untreated polypropylene membrane. Therefore modification is likely to be more suitable for use in membrane gas absorption contactors for CO2 separation, particularly over long operation time.

In Canada, coal-fired power plants are the largest anthropogenic point sources of atmospheric CO₂. The most promising near-term strategy for mitigating CO₂ emissions from these facilities is the post-combustion capture of CO₂ using MEA (monoethanolamine) with subsequent geologic sequestration. While MEA absorption of CO₂ from coal-derived flue gases on the scale proposed above is technologically feasible, MEA absorption is an energy intensive process and especially requires large quantities of low-pressure steam. It is the magnitude of the cost of providing this supplemental energy that is currently inhibiting the deployment of CO₂ capture with MEA absorption as means of combatting global warming. The steam cycle of a power plant ejects large quantities of low-quality heat to the surroundings. Traditionally, this waste has had no economic value. However, at different times and in different places, it has been recognized that the diversion of lower quality streams could be beneficial, for example, as an energy carrier for district heating systems. In a similar vein, using the waste heat from the power plant steam cycle to satisfy the heat requirements of a proposed CO₂ capture plant would reduce the required outlay for supplemental utilities; the economic barrier to MEA absorption could be removed. In this thesis, state-of-the-art process simulation tools are used to model coal combustion, steam cycle, and MEA absorption processes. These disparate models are then combined to create a model of a coal-fired power plant with integrated CO₂ capture. A sensitivity analysis on the integrated model is performed to ascertain the process variables which most strongly influence the CO₂ energy penalty. From the simulation results with this integrated model, it is clear that there is a substantial thermodynamic advantage to diverting low-pressure steam from the steam cycle for use in the CO₂ capture plant. During the course of the investigation, methodologies for using Aspen Plus?? to predict column pressure profiles and for converging the MEA absorption process flowsheet were developed and are herein presented.

As reserves of conventional crude oil are depleted, there is a growing need to develop unconventional oils such as heavy oil and bitumen from oil sands. In terms of recoverable oil, Canadian oil sands are considered to be the second largest oil reserves in the world. However, the upgrading of bitumen from oil sands to synthetic crude oil (SCO) requires nearly ten times more hydrogen (H₂) than the conventional crude oils. The current H₂ demand for oil sands operations is met mostly by steam reforming of natural gas. With the future expansion of oil sands operations, the demand of H₂ for oil sand operations is likely to quadruple in the next decade. As natural gas reforming involves significant carbon dioxide (CO₂) emissions, this sector is likely to be one of the largest emitters of CO₂ in Canada. <br> <br>In the current H₂ plants, CO₂ emissions originate from two sources, the combustion flue gases from the steam reformer furnace and the off-gas from the process (steam reforming and water-gas shift) reactions. The objective of this study is to develop a process that captures CO₂ at minimum energy penalty in typical H₂ plants. <br> <br>The approach is to look at the best operating conditions when considering the H₂ and steam production, CO₂ production and external fuel requirements. The simulation in this study incorporates the kinetics of the steam methane reforming (SMR) and the water gas shift (WGS) reactions. It also includes the integration of CO₂ capture technologies to typical H₂ plants using pressure swing adsorption (PSA) to purify the H₂ product. These typical H₂ plants are the world standard of producing H₂ and are then considered as the base case for this study. The base case is modified to account for the implementation of CO₂ capture technologies. Two capture schemes are tested in this study. The first process scheme is the integration of a monoethanolamine (MEA) CO₂ scrubbing process. The other scheme is the introduction of a cardo polyimide hollow fibre membrane capture process. Both schemes are designed to capture 80% of the CO₂ from the H₂ process at a purity of 98%. <br> <br>The simulation results show that the H₂ plant with the integration of CO₂ capture has to be operated at the lowest steam to carbon (S/C) ratio, highest inlet temperature of the SMR and lowest inlet temperatures for the WGS converters to attain lowest energy penalty. H₂ plant with membrane separation technology requires higher electricity requirement. However, it produces better quality of steam than the H₂ plant with MEA-CO₂ capture process which is used to supply the electricity requirement of the process. Fuel (highvale coal) is burned to supply the additional electricity requirement. The membrane based H₂ plant requires higher additional electricity requirement for most of the operating conditions tested. However, it requires comparable energy penalty than the H₂ plant with MEA-CO₂ capture process when operated at the lowest energy operating conditions at 80% CO₂ recovery. <br> <br>This thesis also investigates the sensitivity of the energy penalty as function of the percent CO₂ recovery. The break-even point is determined at a certain amount of CO₂ recovery where the amount of energy produced is equal to the amount of energy required. This point, where no additional energy is required, is approximately 73% CO₂ recovery for the MEA based capture plant and 57% CO₂ recovery for the membrane based capture plant. <br> <br>The amount of CO₂ emissions at various CO₂ recoveries using the best operating conditions is also presented. The results show that MEA plant has comparable CO₂ emissions to that of the membrane plant at 80% CO₂ recovery. MEA plant is more attractive than membrane plant at lower CO₂ recoveries.

Le CO2 est capté par formation de clathrates hydrates sous l’action d’un promoteur de cristallisation thermodynamique. Les clathrates hydrates sont des composés d’inclusion non stœchiométriques formés de molécules d’eau organisées en réseau de cavités piégeant des molécules de gaz. Ce procédé de captage consiste à piéger de façon sélective le dioxyde de carbone dans les cavités des clathrates hydrates et à le séparer ainsi des autres gaz. Les hydrates mixtes de cyclopentane (CP) + gaz ont été étudiés dans le cadre du projet FUI ACACIA et du projet européen ICAP. Les premières expériences se sont focalisées sur l’étude des équilibres quadri phasiques (gaz CO2/N2, eau liquide, cyclopentane liquide et hydrate). Le cyclopentane est un promoteur thermodynamique qui forme des hydrates mixtes de CO2 + N2 + CP à basse pression et température modérée. La pression d’équilibre des hydrates mixtes est réduite jusqu’à 97% par rapport à la pression d'équilibre initiale des hydrates de gaz. La sélectivité de captage du CO2 dans les hydrates mixtes est augmentée et le volume de gaz stocké est de 40 m3gaz/m3hydrate. Une seconde étude expérimentale, conduite en présence d’une sonde FBRM (Focused Beam Reflectance Measurements) et d’une émulsion stable directe de CP/eau, a montré que la cinétique de cristallisation des hydrates mixtes de CP + CO2 est limitée par la diffusion du gaz à l’interface gaz/liquide. La sonde FBRM permet de détecter parfaitement l’apparition de la nucléation. Le changement de profil de la distribution en longueurs de corde (CLD) est non seulement lié à l’apparition des mécanismes de cristallisation (dont l’agglomération) mais aussi à la disparition des gouttes de CP au profit des hydrates qui cristallisent par un mécanisme à cœur rétrécissant. / CO2 separation and capture by clathrate hydrate crystallization is a non-conventional way of trapping and storing gas molecules from flue gases. Clathrates hydrates are non-stoichiometric ice-like crystalline solids consisting of a combination of water molecules and suitable guest molecules. Mixed hydrates of cyclopentane (CP) + gas have been studied in one national project (FUI ACACIA) and a European program (iCAP). Cyclopentane is an organic additive which forms mixed hydrates of CP + CO2 + N2 at low pressure and moderate temperature. The equilibrium pressure is decreasing up to 97 % (relative to the equilibrium pressure without cyclopentane). CO2 selectivity in hydrates is enhanced and gas storage capacity approaches a roughly constant value of 40 m3gas (STP) /m3hydrate. Crystallization of CP + CO2 mixed hydrates seems limited by gas diffusion through the gas / liquid interface, which gets in the way of the determination of the intrinsic kinetic constants of crystallization. Experimental studies have also been investigated in presence of a Focused Beam Reflectance Measurements (FBRM) probe in stable emulsion of CP in water. FBRM probe can successfully identify hydrate nucleation. The sharp change in the mean chord length and the spread of Chord Length Distribution (CLD) are related to the progressive disappearance of the CP droplets in favor of the CP + CO2 mixed hydrates formation. The change in the mean chord length distribution is not only related to the agglomeration phenomenon of the particles but also to the occurrence of the shrinking core crystallization of the CP droplets.

Processos como a purificação do metano (CH4) e a produção de hidrogênio gasoso (H2) envolvem etapas de separação de CO2. Atualmente, etanolaminas como monoetanolamina (MEA), dietanolamina (DEA), metildietanolamina (MDEA) e trietanolamina (TEA) são as substâncias mais utilizadas no processo de separação/captura de CO2 em processos industriais. Entretanto, o uso destas substâncias apresenta alguns inconvenientes devido à alta volatilidade, dificuldade de se trabalhar com material líquido, também ao alto gasto energético envolvido das etapas de regeneração e à baixa estabilidade térmica e química. Com base nessa problemática, esse trabalho teve por objetivo a síntese de um tipo de sílica mesoporosa altamente ordenada (SBA-15) de modo a utilizá-la no processo de captura de CO2. O trabalho foi dividido em quatro etapas experimentais que envolveram a síntese da SBA-15, o estudo do comportamento térmico de algumas etanolaminas livres, síntese e caracterização de materiais adsorventes preparados a partir de incorporação de etanolaminas à SBA-15 e estudo da eficiência de captura de CO2 por esses materiais. Novas alternativas de síntese da SBA-15 foram estudadas neste trabalho, visando aperfeiçoar as propriedades texturais do material produzido. Tais alternativas são baseadas na remoção do surfatante, utilizado como molde na síntese da sílica mesoporosa, por meio da extração por Soxhlet, utilizando diferentes solventes. O processo contribuiu para melhorar as propriedades do material obtido, evitando o encolhimento da estrutura que pode ser ocasionado durante a etapa de calcinação. Por meio de técnicas como TG/DTG, DSC, FTIR e Análise Elementar de C, H e N foi realizada a caracterização físico-química e termoanalítica da MEA, DEA, MDEA e TEA, visando melhor conhecer as características destas substâncias. Estudos cinéticos baseados nos métodos termogravimétricos isotérmicos e não isotérmicos (Método de Ozawa) foram realizados, permitindo a determinação de parâmetros cinéticos envolvidos nas etapas de volatilização/decomposição térmica das etanolaminas. Além das técnicas acima mencionadas, MEV, MET, SAXS e Medidas de Adsorção de N2 foram utilizadas na caraterização da SBA-15 antes e após a incorporação das etanolaminas. Dentre as etanolaminas estudadas, a TEA apresentou maior estabilidade térmica, entretanto, devido ao seu maior impedimento estérico, é a etanolamina que apresenta menor afinidade com o CO2. Diferentemente das demais etanolaminas estudadas, a decomposição térmica da DEA envolve uma reação intramolecular, levando a formação de MEA e óxido de etileno. A incorporação destes materiais à SBA-15 aumentou a estabilidade térmica das etanolaminas, uma vez que parte do material permanece dentro dos poros da sílica. Os ensaios de adsorção de CO2 mostraram que a incorporação da MEA à SBA-15 catalisou o processo de decomposição térmica da mesma. A MDEA foi a etanolamina que apresentou maior poder de captura de CO2 e sua estabilidade térmica foi consideravelmente aumentada quando a mesma foi incorporada à SBA-15, aumentando também seu potencial de captura de CO2. / Processes as methane (CH4) purification from natural gas and gas hydrogenous (H2) production have stages involving CO2 separation. Nowadays, ethanolamine as monoethanolamine (MEA), diethanolamine (DEA), methyldiethanolamine (MDEA) and triethanolamine (TEA) are the substances more used in industrial processes involving CO2 separation/purification. However, the use of these substances has some inconvenient due to high volatility of these species, the inconvenient working with liquid, the use of high energy during the regeneration processes and low chemical and thermal stability. The object of this work was the synthesis of mesoporous ordinated silica (SBA-15) and its use in the CO2 capture process. This work was divided in four experimental stages: SBA-15 synthesis, the study of ethanolamine thermal behavior, the synthesis and characterization of adsorbent materials prepared using SBA-15 and ethanolamine and the study about the efficiency of CO2 capture using these materials. New alternatives for SBA-15 synthesis were studied in this work, due to increase the material proprieties. This study had the objective removing part of the surfactant used as template in mesoporous materials synthesis, using Soxhlet extractor and different solvents. This work contributed to increase the silica proprieties, eviting the shrinkage of silica structure caused by calcination stage. By means of TG/DTG, DSC, FTIR and Elemental Analysis techniques was realized physical-chemical and thermal characterization of MEA, DEA, MDEA and TEA. Kinetics studies using thermalgravimetric isothermal and no isothermal (Ozawa Method) method were used. This study permitted the determination of kinetics parameters involved in the thermal decomposition of the ethanolamines. Additionally, techniques as SEM, TEM, SAXS and Isotherm Adsorption of N2 were used for the characterization of SBA-15 incorporated with ethanolamine.TEA was the ethanolamine the biggest thermal stability, however, the CO2 absorption is not favorable because the steric impediment. The thermal decomposition of DEA involves the intramolecular reaction, producing MEA and ethylene oxide. The ethanolamines incorporation in SBA-15 increased the thermal stability of the ethanolamines, because part of these substances was in the SBA-15 porous. The experiments of CO2 capture showed that the MEA incorporation in the SBA-15 catalyzed the MEA decomposition process. The MDEA was the ethanolamine that had the major efficiency in the CO2 capture and its thermal stability was considerably increased when this space was incorporated in SBA-15, increasing its CO2 capture potential.

Cryogenic carbon capture process can be used to efficiently eliminate CO2 emissions from fossil-fueled power plants. The energy-storing embodiment of cryogenic carbon capture (ES-CCC) integrates energy storage with cryogenic carbon capture and uses natural gas as a refrigerant. ES-CCC captures CO2 from slowly varying or steady-state sources even as it absorbs and replaces large amounts of energy on the grid for energy storage. These large transients occur in the LNG generation as the process moves through energy storing to energy recovery operations. Additionally, raw natural gas often includes CO2 that forms an azeotrope with ethane. Breaking this azeotrope and separating CO2 from other hydrocarbons to meet natural gas pipeline and liquefied natural gas (LNG) standards is very energy intensive. The purpose of this work is to (a) describe a dynamic heat exchanger that reduces the heat exchanger performance and efficiency losses experienced under transient conditions and (b) introduce an alternative extractive distillation system for CO2 separation from ethane that requires less capital and has a lower operating cost than the conventional system for the same purification. This investigation demonstrates theoretically and experimentally that the dynamic heat exchangers can absorb sudden and large changes in flow rates and other properties without compromising either the heat exchanger efficiency or creating thermal or other stresses. These heat exchangers play an essential role in the ES-CCC process. Designs for retrofitting existing heat exchangers and for replacing existing heat exchangers with new designs are both theoretically and experimentally tested. The ES-CCC process requires natural gas processing to meet pipeline and LNG standards in many applications, depending primarily on the CO2 content of locally available NG. The energy, cost, and dynamic response of such processing hinges primarily on the most difficult step, breaking the CO2-ethane azeotrope. This project proposes and analyzes an alternative process for breaking this azeotrope and a control scheme that dramatically improves the dynamic response of natural gas processing plants, including steady and transient control scheme and processing simulations. These contributions to the ES-CCC capture process all have much broader applications in many chemical and energy processes. These contributions to ES-CCC and other industrial processes improve energy efficiency and dynamic performance of many processes and are ready for larger scale demonstration.

Metal-organic materials (MOMs) represent a unique class of porous materials that captured a great scientific interest in various fields such as chemical engineering, physics and materials science. They are typically assembled from metal ions or metal clusters connected by multifunctional organic ligands. They represent a wide range of families of materials that varied from 0D to 3D networks: the discrete (0D) structures exemplified by metal-organic polyhedra (MOPs), cubes and nanoballs while the polymeric 1D, 2D and 3D structures exemplified by coordination polymers (CPs). Indeed, the porous 3D structures include metal-organic frameworks (MOFs), porous coordination polymers (PCPs) and porous coordination networks (PCNs). Nevertheless, MOMs are long and well-known from more than 50 years ago as exemplified by CPs that were firstly introduced in early 1960s and reviewed in 1964. However, the scientific interest toward MOMs has been enormously grown only since late 1990s, with the discovery of MOMs with novel properties, especially the high permanent porosity as exemplified by MOF-5 and HKUST-1. The inherent tunability of MOMs from the de novo design to the post-synthetic modification along with their robustness, afford numerous important families of nets "platforms" such as pcu, dia, tbo, mtn and rht topology networks. There are more than 20,000 crystal structures of MOMs in the Cambridge Structure Database (CSD). However, only a few of the networks can be regarded as families or platforms where the structure is robust, fine-tunable and inherently modular. Such robustness and inherent modularity of the platforms allow the bottom-up control over the structure "form comes before function" which subsequently facilitates the systematic study of structure/function in hitherto unprecedented way compared with the traditional screening approaches that are commonly used in materials science. In this context, we present the crystal engineering of two MOM platforms; dia and novel fsc platforms as well we introduce the novel two-step synthetic approach using trigonal prismatic clusters to build multinodal 2D and 3D MOM platforms. For the dia platform, we introduce a novel strategy to control over the level of the interpenetration of dia topology nets via solvent-template control and study the impact of the resulting different pore sizes on the squeezing of CH4, CO2 and H2 gases. New benchmark material for methane isosteric heat of adsorption was produced from this novel work. Indeed we introduce the crystal engineering of a novel versatile 4,6-c fsc platform that is formed from linking two of the longest known and most widely studied MBBs: the square planar MBB [Cu(AN)4]2+( AN = aromatic nitrogen donor) and square paddlewheel MBB [Cu2(CO2R)4] that are connected by five different linkers with different length, L1-L5. The resulting square grid nets formed from alternating [Cu(AN)4]2+ and [Cu2(CO2R)4] moieties are pillared at the axial sites of the [Cu(AN)4]2+ MBBs with dianionic pillars to form neutral 3D 4,6-connected fsc (four, six type c) nets. Pore size control in this family of fsc nets was exerted by varying the length of the linker ligand whereas pore chemistry was implemented by unsaturated metal centers (UMCs) and the use of either inorganic or organic pillars. 1,5-naphthalenedisulfonate (NDS) anions pillar in an angular fashion to afford fsc-1-NDS, fsc-2-NDS, fsc-3-NDS, fsc-4-NDS and fsc-5-NDS from L1-L5, respectively. Experimental CO2 sorption studies revealed higher isosteric heat of adsorption (Qst) for the compound with the smaller pore size (fsc-1-NDS). Computational studies revealed that there is higher CO2 occupancy about the UMCs in fsc-1-NDS compared to other extended variants that were synthesized with NDS. SiF62- (SIFSIX) anions in fsc-2-SIFSIX form linear pillars that result in eclipse [Cu2(CO2R)4] moieties at a distance of just 5.86 Å. The space between the [Cu2(CO2R)4] moieties is a strong CO2 binding site that can be regarded as being an example of a single-molecule trap; this finding has been supported by modeling studies. Furthermore, we present herein the implementation of the two-step synthetic approach for the construction of novel multinodal MOM platforms, using the trigonal prism cluster [M3(µ3-O)(RCO2)6] as a precursor to build novel stable multinodal 2D and 3D frameworks. In the first step, the bifunctional carboxylate ligands are reacted with Fe+3 or Cr+3 salts to isolate highly symmetrical decorated trigonal prismatic clusters with diverse decoration such as pyridine, amine and cyano coordinating functional groups using pyridine carboxylate, amino carboxylate, cyano carboxylate type ligands, respectively. Afterward, the isolated highly soluble trigonal prismatic salts were reacted in the second step with another metal that can act as node or linker to connect the discrete trigonal prismatic clusters to build 2D or 3D networks. Indeed, we were able to develop another novel high-symmetry Cu cluster [Cu3(µ3-Cl)(RNH2)6Cl6] by utilizing CuCl2 salt and amine decorated trigonal prismatic cluster. Two novel 3D water stable frameworks with acs and stp topologies have been afforded. Our work on the crystal engineering design and synthesis of new MOM platforms offer an exceptional level of control over the resulting structure including; the resulting topology, pore size, pore chemistry and thereby enable the control over the resulting physicochemical properties in a manner that facilitates the achieving of the desired properties.

Australia is recognising that carbon capture and storage (CCS) may be a feasible pathway for addressing increasing levels of CO2 emissions. This thesis presents a preliminary economic assessment and comparison of the capture costs for different Australian CO2 emission sources. The capture technologies evaluated include solvent absorption, pressure swing adsorption (PSA), gas separation membranes and low temperature separation. The capture cost estimated for hydrogen production, IGCC power plants and natural gas processing is less than A$30/tonne CO2 avoided. CO2 capture cost for iron production ranges from A$30 to A$40 per tonne CO2 avoided. Higher costs of A$40 to over A$80 per tonne CO2 avoided were estimated for flue gas streams from pulverised coal and NGCC power plants, oil refineries and cement facilities, and IDGCC synthesis gas. Based on 2004 and 2005 EU ETS carbon prices (A$30 to A$45 per tonne CO2 avoided), the cost of capture using current commercially available absorption technology may deter wide-scale implementation of CCS, in particular for combustion processes. A sensitivity analysis was undertaken to explore the opportunities for reducing costs. The high cost for capture using solvent absorption is dependent on the energy needed for solvent regeneration and the high capital costs. Cost reductions can be achieved by using new low regeneration energy solvents coupled with recycling the waste heat from the absorption process back to the steam cycle, and using low cost ???fit-for-purpose??? equipment. For membrane and PSA technologies, the capture costs are dominated by the flue gas and post-capture compressors. Operating the permeate or desorption stream under vacuum conditions provides significant cost reductions. Improvements in membrane and adsorbent characteristics such as the adsorbent loading or membrane permeability, CO2 selectivity, and lower prices for the membrane or adsorbent material provide further cost benefits. For low partial pressure CO2 streams, capture using low temperature ???anti-sublimation??? separation can be an alternative option. Low costs could be achieved by operating under low pressures and integrating with external sources of waste heat. Applying the cost reductions achievable with technology and process improvements reduces the capture and CCS costs to a level less than current carbon prices, making CCS an attractive mitigation option.

<p>Membrane gas absorption technology is considered as one of the promising alternatives to conventional techniques for CO₂ separation from the flue gas of fossil fuels combustion. As a hybrid approach of chemical absorption and membrane separation, it may offer a number of important features, including operational flexibility, compact structure, linear scale up and predictable performance. The main challenge is the additional membrane mass transfer resistance, especially when this resistance increases due to the absorbent intruding into the membrane pores.</p><p>In this thesis, the experimental was set up to investigate how the operating parameters affect the absorption performance when using absorbent in hollow fiber contactor, and to obtain the optimal range of operation parameters for the designated membrane gas absorption system . During 20 days’ continuous experiment, we observed that the CO₂ mass transfer rate decreases significantly following the operating time, which is attributed to the increase of membrane mass transfer resistance resulting from partial membrane wetting.</p><p>To better understand the wetting evolution mechanism, the immersion experiments were carried out to assume that the membrane fibers immersed in the absorbents would undergo similar exposure as those used in the membrane contactor. Various membrane characterization methods were used to illustrate the wetting process before and after the membrane fibers were exposed to the absorbents. The characterization results showed that the absorbent molecules diffuse into the polypropylene (PP) polymer during the contact with the membrane, resulting in the swelling of the membrane. In addition, the effects of operating parameters such as immersion time, CO₂ loading, as well as absorbent type on the membrane wetting were investigated in detail. Finally, based on the analysis results, methods to smooth the membrane wetting were discussed. It was suggested that improving the hydrophobicity of PP membrane by surface modification may be an effective way to improve the membrane long-term performance.</p><p>Modification of the polypropylene membrane by depositing a rough layer of PP was carried out in order to improve the non-wettability of membrane. The comparison of long-term CO₂ absorption performance by PP membranes before and after modification proves that the modified polypropylene membranes retained higher hydrophobicity than the untreated polypropylene membrane. Therefore modification is likely to be more suitable for use in membrane gas absorption contactors for CO₂ separation, particularly over long operation time.</p>