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DESIGNED SYNTHESIS OF NANOPOROUS ORGANIC POLYMERS FOR SELECTIVE GAS UPTAKE AND CATALYTIC APPLICATIONSArab, Pezhman 01 January 2015 (has links)
Design and synthesis of porous organic polymers have attracted considerable attentions during the past decade due to their wide range of applications in gas storage, gas separation, energy conversion, and catalysis. Porous organic polymers can be pre-synthetically and post-synthetically functionalized with a wide variety of functionalities for desirable applications. Along these pursuits, we introduced new synthetic strategies for preparation of porous organic polymers for selective CO2 capture.
Porous azo-linked polymers (ALPs) were synthesized by an oxidative reaction of amine-based monomers using copper(I) as a catalyst which leads to azo-linkage formation. ALPs exhibit high surface areas of up to 1200 m2 g-1 and have high chemical and thermal stabilities. The nitrogen atoms of the azo group can act as Lewis bases and the carbon atom of CO2 can act as a Lewis acid. Therefore, ALPs show high CO2 uptake capacities due to this Lewis acid-based interaction. The potential applications of ALPs for selective CO2 capture from flue gas, natural gas, and landfill gas under pressure-swing and vacuum swing separation settings were studied. Due to their high CO2 uptake capacity, selectivity, regenerability, and working capacity, ALPs are among the best porous organic frameworks for selective CO2 capture.
In our second project, a new bis(imino)pyridine-linked porous polymer (BIPLP-1) was synthesized and post-synthetically functionalized with Cu(BF4)2 for highly selective CO2 capture. BIPLP-1 was synthesized via a condensation reaction between 2,6-pyridinedicarboxaldehyde and 1,3,5-tris(4-aminophenyl)benzene, wherein the bis(imino)pyridine linkages are formed in-situ during polymerization. The functionalization of the polymer with Cu(BF4)2 was achieved by treatment of the polymer with a solution of Cu(BF4)2 via complexation of copper cations with bis(imino)pyridine moieties of the polymer. BF4- ions can act Lewis base and CO2 can act as a Lewis acid; and therefore, the functionalized polymer shows high binding affinity for CO2 due to this Lewis acid-based interaction. The functionalization of the pores with Cu(BF4)2 resulted in a significant enhancement in CO2 binding energy, CO2 uptake capacity, and CO2 selectivity values. Due to high reactivity of bis(imino)pyridines toward transitions metals, BIPLP-1 can be post-synthetically functionalized with a wide variety of inorganic species for CO2 separation and catalytic applications.
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Bio(molecular) control of selective ion transport, gas separation and catalytic enzyme-based reactions using functionalized membranes / Contrôle bio-moléculaire du transport sélectif d’ions, de la séparation de gaz et de réactions catalytiques enzymatiques grâce aux membranes fonctionnaliséesYahia Marei Abdelrahim, Mohamed 21 December 2015 (has links)
Différents travaux de recherche ont été décrits dans cette thèse. Les travaux de recherche peuvent être résumés comme suit. Le premier chapitre a porté sur l'identification d’inhibiteurs puissants efficaces vis-à-vis de de l'isoenzyme anhydrase carbonique humaine I (hCAI). Considérant l'importance pharmacologique de trouver des inhibiteurs (CAIs) et des activateurs (AACs) sélectifs aux isoformes de l’anhydrase carbonique ), l'anhydrase carbonique humaine I (hCAI) a été confrontée en parallèle à diverses bibliothèques dynamiques constitutionnelles (CDL). Dans le deuxième chapitre, des réseaux constitutionnels dynamiques ont été préparés sous forme de systèmes membranaires liquides et solides agissant comme un réseau pour le transport spécifique des ions lanthanides. Le transport est basé sur la capacité de complexation des lanthanides (La + 3, Lu + 3, Eu + 3) avec les groupes polyéther fonctionnels situés dans les matériaux membranaires. Dans le troisième chapitre, l'approche proposée consiste en l'utilisation de membranes liquides ioniques supportées (SILMs) comprenant deux enzymes différentes de l'anhydrase carbonique, l’enzyme thermo-résistante SspCA et l'enzyme bovine-CA, qui catalysent la réaction de conversion réversible du CO2 en bicarbonate en favorisant la force motrice vers le transport de CO2. La stabilité des membrane, leur perméabilité vis-à-vis de CO2 et de N2 ainsi que la sélectivité idéale (CO2 / N2) ont été déterminées pour les membranes développées. Le quatrième chapitre porte sur la synthèse et la caractérisation de membranes polymères denses pour une application en séparation de gaz. Les mesures de perméabilité aux gaz des membranes polymères synthétisées ont montré que la perméabilité de CO2 est supérieure à celle des autres gaz testés (CH4 et N2). Dans le dernier chapitre, des membranes de PVDF ont été fonctionnalisées avec une enzyme, la phosphotriestérase (PTE), selon deux méthodes différentes pour construire un réacteur à membrane biocatalytique (BMR) avec pour finalité la bioconversion et la séparation sélective du substrat paraoxon. La première méthode met en œuvre une dispersion réversible de nanoparticules magnétiques de PTE qui est immobilisée à la surface de la membrane de PVDF sous l’effet d'un champ magnétique externe. A l’inverse, la seconde méthode porte sur le greffage chimique de l'enzyme PTE, après modification de la surface de la membrane de PVDF native (DAMP-GA-enzymatique). Les deux techniques d'immobilisation d'enzymes ont montré une bonne efficacité et une sensibilité à l'égard de la bioconversion du paraoxon dans les différentes conditions appliquées dans un réacteur à membrane biocatalytique (BMR).De façon globale, les concepts développés dans ce travail de thèse permettront d’ouvrir de nouvelles pistes de recherche allant vers le développement d'une membrane polymère sélective au transport d’ions, de gaz mais aussi active dans les réactions catalytiques enzymatiques grâce à un contrôle bio-moléculaire au niveau des matériaux membranaires. / Different research works have been described in this thesis. The research works can be summarized as the following. The first chapter deals with the identification of effective potent inhibitors for the human carbonic anhydrase I (hCAI) isozyme. Considering the pharmacological importance to find selective CA inhibitors (CAIs) and CA activators (CAAs), human carbonic anhydrase I (hCAI) has been subjected to a parallel screening of various constitutional dynamic libraries (CDL). In the second chapter, constitutional dynamic networks have been used in liquid and solid membrane systems as a carrier network for transporting lanthanides. The transport is based on the complexing ability of lanthanides metals (La+3, Lu+3, and Eu+3) with the functional polyether groups in the membrane materials. In the third chapter, the proposed approach consists in using supported ionic liquid membranes (SILMs) comprising two different carbonic anhydrase enzymes, the thermo-resistant SspCA enzyme and the Bovine-CA enzyme, which catalyze the reaction of reversible conversion of CO2 to bicarbonate, enhancing the driving force for CO2 transport. Membrane stability, CO2 and N2 permeability and (CO2/N2) ideal selectivity were determined for the membranes developed. In the fourth chapter, the research work consists in the synthesis and characterization of dense polymeric membranes for gas separation application. The gas permeability measurements for the synthesized polymeric membranes showed that the permeability of CO2 is higher than other used gases (N2 and CH4). In the last chapter, two different methods of PVDF membrane functionalization with a phosphotriesterase (PTE) enzyme have been developed to construct biocatalytic membrane reactor (BMR) for bioconversion and selective separation of paraoxon substrate. The first method employs reversible dispersion of magnetic nanoparticle immobilized with PTE using an external magnetic field on the surface of native PVDF membrane. On the contrary, the second method comprises chemical grafting of the PTE enzyme, after surface modification of the native PVDF membrane (DAMP-GA-Enzyme). Both methods of enzyme immobilization showed good efficiency and sensitivity towards the bioconversion of paraoxon substrate at different conditions applied in a biocatalytic membrane reactor (BMR).In general, the concepts developed in this thesis research work will help bring new tracks on the way to the development of a polymeric membrane for selective ion and gas separation but also for selective catalytic reaction under bio(molecular) control.
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Control of water and toxic gas adsorption in metal-organic frameworksMcPherson, Matthew Joseph January 2016 (has links)
The research presented in this thesis aims to determine the effectiveness of the uptake of toxic gases by several MOFs for future use in gas-mask cartridges, and to attempt to compensate for any deficiencies they show in “real-world” conditions. The main findings of this thesis confirm that MOFs are suitable candidates for the use in respirator cartridge materials and provide high capacity for adsorption of toxic gases like ammonia and STAM-1 in particular showed an impressive improvement in humid conditions, which normally decrease the performance of MOFs made from the same materials, such as HKUST-1. STAM-1's improved performance in humid conditions is attributed to the structural shift it displays upon dehydration and rehydration and this was shown to be the case in a structural analogue, CuEtOip, which was synthesised in the author's research group. This analogue was analysed using a combination of single crystal XRD and solid state MAS-NMR, both of which showed the structural change occurring and displays similar gas sorption behaviours, suggesting that this mechanism is the source of STAM-1's improved performance in humid conditions. This thesis also examines the “Armoured MOF” process and investigates the transferability of the process of deposition of mesoporous silica onto MOFs with vastly different properties and synthetic methods compared to those published in the original publication. Alongside this, attempts to protect MOFs using mesoporous silicates were investigated for their viability.
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PEBAX-based mixed matrix membranes for post-combustion carbon captureBryan, Nicholas James January 2018 (has links)
Polymeric membranes exhibit a trade-off between permeability and selectivity in gas separations which limits their viability as an economically feasible post-combustion carbon capture technology. One approach to improve the separation properties of polymeric membranes is the inclusion of particulate materials into the polymer matrix to create what are known as mixed matrix membranes (MMMs). By combining the polymer and particulate phases, beneficial properties of both can be seen in the resulting composite material. One of the most notable challenges in producing mixed matrix membranes is in the formation of performance-hindering defects at the polymer-filler interface. Non-selective voids or polymer chain rigidification are but two non-desirable effects which can be observed. The material selection and synthesis route are key to minimising these defects. Thin membranes are also highly desirable to achieve greater gas fluxes and improved economical separation processes. Hence smaller nano-sized particles are of particular interest to minimise the disruption to the polymer matrix. This is a challenge due to the tendency of some small particles to form agglomerations. This work involved introducing novel nanoscale filler particles into PEBAX MH1657, a commercially available block-copolymer consisting of poly(ethylene oxide) and nylon 6 chains. Poly(ether-b-amide) materials possess an inherently high selectivity for the CO2/N2 separation due to polar groups in the PEO chain but suffer from low permeabilities. Mixed matrix membranes were fabricated with PEBAX MH1657 primarily using two filler particles, nanoscale ZIF-8 and novel nanoscale MCM-41 hollow spheres. This work primarily investigated the effects of the filler loading on both the morphology and gas transport properties of the composite materials. The internal structure of the membranes was examined using scanning electron microscopy (SEM), and the gas transport properties determined using a bespoke time-lag gas permeation apparatus. ZIF-8 is a zeolitic imidazolate framework which possesses small pore windows that may favour CO2 transport over that of N2. ZIF-8-PEBAX membranes were successfully synthesised up to 7wt.%. It was found that for filler loadings below 5wt.%, the ZIF-8 was well dispersed within the polymer phase. At these loadings modest increases in the CO2 permeability coeffcient of 0-20% compared to neat PEBAX were observed. Above this 5wt.% loading large increases in both CO2, N2 and He permeability coeffcients coincided with the presence of large micron size clusters formed of hundreds of filler ZIF-8 particles. The increases in permeability were attributed to voids observed within the clusters. MCM-41 is a metal organic framework that has seen notable interest in the field of carbon capture, due to its tunable pore size and ease of functionalisation. Two types of novel MCM-41 hollow sphere (MCM-41-HS) of varying pore size were incorporated into PEBAX and successfully used to fabricate MMMs up to 10wt.%. SEM showed the MCM-41 generally interacted well with the polymer with no signs of voids and was generally well dispersed. However, some samples of intermediate loading in both cases showed highly asymmetric distribution of nanoparticles and high particle density regions near one external face of the membrane which also showed the highest CO2 permeability coeffcients. It is suspected that these high permeabilities are due to the close proximity of nanoparticles permitting these regions to act in a similar way to percolating networks. It was determined that there was no observable effect of the varying pore size which was expected given the transport in the pores should be governed by Knudsen diffusion.
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Simulation, Design and Optimization of Membrane Gas Separation, Chemical Absorption and Hybrid Processes for CO2 CaptureChowdhury, Mohammad Hassan Murad 14 December 2011 (has links)
Coal-fired power plants are the largest anthropogenic point sources of CO2 emissions worldwide. About 40% of the world's electricity comes from coal. Approximately 49% of the US electricity in 2008 and 23% of the total electricity generation of Canada in 2000 came from coal-fired power plant (World Coal Association, and Statistic Canada). It is likely that in the near future there might be some form of CO2 regulation. Therefore, it is highly probable that CO2 capture will need to be implemented at many US and Canadian coal fired power plants at some point.
Several technologies are available for CO2 capture from coal-fired power plants. One option is to separate CO2 from the combustion products using conventional approach such as chemical absorption/stripping with amine solvents, which is commercially available. Another potential alternative, membrane gas separation, involves no moving parts, is compact and modular with a small footprint, is gaining more and more attention. Both technologies can be retrofitted to existing power plants, but they demands significant energy requirement to capture, purify and compress the CO2 for transporting to the sequestration sites.
This thesis is a techno-economical evaluation of the two approaches mentioned above along with another approach known as hybrid. This evaluation is based on the recent advancement in membrane materials and properties, and the adoption of systemic design procedures and optimization approach with the help of a commercial process simulator. Comparison of the process performance is developed in AspenPlus process simulation environment with a detailed multicomponent gas separation membrane model, and several rigorous rate-based absorption/stripping models.
Fifteen various single and multi-stage membrane process configurations with or without recycle streams are examined through simulation and design study for industrial scale post-combustion CO2 capture. It is found that only two process configurations are capable to satisfy the process specifications i.e., 85% CO2 recovery and 98% CO2 purity for EOR. The power and membrane area requirement can be saved by up to 13% and 8% respectively by the optimizing the base design. A post-optimality sensitivity analysis reveals that any changes in any of the factors such as feed flow rate, feed concentration (CO2), permeate vacuum and compression condition have great impact on plant performance especially on power consumption and product recovery.
Two different absorption/stripping process configurations (conventional and Fluor concept) with monoethanolamine (30 wt% MEA) solvent were simulated and designed using same design basis as above with tray columns. Both the rate-based and the equilibrium-stage based modeling approaches were adopted. Two kinetic models for modeling reactive absorption/stripping reactions of CO2 with aqueous MEA solution were evaluated. Depending on the options to account for mass transfer, the chemical reactions in the liquid film/phase, film resistance and film non-ideality, eight different absorber/stripper models were categorized and investigated. From a parametric design study, the optimum CO2 lean solvent loading was determined with respect to minimum reboiler energy requirement by varying the lean solvent flow rate in a closed-loop simulation environment for each model. It was realized that the success of modeling CO2 capture with MEA depends upon how the film discretization is carried out. It revealed that most of the CO2 was reacted in the film not in the bulk liquid. This insight could not be recognized with the traditional equilibrium-stage modeling. It was found that the optimum/or minimum lean solvent loading ranges from 0.29 to 0.40 and the reboiler energy ranges from 3.3 to 5.1 (GJ/ton captured CO2) depending on the model considered. Between the two process alternatives, the Fluor concept process performs well in terms of plant operating (i.e., 8.5% less energy) and capital cost (i.e., 50% less number of strippers).
The potentiality of hybrid processes which combines membrane permeation and conventional gas absorption/stripping using MEA were also examined for post-combustion CO2 capture in AspenPlus®. It was found that the hybrid process may not be a promising alternative for post-combustion CO2 capture in terms of energy requirement for capture and compression. On the other hand, a stand-alone membrane gas separation process showed the lowest energy demand for CO2 capture and compression, and could save up to 15 to 35% energy compare to the MEA capture process depending on the absorption/stripping model used.
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Development and evaluation of aromatic polyamide-imide membranes for H₂S and CO₂ separations from natural gasVaughn, Justin 15 March 2013 (has links)
Over the past decade, membrane based gas separations have gained traction in industry as an attractive alternative to traditional thermally based separations due to their potential to offer lower operational and capital expenditures, greater ease of operation and lower environmental impact. As membrane research evolves, new state-of-the-art membrane materials as well as processes utilizing membranes will likely be developed. Therefore, their incorporation into existing thermally based units as a debottlenecking step or as a stand-alone separation unit is expected to become increasingly more common. Specifically for natural gas, utilization of smaller, more remote natural gas wells will require the use of less equipment intensive and more flexible separation technologies, which precludes the use of traditional, more capital and equipment intensive thermally based units.
The use of membranes is, however, not without challenges. Perhaps the most important hurdle to overcome in membrane development for natural gas purification is the ability to maintain high efficiency in the presence of harsh feed components such as CO₂ and H₂S, both of which can swell and plasticize polymer membranes. Additionally, as this project demonstrates, achievement of similarly high selectivity for both CO₂ and H₂S is challenged by the different governing factors that control their transport through polymeric membranes. However, as others have suggested and shown, as well as what is demonstrated in this project, when CO₂ is the primary contaminant of interest, maintaining high CO₂/CH₄ efficiency appears to be more important in relation to product loss in the downstream. This work focuses on a class of fluorinated, glassy polyamide-imides which show high plasticization resistance without the need for covalent crosslinking. Membranes formed from various polyamide-imide materials show high mixed gas selectivities with adequate productivities when subjected to feed conditions that more closely resemble those that may be encountered in a real natural gas well. The results of this project highlight the polyamide-imide family as a promising platform for future membrane material development for materials aimed at aggressive natural gas purifications due to their ability to maintain high selectivities under aggressive feed conditions without the need for extensive stabilization methods.
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Studies on Poly(N,N-dimethylaminoethyl methacrylate) Composite Membranes for Gas Separation and PervaporationDu, Runhong January 2008 (has links)
Membrane-based acid gas (e.g., CO2) separation, gas dehydration and humidification, as well as solvent dehydration are important to the energy and process industries. Fixed carrier facilitated transport membranes can enhance the permeation without compromising the selectivity. The development of suitable fixed carrier membranes for CO2 and water permeation, and understanding of the transport mechanism were the main objectives of this thesis.
Poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) composite membranes were developed using microporous polysulfone (PSF) or polyacrylonitrile (PAN) substrates. The PDMAEMA layer was crosslinked with p-xylylene dichloride via quaternization reaction. Fourier transform infrared, scanning electron microscopy, adsorption tests, and contact angle measurements were conducted to analyze the chemical and morphological structure of the membrane. It was shown that the polymer could be formed into thin dense layer on the substrates, while the quaternary and tertiary amino groups in the side chains of PDMAEMA offered a high polarity and hydrophilicity.
The solid-liquid interfacial crosslinking of PDMAEMA led to an asymmetric crosslinked network structure, which helped minimize the resistance of the membrane to the mass transport. The interfacially formed membranes were applied to CO2/N2 separation, dehydration of CH4, gas humidification and ethylene glycol dehydration. The membranes showed good permselectivity to CO2 and water. For example, a CO2 permeance of 85 GPU and a CO2/N2 ideal separation factor of 50 were obtained with a PDMAEMA/PSF membrane at 23oC and 0.41 MPa of CO2 feed pressure. At 25oC, the permeance of water vapor through a PDMAEMA/PAN membrane was 5350 GPU and the water vapor/methane selectivity was 4735 when methane was completely saturated with water vapor. On the other hand, the relative humidity of outlet gas was up to 100 % when the membrane was used as a hydrator at 45oC and at a carrier gas flow rate of 1000 sccm. For used for dehydration of ethylene glycol at 30oC, the PDMAEMA/PSF membrane showed a permeation flux of ~1 mol/(m2.h) and a permeate concentration of 99.7 mol% water at 1 mol% water in feed.
This work shows that the quaternary and tertiary amino groups can be used as carriers for CO2 transport through the membrane based on the weak acid-base interaction. In the presence of water, water molecules in the membrane tend to form a water "path" or water "bridge" which also help contribute to the mass transport though the membrane. In addition, CO2 molecules can be hydrated to HCO3-, which reaction can be catalyzed by the amino groups, the hydrated CO2 molecules can transport through the water path as well as the amino groups in the membrane. On the other hand, for processes involving water (either vapor or liquid) permeation, the amino groups in the membrane are also helpful because of the hydrogen bonding effects.
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Studies on Poly(N,N-dimethylaminoethyl methacrylate) Composite Membranes for Gas Separation and PervaporationDu, Runhong January 2008 (has links)
Membrane-based acid gas (e.g., CO2) separation, gas dehydration and humidification, as well as solvent dehydration are important to the energy and process industries. Fixed carrier facilitated transport membranes can enhance the permeation without compromising the selectivity. The development of suitable fixed carrier membranes for CO2 and water permeation, and understanding of the transport mechanism were the main objectives of this thesis.
Poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) composite membranes were developed using microporous polysulfone (PSF) or polyacrylonitrile (PAN) substrates. The PDMAEMA layer was crosslinked with p-xylylene dichloride via quaternization reaction. Fourier transform infrared, scanning electron microscopy, adsorption tests, and contact angle measurements were conducted to analyze the chemical and morphological structure of the membrane. It was shown that the polymer could be formed into thin dense layer on the substrates, while the quaternary and tertiary amino groups in the side chains of PDMAEMA offered a high polarity and hydrophilicity.
The solid-liquid interfacial crosslinking of PDMAEMA led to an asymmetric crosslinked network structure, which helped minimize the resistance of the membrane to the mass transport. The interfacially formed membranes were applied to CO2/N2 separation, dehydration of CH4, gas humidification and ethylene glycol dehydration. The membranes showed good permselectivity to CO2 and water. For example, a CO2 permeance of 85 GPU and a CO2/N2 ideal separation factor of 50 were obtained with a PDMAEMA/PSF membrane at 23oC and 0.41 MPa of CO2 feed pressure. At 25oC, the permeance of water vapor through a PDMAEMA/PAN membrane was 5350 GPU and the water vapor/methane selectivity was 4735 when methane was completely saturated with water vapor. On the other hand, the relative humidity of outlet gas was up to 100 % when the membrane was used as a hydrator at 45oC and at a carrier gas flow rate of 1000 sccm. For used for dehydration of ethylene glycol at 30oC, the PDMAEMA/PSF membrane showed a permeation flux of ~1 mol/(m2.h) and a permeate concentration of 99.7 mol% water at 1 mol% water in feed.
This work shows that the quaternary and tertiary amino groups can be used as carriers for CO2 transport through the membrane based on the weak acid-base interaction. In the presence of water, water molecules in the membrane tend to form a water "path" or water "bridge" which also help contribute to the mass transport though the membrane. In addition, CO2 molecules can be hydrated to HCO3-, which reaction can be catalyzed by the amino groups, the hydrated CO2 molecules can transport through the water path as well as the amino groups in the membrane. On the other hand, for processes involving water (either vapor or liquid) permeation, the amino groups in the membrane are also helpful because of the hydrogen bonding effects.
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Herstellung und Charakterisierung von Kompositmembranen aus seitlich von einer Polymermatrix eingefassten ZeolithpartikelnKiesow, Ina 23 March 2012 (has links) (PDF)
Für die hochselektive technische Trennung von Stoffen hält die Natur eine optimale Lösung namens Zeolithe bereit. In dieser Arbeit wurden Zeolith 4A in Form von Partikeln und wenig permeables Polymer in einer Membran kombiniert. Die Partikel lagen dabei in einer Monolage vor und wurden lediglich seitlich vom Polymer eingefasst, sodass sie beide Oberflächen der Polymerschicht durchbrachen. Diese Einbettung zu so genannten Zeolithkompositmembranen erlaubt einen Stofftransport ausschließlich durch die hochselektiven Zeolithpartikel. Die Herstellung und Charakterisierung der Zeolithkompositmembranen stehen im Mittelpunkt der vorliegenden Arbeit.
Für die Membranherstellung kam das Prinzip der partikelassistierten Benetzung einer Wasseroberfläche zum Einsatz. Hierfür wurden die Zeolithpartikel beschichtet und anschließend das unverändert zugängliche Porensystem mittels Thermogravimetrie in Wasseradsorptions-Desorptionsmessungen nachgewiesen. Aus beschichteten Partikeln und passendem Monomer konnten schichtdickenoptimierte Zeolithkompositmembranen hergestellt werden. Es wurde eine Permeabilität P für Wasserdampf von 49 barrer festgestellt, während die Gase Stickstoff und Sauerstoff keinen Transportnachweis zuließen (P < 0,03 barrer). Daraus ergeben sich Selektivitäten von über 1600.
Die Durchlässigkeit für Wasser beweist ein offenes Porensystem, die Impermeabilität für Stickstoff und Sauerstoff deutet auf eine sehr geringe Defektdichte hin, was beste Voraussetzungen für Trennmembranen darstellt.
Das Herstellungsprinzip soll als Vorlage für die Präparation maßgeschneiderter Kompositmembranen mit wählbarer Porengröße dienen. Vergleiche zu konventionellen Zeolithmembranen belegen, dass die partikelassistierte Benetzung die Methode der Wahl ist, partikelförmiges hochselektives Material optimal einzubetten, ohne die begehrten Permeationseigenschaften zu beeinträchtigen. / An optimal material for highly selective separation processes can be found in zeolites. We prepared composite membranes composed of zeolite 4A particles and a polymer of low permeability. The particles formed a dense monolayer which were embedded into the polymer sheet in such a way that each particle prenetrates both the top and the bottom surface of the sheet. Only this embedding offffers a transport through the highly selective particles exclusively. This work focusses on these so called zeolite composite membranes, on their preparation and characterization.
The preparation of the membranes was done via particle assisted wetting on a water surface. Therefore the zeolite particles were coated by a suitable silane agent and a blocking of the pore openings by the coating process was disproved by water adsorption-desorption measurements via TGA. Using the coated particles and a suitable monomer composite membranes could be formed and the optimum thickness was found. The membranes were permeable for water vapor (permeability P = 49 barrer), but impermeable for nitrogen and oxygene (P < 0,03 barrer (detection limit)). This results in a selectivity of above 1600.
The permeability for water indicates that the molecules are transported through the zeolite channels. The impermeability for nitrogene and oxygene indicates a very low amount of defects. Furthermore the composite nature of the membrane reduces brittleness thus rendering it a promising candidate for separation technology with tailoring the pore size.
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Engineering nanoporous materials for application in gas separation membranesBae, Tae-Hyun 11 August 2010 (has links)
The main theme of this dissertation is to engineer nanoporous materials and nanostructured surfaces for applications in gas separation membranes. Tunable methods have been developed to create inorganic hydroxide nanostructures on zeolite surfaces, and used to control the inorganic/polymer interfacial morphology in zeolite/polymer composite membranes. The study of the structure-property relationships in this material system showed that appropriate tuning of the surface modification methods leads to quite promising structural and permeation properties of the membranes made with the modified zeolites. First, a facile solvothermal deposition process was developed to prepare roughened inorganic nanostructures on zeolite pure silica MFI crystal surfaces. The functionalized zeolite crystals resulted in high-quality ̒mixed matrix̕ membranes, wherein the zeolite crystals were well-adhered to the polymeric matrix. Substantially enhanced gas separation characteristics were observed in mixed matrix membranes containing solvothermally modified MFI crystals. Gas permeation measurements on membranes containing nonporous uncalcined MFI revealed that the performance enhancements were due to significantly enhanced MFI-polymer adhesion and distribution of the MFI crystals. Solvothermal deposition of inorganic nanostructures was successfully applied to aluminosilicate LTA surfaces. Solvothermal treatment of LTA was tuned to deposit smaller/finer Mg(OH)₂ nanostructures, resulting in a more highly roughened zeolite surface. Characterization of particles and mixed matrix membranes revealed that the solvothermally surface-treated LTA particles were promising for application in mixed matrix membranes. Zeolite LTA materials with highly roughened surfaces were also successfully prepared by a new method: the ion-exchange-induced growth of Mg(OH)₂ nanostructures using the zeolite as the source of the Mg²⁺ ions. The size/shape of the inorganic nanostructures was tuned by adjusting several parameters such as the pH of the reagent solution and the amount of magnesium in the substrates and systematic modification of reaction conditions allowed generation of a good candidate for application in mixed matrix membranes. Zeolite/polymer adhesion properties in mixed matrix membranes were improved after the surface treatment compared to the untreated bare LTA. Surface modified zeolite 5A/6FDA-DAM mixed matrix membranes showed significant enhancement in CO₂ permeability with slight increases in CO₂/CH₄ selectivity as compared to the pure polymer membrane. The CO₂/CH₄ selectivity of the membrane containing surface treated zeolite 5A was much higher than that of membrane with untreated zeolite 5A. In addition, the use of metal organic framework (MOF) materials has been explored in mixed matrix membrane applications. ZIF-90 crystals with submicron and 2-μm sizes were successfully synthesized by a nonsolvent induced crystallization technique. Structural investigation revealed that the ZIF-90 particles synthesized by this method had high crystallinity, microporosity and thermal stability. The ZIF-90 particles showed good adhesion with polymers in mixed matrix membranes without any compatibilization. A significant increase in CO₂ permeability was observed without sacrificing CO₂/CH₄ selectivity when Ultem® and Matrimd® were used as the polymer matrix. In contrast, mixed matrix membranes with the highly permeable polymer 6FDA-DAM showed substantial enhancement in both permeability and selectivity, as the transport properties of the two phases were more closely matched.
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