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Development of next generation mixed matrix hollow fiber membranes for butane isomer separationLiu, Junqiang 13 October 2010 (has links)
Mixed matrix hollow fiber membranes maintain the ease of processing polymers while enhancing the separation performance of the pure polymer due to inclusion of molecular sieve filler particles. This work shows the development process of high loading mixed matrix hollow fiber membranes for butane isomer separation, from material selection and engineering of polymer-sieve interfacial adhesion to mixed matrix hollow fiber spinning.
The matching of gas transport properties in polymer and zeolite is critical for forming successful mixed matrix membranes. The nC4 permeability in glassy commercial polymers such as Ultem® and Matrimid® is too low (< 0.1 Barrer) for commercial application. A group of fluorinated (6FDA) polyimides, with high nC4 permeability and nC4/iC4 selectivity, are selected as the polymer matrix. No glassy polymers can possibly match the high permeable MFI to make mixed matrix membranes with selectivity enhancement for C4s separation. Zeolite 5A, which has a nC4 permeability (~3 Barrer) and nC4/iC4 selectivity (essentially ∞), matches well with the 6FDA polymers. A 24% nC4/iC4 selectivity enhancement was achieved in mixed matrix membranes containing 6FDA-DAM and 25 wt% treated 5A particles. A more promising mixed matrix membrane contains 6FDA-DAM-DABA matrix and 5A, because of a better match of gas transport properties in polymer and zeolite.
Dual layer hollow fibers, with cellulose acetate core layer and sheath layers of 6FDA polyimides, were successfully fabricated. Successive engineering of the 6FDA sheath layer and the dense skin is needed for the challenging C4s separation, which is extremely sensitive to the integrity of the dense skin layer. The delamination-free, macrovoid-free dual layer hollow fiber membranes provide the solution for the expensive 6FDA polyimides spinning. Mixed matrix hollow fiber membranes are spun base on the platform of 6FDA/Cellulose acetate dual layer hollow fibers. Preliminary results suggest that high loading mixed matrix hollow fiber membranes for C4s is feasible. Following research is needed on the fiber spinning with well treated zeolite 5A nanoparticles.
The key aspect of this research is elucidating the three-step (sol-gel-precipitation) mechanism of sol-gel-Grignard treatment, based on which further controlling of Mg(OH)2 whisker morphologies is possible. A Mg(OH)2 nucleation process promoted by acid species is proposed to explain the heterogeneous Mg(OH)2 growing process. Different acid species were tried: 1) HCl solution, 2) AlClx species generated by dealumination process and 3) AlCl3 supported on zeolite surfaces. Acids introduced through HCl solution and dealumination are effective on commercial 5A particles to generate Mg(OH)2 whiskers in the sol-gel-Grignard treatment. Supported AlCl3 is effective on both commercial and synthesized 5A particles (150 nm-1 µm) during the sol-gel-Grignard treatment, in terms of promoting heterogeneous Mg(OH)2 whiskers formation. But the byproduct of Al(OH)3 layer separates the Mg(OH)2 whiskers from zeolite surface, and leads to undesirable morphologies for polymer-zeolite interfacial adhesion. The elucidation of sol-gel-Grignard mechanism and importance of zeolite surface acidity on Mg(OH)2 formation, builds a solid foundation for future development towards ''universal'' method of growing Mg(OH)2 whiskers on zeolite surfaces.
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Membranes via particle assisted wettingMarczewski, Dawid 24 July 2009 (has links) (PDF)
Spreading of mixtures of oil with suitable silica particles onto a water surface leads to the
formation of composite layers in which particles protrude at the top and at the bottom from the
oil. Solidification of the oil and removal of the particles give rise to porous membranes. Pore
widths and membrane thicknesses depend on particle sizes and usually are in the range of 70 –
80% of their diameters. Often freely suspended porous membranes are too fragile to operate them
in pressure filtration without supportive structure.
To improve mechanical stability of porous membranes, a mixture of silica particles with
an oil is spread onto a nonwoven fibrous support that was drenched with water. Solidification of
the oil and removal of particles yields porous membrane attached to the fibers of the support. Due
to inhomogeneous surface of the fabric, the membranes that are attached to it are corrugated.
To obtain flat supportive structures, glass beads with 75 μm in diameter are spread onto
the water surface with the oil. Solidification of the oil and then removal of particles gives rise to
porous membranes with pore diameters in micrometer range.
Another concept of improvement of mechanical stability is the preparation of asymmetric
membranes via spreading of a mixture of two sorts of particles with opposite surface properties
with the oil onto the water surface. After solidification of the oil and removal of particles, membranes
with pores width in the range from 30 – 50 nm are obtained.
Slow removal of silica particles from composite monolayer that floats on the water surface
gives rise to silica rings in intermediate stages of removal.
Mixed matrix membranes with embedded carbon molecular sieves are prepared in a similar
process as detailed above by using carbon particles instead of silica. Carbon molecular sieves
protrude at the top and bottom from the polymeric matrix. Theoretical prediction of permeability
and selectivity through these membranes are much higher than in membranes where particles are
smaller than the membrane thickness. / Spreitet man Mischungen eines Öls mit geeigneten Kieselgelpartikeln auf eine Wasseroberfläche,
führt dies zur Bildung gemischter Schichten, in denen die Partikel auf der Ober- und
Unterseite aus dem Öl herausragen. Härtet man das Öl aus und entfernt die Partikel, erhält man
poröse Membranen mit einheitlichen Poren. Dabei hängen die Porenweiten und Membrandicken
von der Partikelgröße ab und betragen üblicherweise 70 – 80 % von deren Durchmesser. Oft sind
freitragende poröse Membranen zu zerbrechlich um mit ihnen Druckfiltration ohne Stützstruktur
durchzuführen.
Um die mechanische Stabilität von porösen Membranen zu erhöhen spreitet man eine Mischung
aus Kieselgelpartikeln und einem Öl auf einem Vliesstoff, der mit Wasser getränkt ist.
Das Aushärten des Öls und die Entfernung der Partikel führt zu einer porösen Membran, die an
die Fasern der Stützstruktur angeheftet ist. Durch die inhomogene Oberfläche des Vliesgewebes
sind die daran angehefteten Membranen gewellt.
Um eine ebene Stützstruktur zu erhalten, werden Mischungen aus dem Öl und Glaskugeln
mit einem Durchmesser von 75 μm verwendet. Das Aushärten des Öls und die Entfernung der
Partikel führt zu ebenen porösen Membranen mit Porendurchmessern im Mikrometerbereich.
Ein weiteres Konzept, um die mechanische Stabilität zu erhöhen, ist die Herstellung asymmetrischer
Membranen mit Hilfe des Spreitens einer Mischung zweier Partikelsorten mit unterschiedlichen
Oberflächeneigenschaften mit dem Öl auf die Wasseroberfläche. Nach dem Aushärten
des Öls und der Entfernung der Partikel erhält man eine asymmetrische Membran mit kleinen
Porenweiten an der Oberseite und großen Porenweiten an der Unterseite.
Durch langsames Entfernen der Kieselgelpartikel aus der gemischten Schicht, die auf der
Wasseroberfläche schwimmt, kann man in einem Zwischenstadium Kieselgelringe erhalten.
Kompositmembranen (mixed matrix membranes) mit eingebetteten Kohlenstoffmolekularsieben
werden in einem gleichen Prozess wie oben beschrieben hergestellt, indem man Kohlenstoffpartikel
anstatt der Kieselgelpartikel verwendet. Die Kohlenstoffmolekularsiebe ragen auf
der Ober- und Unterseite aus der Polymermatrix heraus. Die theoretisch vorhersagten Durchlässigkeiten
und Selektivitäten solcher Membranen sind wesentlich höher als bei Membranen, in
denen die Partikel kleiner als der Membrandicke sind.
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Σύνθεση μεμβρανών φωγιασίτη σε υποστρώματα α-Al2O3 και μελέτη της χρήσης αυτών σε διαχωρισμούς αερίων μιγμάτωνΓιαννακόπουλος, Ιωάννης 30 June 2008 (has links)
Οι ζεόλιθοι είναι κρυσταλλικά αργιλοπυριτικά υλικά με πόρους μοριακών διαστάσεων και για το λόγο αυτό συχνά καλούνται και ως μοριακά κόσκινα. Χαρακτηρίζονται από την ικανότητα ρόφησης αερίων και ατμών, ανταλλαγής των κατιόντων της δομής τους, καθώς και κατάλυσης σημαντικού αριθμού χημικών αντιδράσεων. Λόγω των ιδιαίτερων φυσικοχημικών ιδιοτήτων τους, οι ζεόλιθοι αποτελούν ιδανικά υλικά για το διαχωρισμό μορίων με διαφορετικό σχήμα, μέγεθος ή πολικότητα γι’αυτό την τελευταία δεκαετία μέρος του ερευνητικού ενδιαφέροντος έχει επικεντρωθεί στην ανάπτυξη πολυκρυσταλλικών μεμβρανών από ζεόλιθους με σκοπό το διαχωρισμό αερίων και υγρών μιγμάτων.
Στην παρούσα Διατριβή μελετήθηκε η κρυστάλλωση μεμβρανών φωγιασίτη πάνω σε πορώδη υποστρώματα από α-Al2O3 με επίπεδη και κυλινδρική γεωμετρία συναρτήσει διαφόρων παραμέτρων σύνθεσης όπως ήταν η σύσταση, η θερμοκρασία, ο χρόνος και η γήρανση των αιωρημάτων σύνθεσης των μεμβρανών Συνολικά εξετάστηκαν πέντε διαφορετικές συστάσεις. Η σύσταση 4.17Na2O : 1.0Al2O3 : 10TEA (τριαιθανολαμίνη) : 1.87SiO2 : 460H2O οδήγησε στην ανάπτυξη μεμβρανών φωγιασίτη με λιγότερες ατέλειες και για αυτό μελετήθηκε περισσότερο. Η ικανότητα των μεμβρανών να διαχωρίζουν μίγματα CO2 / H2, CO2 / N2, CO2 / CH4, CO2 / H2 / N2 / CH4, C3H6 / C3H8, C3H6 / N2, C3H8 / N2 και C3H6 / C3H8 / N2 εξετάστηκε συναρτήσει της θερμοκρασίας, της σύστασης και της πίεσης της τροφοδοσίας καθώς και της παρουσίας ή μη υγρασίας στο ρεύμα της τροφοδοσίας. Τα πειράματα διαπερατότητας απέδειξαν, ότι ευνοείται η εκλεκτική μεταφορά κυρίως του CO2 και του C3H6 μέσα από τις μεμβράνες. Η εκλεκτικότητα μπορεί να αποδοθεί στην ισχυρή αλληλεπίδραση των μορίων αυτών με τα κατιόντα Na+ που περιέχονται στη δομή του φωγιασίτη.
Τέλος, μελετήθηκαν οι μηχανισμοί μεταφοράς μάζας των μιγμάτων CO2 / H2 και CO2 / H2 / N2 / CH4 με τη χρήση της θεωρίας Stefan-Maxwell. Επιπρόσθετα εξετάστηκαν διάφορες περιπτώσεις αργού σταδίου (διάχυση και εκρόφηση) καθώς και συνδυασμοί διαφορετικών μηχανισμών διάχυσης (επιφανειακή διάχυση και ενεργοποιημένη διάχυση αερίων). Οι συντελεστές διάχυσης υπολογίστηκαν από το συνδυασμό των πειραματικών δεδομένων ρόφησης και διαπερατότητας των καθαρών συστατικών. Η ανάλυση που πραγματοποιήθηκε οδήγησε στο συμπέρασμα ότι η μεταφορά των μιγμάτων μέσα από τις μεμβράνες μπορεί να προβλεφθεί κυρίως από το μηχανισμό της επιφανειακής διάχυσης. / Zeolites are crystalline aluminosilicate materials. They are frequently called molecular sieves because they have pores of molecular dimensions. They are able to adsorb gases or vapors, to exchange framework cations and to catalyze a large number of chemical reactions. Due to their physicochemical properties they are ideal materials for the discrimination of molecules based on their shape, size or polarity. The last decade part of the research attention has been focused on the synthesis of polycrystalline zeolite membranes for the separation of gas and vapor mixtures.
In the present thesis the crystallization of faujasite membranes on porous flat or tubular α-Al2O3 substrates was studied as a function of several synthesis parameters such as composition, temperature, time and aging of sol mixtures. Five different compositions were examined. Membranes synthesized using sols with composition 4.17Na2O : 1.0Al2O3 : 10TEA (triethanolamine) : 1.87SiO2 : 460H2O, had the best separation performance. The ability of the membranes to separate CO2 / H2, CO2 / N2, CO2 / CH4, CO2 / H2 / N2 / CH4, C3H6 / C3H8, C3H6 / N2, C3H8 / N2 and C3H6 / C3H8 / N2 mixtures was examined as a function of temperature, feed mixture composition, total feed pressure and the presence or not of humidity in the feed side. In all cases the membranes were either CO2 or C3H6 selective. The separation ability can be attributed to the strong interaction between those molecules with the Na+ cations of the faujasite framework.
The transport of CO2, H2, N2 and CH4 through the membranes was modeled using the Maxwell-Stefan theory. Two different cases of rate limiting step (diffusion and desorption) as well as several combinations of different diffusion mechanisms (surface diffusion and activated gaseous diffusion) were considered. The diffusion coefficients were calculated using the single-component permeation and adsorption data. It has been possible to predict the multicomponent permeation fluxes when surface diffusion was assumed the transport mechanism of all species.
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THE GAS HYDRATE PROCESS FOR SEPARATION OF CO2 FROM FUEL GAS MIXTURE: MACRO AND MOLECULAR LEVEL STUDIESRipmeester, John A., Englezos, Peter, Kumar, Rajnish 07 1900 (has links)
The “Integrated Coal Gasification Combined Cycle” (IGCC) represents an advanced approach for green field projects for power generation. This process requires separation of carbon dioxide from the shifted-synthesis gas mixture (fuel gas). Treated fuel gas consists of approximately 40% CO2 and rest H2. Gas hydrate based separation technology for hydrate forming gas mixtures is one of the novel approaches for gas separation. The present study illustrates the gas hydrate-based separation process for the recovery of CO2 and H2 from the fuel gas mixture and discusses relevant issues from macro and molecular level perspectives. Propane (C3H8) is used as an additive to reduce the operating pressure for hydrate formation and hence the compression costs. Based on gas uptake measurement during hydrate formation, a hybrid conceptual process for pre-combustion capture of CO2 is presented. The result shows that it is possible to separate CO2 from hydrogen and obtain a hydrate phase with 98% CO2 in two stages starting from a mixture of 39.2% CO2. Molecular level work has also been performed on CO2/H2 and CO2/H2/C3H8 systems to understand the mechanism by which propane reduces the operating pressure without compromising the separation efficiency.
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Carbon molecular sieve dense film membranes for ethylene/ethane separationsRungta, Meha 07 November 2012 (has links)
The current work focused on defining the material science options to fabricate novel, high performing ethylene/ethane (C₂H₄/C₂H₆) separation carbon molecular sieve (CMS) dense film membranes. Three polymer precursors: Matrimid®, 6FDA-DAM and 6FDA:BPDA-DAM were used as precursors to the CMS membranes. CMS performances were tailored by way of tuning pyrolysis conditions such as the pyrolysis temperature, heating rate, pyrolysis atmosphere etc. The CMS dense film membranes showed attractive C₂H₄/C₂H₆ separation performance far exceeding the polymeric membrane performances. Semi-quantitative diffusion size pore distributions were constructed by studying the transport performance of a range of different penetrant gases as molecular sized probes of the CMS pore structure. This, in conjunction with separation performance data, provided critical insights into the structure-performance relationships of the CMS materials. The effects of testing conditions, i.e. the testing temperature, pressure and feed composition on C₂H₄/C₂H₆ separation performance of CMS dense films were also analyzed. These studies were useful not just in predicting the membrane behavior from a practical stand-point, but also in a fundamental understanding of the nature of CMS membrane separation. The study helped clarify why CMS membranes outperform polymeric membrane performance, as well as allowed comparison between CMS derived from different precursors and processing conditions. The effects on C₂H₄/C₂H₆ separation in the presence of binary gas mixture were also assessed to get a more realistic measure of the CMS performance resulting from competition and bulk flow effects. The current work thus establishes a framework for guiding research ultimately aimed at providing a convenient, potentially scalable hollow fiber membrane formation technology for C₂H₄/C₂H₆ separation
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Carbon molecular sieve hollow fiber membranes for olefin/paraffin separationsXu, Liren 25 September 2013 (has links)
Olefin/paraffin separation is a large potential market for membrane applications. Carbon molecular sieve membranes (CMS) are promising for this application due to the intrinsically high separation performance and the viability for practical scale-up. Intrinsically high separation performance of CMS membranes for olefin/paraffin separations was demonstrated. The translation of intrinsic CMS transport properties into the hollow fiber configuration is considered in detail. Substructure collapse of asymmetric hollow fibers was found during Matrimidᆴ CMS hollow fiber formation. To overcome the permeance loss due to the increased separation layer thickness, 6FDA-DAM and 6FDA/BPDA-DAM polyimides with higher rigidity were employed as alternative precursors, and significant improvement has been achieved. Besides the macroscopic morphology control of asymmetric hollow fibers, the micro-structure was tuned by optimizing pyrolysis temperature protocol and pyrolysis atmosphere. In addition, unexpected physical aging was observed in CMS membranes, which is analogous to the aging phenomenon in glassy polymers. For performance evaluation, multiple "proof-of-concept" tests validated the viability of CMS membranes under realistic conditions. The scope of this work was expanded from binary ethylene/ethane and propylene/propane separations for the debottlenecking purpose to mixed carbon number hydrocarbon processing. CMS membranes were found to be olefins-selective over corresponding paraffins; moreover, CMS membranes are able to effectively fractionate the complex cracked gas stream in a preferable way. Reconfiguration of the hydrocarbon processing in ethylene plants is possible based on the unique CMS membranes.
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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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Clathrates d’Hydroquinone : aspects fondamentaux et appliqués pour la séparation du CO2 d’un mélange CO2/CH4 / Hydroquinone Clathrates : Fundamental and applied aspects of capturing CO2 from a CO2/CH4 gas mixtureCoupan, Romuald 26 September 2017 (has links)
Les clathrates organiques, particulièrement ceux formés entre l’hydroquinone (HQ) et les gaz, sont des entités supramoléculaires montrant un potentiel intéressant comme matériau alternatif pour les applications de stockage et de séparation de gaz. Cette étude traite de l’évaluation du clathrate d’HQ pour la séparation du CO2 contenu dans les mélanges CO2/CH4 par réaction gaz-solide. D’un point de vue fondamental, différentes propriétés des clathrates d’HQ-CO2, -CO2/CH4 et -CH4 ont été analysées: signatures spectroscopiques, structures cristallines, morphologies, capacités de stockage de gaz, températures de relargage de gaz et températures de transition structurales. Ce travail offre aussi de nouveaux éléments de compréhension des mécanismes de formation et de dissociation des clathrates d’HQ. Il est montré que, pour capturer efficacement et sélectivement le CO2, la réaction d’enclathration doit être faite en utilisant l’intermédiaire « clathrate vide » formé à partir du clathrate d’HQ-CO2. D’un point de vue pratique, les courbes d’équilibre, les enthalpies de dissociation, et les occupations dans les conditions d’équilibre ont été déterminées pour les clathrates d’HQ-CO2 et -CH4 dans une gamme étendue de température allant de 288 à 354 K. De plus, la cinétique de la réaction d’enclathration a été étudiée expérimentalement et modélisée. Dans cette optique, un matériau composite à base d’hydroquinone a été développé, et permet de capter et stocker le gaz de manière réversible, et d’améliorer significativement la cinétique d’enclathration. Le procédé de séparation de gaz basé sur la formation du clathrate d’hydroquinone a aussi été étudié. L’influence des paramètres opératoires (i.e. temps de réaction, pression, température et composition du gaz d’alimentation) sur la cinétique de capture, la sélectivité et la capacité de stockage de gaz ont été évaluées à travers des expériences menées à l’échelle pilote. / Organic clathrate compounds, particularly those formed between hydroquinone (HQ) and gases, are supramolecular entities recently highlighted as promising alternatives for applications such as gas storage and separation processes. This study deals with an evaluation of the HQ clathrates to separate CO2 from CO2/CH4 gas mixtures through direct gas-solid reaction. On the fundamental point of view, new insights into several properties of the CO2-, CO2/CH4-, and CH4-HQ clathrates were studied: spectroscopic signatures, crystal structures, morphologies, gas storage capacities, guest release temperatures and structural transition temperatures. This work also offers new elements of understanding HQ clathrate formation and dissociation mechanisms. It is shown that, for capturing CO2 the most selectively and efficiently, the enclathration reaction has to be done with the “guest-free intermediate” derived from the CO2−HQ clathrates. On a practical point of view, the equilibrium curves, the dissociation enthalpies, and the occupancies at the equilibrium clathrate forming conditions, were determined for the CO2- and CH4-HQ clathrates in an extended range of temperature from about 288 to 354 K. Moreover, the kinetics of the gas-solid enclathration reaction were studied experimentally and modelled. In this way, HQ-based composite materials were developed and allows to reversibly capture and store gases, and to significantly improve the enclathration kinetics. The hydroquinone clathrate based gas separation (HCBGS) process was also investigated. The influence of the process operating parameters (i.e. reaction time, pressure, temperature and feed gas composition) on the CO2 capture kinetics, the selectivity toward CO2, and the storage capacity were assessed through experiments performed at pilot scale.
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Développement de membranes à base de polybenzimidazole et de liquides ioniques pour applications à haute température comme membranes échangeuses de protons (PEMs) et pour la séparation de gaz / Development of polybenzimidazole and ionic liquid based membranes for high temperature proton exchange membranes (PEMs) and gas separation applicationsKallem, Parashuram 15 June 2017 (has links)
1. Membranes échangeuses de protons à haute température (HT-PEM) pour application dans les piles à combustible:Le succès des piles à combustible à base de HT-PEM dépend fortement du matériau membranaire. D’importants progrès ont été accomplis dans la conception de PEMs à transport facilité de protons. L'objectif de la première partie de ce travail de thèse était de fabriquer des membranes électrolytes à haute conductivité, capables de fonctionner au-dessus de 120°C dans des conditions anhydres, sans acides minéraux, et sans sacrifier la résistance mécanique. La stratégie suivie combine l’utilisation de micro-filtres (support) à base de polybenzimidazole (PBI) présentant un réseau de pores ordonnés, et de liquides ioniques (ILs)à base de polyimidazolium comme phase conductrice. Deux types de micro-filtres de PBI ont été préparés: avec un réseau de pores droits (SPBI), ou avec une structure poreuse hiérarchique (HPBI). Les ILs polymérisés (PIL) suscitent un grand intérêt comme tous les électrolytes flexibles à l'état solide en raison de leur sécurité d’utilisation et de leur bonne stabilité thermique, chimique et électrochimique. Dans ce travail, un IL monomèrique protique 1-H-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide a été choisi pour sa conductivité protonique élevée, sa faible rétention d'eau et sa bonne stabilité thermique. Puisque les performances d’une PEM formée par immersion d’un support poreux dans un IL dépendent surtout de la structure poreuse du support, il est essentiel d’optimiser l’architecture des pores réservoirs. Ainsi, nos travaux visent à améliorer à la fois la conductivité ionique et la stabilité dimensionnelle des PEMs à base de PIL par une conception appropriée de l'architecture poreuse. En effet, la faible stabilité dimensionnelle et mécanique du poly[1-(3H-imidazolium)éthylène] bis(trifluorométhanesulfonyl) imide est améliorée grâce à son infiltration dans un support PBI architecturé. La configuration d'infiltration, l'addition d’agent réticulant et les conditions de polymérisation UV "in situ" ont été considérées comme paramètres d'optimisation pour les deux types de micro-tamis en PBI.2. Membranes à base de liquide ionique supporté (SILM) pour la valorisation du méthane:La valorisation du gaz naturel, intégrant l'élimination de CO2 et N2, est l’une des applications de séparation des gaz industriels où les membranes sont une alternative prometteuse à petite échelle. L'objectif de nos travaux était de développer des membranes de type SILM, sélectives au CH4. Notre stratégie combine des micro-tamis à base polybenzimidazole (PBI) comme supports présentant une bonne endurance et de bonnes propriétés thermiques, et des liquides ioniques (ILs) protiques avec des ions imidazolium et trifluorométhane sulfonylimide pour la solubilité du CH4. Bien que la faible pression de vapeur du IL protique atténue sa volatilité dans les SILMs traditionnels, son expulsion hors des pores reste une préoccupation majeure. Un design approprié du support, avec des pores submicroniques, combiné à un IL de tension superficielle élevée, devrait générer des SILMs plus stables, adaptées aux applications à pression transmembranaire modérée ou élevée. Ainsi, des supports PBI à porosité aléatoire (RPBI), obtenus par séparation de phase, ont été largement utilisés. En outre, la polymérisation des RTILs peut fournir d’autres avantages en termes de sécurité, de stabilité et de propriétés mécaniques. Dans cette étude, trois classes de SILMs à base de PBI, avec le IL protique 1-H-3-methylimidazolium bis(trifluoromethane sulfonyl)imide (IL), le monomérique 1-H-3-vinyllimidazolium bis(trifluoromethane sulfonyl)imide (MIL) et le polymérique poly[1-(3H-imidazolium)ethylene] bis(trifluoromethanesulfonyl)imide (PIL) ont été fabriqués avec succès et caractérisées en perméation de gaz purs. Des membranes hautement permsélectives au méthane ont été obtenues, qui sont très prometteuses pour la séparation de mélanges de gaz tels que CH4/N2 / 1. High temperature Proton Exchange Membranes (HT-PEMs) for Fuel Cell applications:The success of the High temperature proton exchange membrane fuel cell (HT-PEMFC) direction is very much dependent on the development of the membrane material. With facilitated proton transport chemistries, great progresses in designing and fabricating facilitated PEMs have been accomplished. The objective of this first part of the PhD work was to fabricate highly conductive electrolyte membranes capable to operate above 120°C under anhydrous conditions and in the absence of mineral acids, without sacrificing the mechanical behavior. The followed rationale is based on the combination of polybenzimidazole (PBI) microsieves as structural supports and poly-imidazolium based ionic liquid (IL) moieties as conducting phase. Two types of PBI microsieves have been prepared following two different microfabrication processes: straight porous PBI and hierarchically structured PBI microsieves.Polymeric ionic liquids (PILs) have triggered great interest as all solid-state flexible electrolytes because of safety and superior thermal, chemical and electrochemical stability. In this part, the 1-H-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide has been mainly selected due to its high proton conductivity, low water uptake values as well as thermal stability.The consecution of a polymeric container with optimized pore architecture is extremely essential since the performance of PEM based on immersing a porous support into ILs, mainly depends on the porous structure. Thus, our research efforts have been directed to improve both, the ion conductivity and the dimensional stability of the PIL supported PEMs by a proper design of the porous architecture. Herein, the diminished dimensional and mechanical stability of poly[1-(3H-imidazolium)ethylene]bis(trifluoromethanesulfonyl)imide has been improved thanks to its infiltration on a PBI support with specific pore architecture. The infiltration configuration, cross-linker addition and “in situ” UV polymerization conditions were taken as optimization parameters for both PBI type microsieves.2. Supported Ionic liquid membranes (SILMs) for methane upgrading:The natural gas upgrading, i.e. removal of CO2 and N2, is one of the major industrial gas separation application where membranes arise as promising alternative at small scale.The objective of this second part of the work was to develop CH4 selective Supported Ionic Liquid Membranes (SILMs). Once again, the rationale followed is based on the combination of PBI microsieves as structural supports, to take advantage of its endurance and thermal properties, and protic ILs with imidazolium and trifluoromethane sulfonyl)imide ions due to their CH4 solubility properties. Although the negligible protic IL vapor pressure alleviates one of the problems associated with traditional SILMs, namely liquid volatility; expulsion of the liquid from the membrane pores is a major concern. A proper design of the support, with sub-micron pores, combined with IL having high surface tension could lead to SILM with adequate physical stability for applications involving moderate to high trans-membrane pressures. Therefore, random porous PBI supports, obtained by phase separation method, have been extensively used. In addition, polymerization of RTILs could provide additional advantages in terms of safety, stability and mechanical properties.In this study, three classes of SILMs, based on PBI with the 1-H-3-methylimidazolium bis(trifluoromethane sulfonyl)imide, the 1-H-3-vinylimidazolium bis(trifluoromethane sulfonyl)imide and the poly[1-(3H-imidazolium)ethylene] bis(trifluoromethanesulfonyl)imide have been successfully fabricated and characterized by single gas permeation measurements. Results revealed that the prepared membranes were highly selective to CH4 and thus very promising for CH4/N2 gas mixture separation.
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Membranes polymères fonctionnalisées par des poly(liquide ionique)s et des nanoparticules de palladium : applications au captage de CO2 et aux membranes catalytiques / Polymeric membranes functionalized by poly(ionic liquid)s and palladium nanoparticles : application for CO² capture and catalytic membranesGu, Yingying 21 July 2015 (has links)
Des membranes supports en polymère ont été photo-greffées par des poly(liquide ionique)s (polyLIs) à base d'imidazolium. Les polyLIs permettent de séparer le CO2 d'autres gaz et de stabiliser des nanoparticules. Dans le cas du captage de CO2, les expériences montrent qu'une couche fine homogène de gel réticulé en polyLI gonflé par du liquid ionique (LI) est obtenue sur la surface de fibres creuses. Les fibres ainsi obtenues ont montré des perméances au CO2 plus élevées (600-700 GPU) que des membranes commerciales et des sélectivités de CO2/N2 comparables (13 et 17). Dans le cas de membranes catalytiques, des nanoparticules de palladium (NPPd) servant de catalyseur ont été immobilisées en forte concentration locale au sein d'une couche de polyLI greffée à la surface de membranes. La réactivité des membranes catalytiques a été testée en configuration de contacteur traversé sur différentes réactions (couplage croisé C-C, hydrogénation, etc). Une conversion totale est obtenue pour des temps de séjours de quelques secondes, sans aucun sous-produit formé. Comparée aux NPPd colloïdaux dans un réacteur en batch, la membrane catalytique accélère les réactions d'environ 2000 fois en terme de temps de réaction sans perte de NPPd; la sélectivité est aussi accrue. Le réacteur membranaire catalytique a été modélisé afin d'obtenir les profils de concentration et de température et une meilleure compréhension des performances obtenues. Les membranes catalytiques se révèlent isothermes et les constantes cinétiques sont calculées. Enfin, les capacités de production de ces membranes catalytiques à une échelle industrielle sont estimées à environ 3 t/(hm3) pour le couplage de Suzuki. / Polymeric support membranes were modified via photo-grafting by poly(ionic liquid)s (polyILs), featuring in the capability to separate CO2 from other gases and to stabilize metallic nanoparticles (MNPs). For CO2 capture, a thin polyIL-IL gel layer was homogenously coated on support hollow fibers. The composite fibers show high CO2 permeance and reasonable CO2/N2 selectivity. For the catalytic membrane, palladium NPs were generated inside a grafted polyLI layer. Compared to colloidal palladium system in a batch reactor, the catalytic membrane, as a contactor membrane reactor, is more efficient in terms of reaction time (ca. 2000 times faster), selectivity and MNP retainability. Theoretical study on reactor modeling, concentration & temperature profiles, and production capacity was done for an overall understanding of the catalytic membrane.
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