Philosophiae Doctor - PhD / In South Africa, almost 90 % of the country’s electricity is generated from coal combustion. This reliance on coal for energy production is projected to continue in the near and medium term due to the increasing demand for industrial and domestic energy. During coal combustion, a large quantity of fly ash is produced as the main waste product and in South Africa approximately 36 - 37 million tons of fly ash is produced on a yearly basis. The management of huge quantities of fly ash has been and still is a continuing challenge that requires urgent intervention. In this regard, there exists an urgent need to maximize fly ash beneficiation, thus forming the motivation for this research. The overall objectives of this thesis was to synthesize high pure phase zeolites A and X from South African fly ash, study their formation mechanism, and explore the potential of mine waters during the synthesis process as well as developing new and efficient zeolite synthetic protocols by the use of ultrasound. In order to address these objectives, the research was designed in a sequential manner so that the preceding results could act as a platform for the attainment of the next objective. In this case, the identification and optimization of synthesis conditions for producing zeolite A and X acted as a basis for understanding the influence of use of mine waters as a substitute for pure water. This further laid the foundation for the in-situ ultrasonic monitoring of the formation process of zeolite A and X from fly ash. The final stages of the study involved use of ultrasonic energy as an ageing tool to improve the conditions obtained during the hydrothermal synthesis of zeolite A as well as investigate the potential to synthesize zeolites directly by use of ultrasound without the need for the fusion, aging or conventional hydrothermal treatment step. The result of the optimized synthesis conditions for producing zeolite A starting either from clear extract of fused fly ash or unseparated, fused South African class F fly ash slurry were molar regimes of 1 Al2O3 : 30.84 Na2O : 4 SiO2 : 414.42 H2O or 1 Al2O3 : 5.39 Na2O : 2.75 SiO2 : 111.82 H2O respectively and at a hydrothermal synthesis temperature of 100 °C for 2 hours. The optimized procedure was simple, efficient and resulted in a considerable improvement of the quality and phase purity of the zeolite A product when the clear extract of fused fly ash was used instead of starting from unseparated, fused fly ash slurry. On the other hand, the optimized synthesis conditions for preparing the typical octahedral shaped zeolite X from South African fly ash was found to be a molar regime of 1 Al2O3 : 4.90 Na2O : 3.63 SiO2 : 115.92 H2O at a hydrothermal synthesis temperature of 80 ºC for hours.

>Magister Scientiae - MSc / Coal is the main source of electricity in South Africa, the combustion of which produces a large amount of waste (coal fly ash) annually. The large-scale generation of coal fly ash places major strain on landfills and the material is toxic in nature. The high silicon and aluminium content in fly ash makes it a suitable starting material for zeolite synthesis. Utilisation of fly ash as a starting material for zeolite synthesis alleviates an environmental burden by converting a waste product to an industrially applicable material. In this study, hierarchical zeolite X was synthesised from coal fly ash via the fusion method. The clear fused fly ash (FFA) extract (with molar composition 0.12 Al·14.6 Na·1.00 Si·163 H₂O) served as the synthesis solution for hydrothermal treatment. The influence of synthesis parameters (such as Si/Al ratio, aluminium source, hydrothermal temperature and stirring) on hierarchical zeolite X formation was studied to determine the cause behind the formation of this material. Synthesised zeolites and starting materials (Arnot coal fly ash and fused fly ash) were characterised by various analytical techniques such as XRD and SEM-EDS to determine the phase purity, morphology and elemental composition (framework Si/Al ratio) of these materials. The synthesis of hierarchical zeolite X under hydrothermal conditions was found to be highly sensitive to the aluminium content of the synthesis solution. The hierarchical morphology of zeolite X was formed preferentially in relatively aluminium-deficient (i.e. high Si/Al ratio) synthesis environments under stirred hydrothermal conditions of 90 °C for 16 hours. In the case of sodium aluminate addition, octahedral shaped zeolite X crystals were formed in relatively low Si/Al ratio synthesis environments, which was attributed to the presence of excess sodium cation content in the synthesis solution. Selected hierarchical zeolites (D2 and E2) were characterised further to gain more insight into the properties of this material. HR-TEM and FTIR revealed that hierarchical zeolite D2 and E2 exhibited the typical structural features of zeolite X. Zeolite D2 and E2 contained both micropores and mesopores and had a high BET surface area of 338-362 m²/g. These zeolites also exhibited appreciable solid acidity (0.81-1.12 mmol H/g zeolite). These properties make hierarchical zeolite X a favourable material for application in catalysis or adsorption. Overall, the formation of zeolite X with hierarchical morphology was proposed to be linked to the presence of zeolite P1 structural units in the framework of the zeolite. / National Research Foundation

The overall objective of this thesis is to evaluate the fundamentals of current low concentration CO2 separation technologies and to provide an alternate method using adsorption technology with existing as well as new adsorbents. Two different applications for the adsorption of CO2 are explored; Direct Air Capture (DAC) and excimer gas purification. The investigation of aerogels as possible adsorbent for these applications was also explored. The first application, DAC of CO2 using adsorbents, addresses climate change by reducing the amount of atmospheric CO2 levels that are directly correlated to global warming. Because of DAC being carbon negative, this field has gained significant attention in the literature. DAC as a CO2 reduction strategy was approached in two ways: 1. Chapter 2 investigates capturing and concentrating CO2 from 0.04% in the air to 95% to be able to sequester it into the ground. This research began by doing an adsorbent selection using pure gas gravimetric measurements on seven different commercially available type X zeolites that were determined to have potential for this separation. Breakthrough experiments were then carried out with the most promising zeolite by perturbing the bed with compressed ambient air. In the process studied, a basic four step temperature vacuum swing adsorption (TVSA) cycle was investigated comprising the following steps: pressurization, adsorption, blowdown, and desorption. Four different regeneration temperatures were tested along with four different gas space velocities. With this cycle configuration, CO2 was concentrated to 95% from 0.04% with total capture fractions as high as 81%. This study highlighted methods to reduce the energy consumption per ton of CO2 captured in the system as well as the potential of using low Si/Al ratio faujasite structured zeolites in DAC of CO2 for greenhouse gas reduction. 2. Chapter 3 expands on the research of Chapter 2 by capturing CO2 from 0.04% in the air and concentrating it to high purity CO2 levels where the cost for operating the process will be reimbursed through the value of the produced CO2. The goal of this research was to increase the CO2 to as high as possible because the purer the CO2, the more valuable it is. This research started by conducting an in-depth investigation into the pure gas adsorption of CO2, N2, O2, and Ar on the most promising zeolite from Chapter 2. The data was then fitted to the TD-Toth model which allowed for the evaluation of the TVSA cycle and showed the potential of reducing the pressure and/or elevating the temperature during the blowdown step in order to produce high purity CO2. To confirm this, the TVSA cycle was run on a fixed bed breakthrough experiment where high purity CO2 was produced between a concentration of 99.5% and 99.96% by lowering the blowdown pressure. By controlling the blowdown temperature, the concentration of the product was increased from 99.8% to 99.95%, however with a significant loss of CO2. This effect of N2, O2, and Ar desorbing during the blowdown step with CO2 desorbing during the evacuation step is shown graphically by measuring the concentration and flow rate of the exiting gas species. The results from this study show the potential for producing a valuable product of high purity CO2 from atmospheric concentrations. The second application in this thesis that is explored in Chapter 4 is the purification of trace impurities of CO2, CF4, COF2, and O2 from F2, Kr, and Ne for applications in excimer lasers. Due to the incompatibility of many adsorbents to F2 and HF, aluminas and polymeric adsorbents were selected as potentially compatible materials. To increase the compatibility of these adsorbents, the use of a cryo-cooler was determined to be feasible to precool the feed stream before separation, which increases the adsorption capacity and compatibility of the material to F2 and HF. To determine the adsorption potential in the low concentration of these adsorbents, the concentration pulse chromatographic technique was chosen to determine the Henry’s Law constants of CO2, CF4, and O2. This data was then plotted on the van’t Hoff plot and extrapolated to colder temperatures to determine the benefit of using a cryo-cooler. From this study, it was determined that HayeSep Q was the best polymeric adsorbent with significant adsorption of CO2 at temperatures below -50˚C while being the best performing CF4 adsorbent. AA-300 was the best performing alumina in this study while having significant adsorption of CF4 at temperatures below -135˚C. However, from a compatibility standpoint, both of these materials need to be tested to determine their robustness in the presence of F2 and HF at room and reduced temperatures. Chapters 5 & 6 in this thesis explore the fundamentals of adsorption on aerogels as a prelude to using aerogels as possible adsorbents for DAC of CO2. This investigation into aerogels looks at silica aerogels and carbon aerogels, which are both industrially produced and explores their adsorption with relation to like materials such as silica gel and activated carbons. Both of these Chapters utilize experimentally determined adsorption isotherms of CO2, N2, O2, and Ar as well as characterization to determine adsorption trends in the materials. Some major conclusions for silica aerogels were that common surface modifications to make the material more resilient against water adsorption impacts the adsorption of CO2 significantly with roughly 4 fold difference in adsorption capacity. For carbon aerogels some major conclusions were that the adsorption was increasingly dominated by the heterogeneous nature of the surface at lower pressures and increasingly dominated by the pore size at the higher pressures. Both chapters discuss the adsorption of air along with ideas such as the influence of gas thermal conductivity in the pores with respects to adsorption. L'objectif général de cette thèse est d'évaluer les principes fondamentaux des technologies actuelles de séparation du CO2 à faible concentration et de fournir une méthode alternative utilisant la technologie d’adsorption avec des adsorbants actuels ainsi que d'en découvrir de nouveaux. Deux applications différentes pour l'adsorption du CO2 ont été explorées; la capture directe dans l’air ambient (CAD) et la purification des gaz excimères, ainsi que la recherche d'aérogels comme adsorbant possible pour ces applications. La première application, le CAD du CO2 utilisant des adsorbants, pourrait répondre aux changements climatiques puisque les niveaux de CO2 atmosphérique sont directement corrélés au réchauffement climatique. Dernièrement, le CAD a fait l'objet d'une attention particulière en tant que stratégie de réduction du CO2, par conséquent, deux voies différentes ont été explorées dans cette thèse: 1. Le chapitre 2 étudie la capture et la concentration du CO2 de 0,04% dans l'air à 95% afin de pouvoir l’enfermer dans la terre. Pour ce faire, une sélection d'adsorbant a été effectué en utilisant des mesures gravimétriques à gaz pur sur sept zéolithes de type X disponibles dans le commerce qui ont été déterminés comme ayant un potentiel pour cette séparation. Des expériences révolutionnaires ont ensuite été réalisées avec la zéolite la plus prometteuse en perturbant le lit avec de l'air ambiant comprimé. Dans le processus étudié, un cycle basique à quatre étapes d’adsorption modulée en température et pression (AMTP) a été étudié, comprenant les étapes suivantes: pressurisation, adsorption, purge et désorption. Quatre températures de régénération différentes ont été testées ainsi que quatre vitesses spatiales de gaz différents. Avec cette configuration de cycle, le CO2 était concentré à 95% de 0,04% avec des fractions de capture totales aussi élevées que 81%. Cette étude a mis en évidence des méthodes pour réduire la consommation d'énergie par tonne de CO2 captée dans le système ainsi que le potentiel d'utilisation de zéolithes structurées à base de faujasite à faible rapport Si/Al dans le CAD du CO2 pour la réduction des gaz à effet de serre. 2. Le chapitre 3 approfondit les recherches du chapitre 2 en capturant le CO2 de 0,04% dans l'air et en le concentrant à des niveaux de très haute pureté où le processus sera remboursé par la valeur du CO2 produit. L'objectif de cette partie était d'augmenter la pureté du CO2 le plus possible car plus le CO2 est pur, plus il est précieux. Une enquête approfondie sur l'adsorption de gaz pur de CO2, N2, O2 et Ar sur la zéolite la plus prometteuse du chapitre 2. Les données ont ensuite été ajustées au modèle TD-Toth qui a permis d'évaluer le cycle AMTP et a montré le potentiel de réduire la pression et/ou d'élever la température pendant l'étape de purge afin de produire du CO2 de haute pureté. Pour confirmer cela, le cycle AMTP a été fait par le biais d’une expérience dans un lit fixe où du CO2 de haute pureté a été produit entre une concentration de 99,5% et 99,96% en abaissant la pression de purge. En contrôlant la température de purge, la concentration du produit est passée de 99,8% à 99,95%, mais avec une perte importante de CO2. Cet effet de la désorption de N2, O2 et Ar pendant l'étape de purge avec la désorption du CO2 pendant l'étape d'évacuation est illustré graphiquement en mesurant la concentration et le débit des espèces de gaz sortant. Les résultats de cette étude montrent le potentiel de production d'un produit précieux de CO2 de haute pureté à partir des concentrations atmosphériques. La deuxième application de cette thèse qui est explorée au Chapitre 4 est la purification des traces d'impuretés de CO2, CF4, COF2 et O2 de F2, Kr et Ne pour des applications dans les lasers à excimère. En raison de l'incompatibilité de nombreux adsorbants avec le F2 et le HF, les alumines et les adsorbants polymères ont été sélectionnés comme matériaux potentiellement compatibles. Pour augmenter la compatibilité de ces adsorbants, l'utilisation d'un cryoréfrigérant a été jugée possible pour pré-refroidir le flux d'alimentation avant la séparation, ce qui augmente la capacité d'adsorption et la compatibilité du matériau en F2 et HF. Pour déterminer le potentiel d'adsorption dans la faible concentration de ces adsorbants, la technique de chromatographie pulsée de concentration a été choisie pour déterminer les constantes de la loi de Henry de CO2, CF4 et O2. Ces données ont ensuite été tracées sur le graphique van’t Hoff et extrapolées à des températures plus froides pour déterminer les avantages de l’utilisation d’un cryoréfrigérant. À partir de cette étude, il a été déterminé que HayeSep Q était le meilleur adsorbant polymère avec une adsorption significative de CO2 à des températures inférieures à -50 ° C tout en étant l'adsorbant CF4 le plus performant. L'AA-300 était l'alumine la plus performante de cette étude tout en ayant une adsorption significative de CF4 à des températures inférieures à -135 °C. Cependant, du point de vue de la compatibilité, ces deux matériaux doivent être testés pour déterminer leur robustesse en présence de F2 et de HF à température ambiante et réduite. Les chapitres 5 et 6 explorent les principes fondamentaux de l'adsorption sur les aérogels en prélude à l'utilisation d'aérogels comme adsorbants possibles pour le CAD du CO2. Cette enquête sur les aérogels examine les aérogels de silice et les aérogels de carbone, qui sont tous les deux fabriqués industriellement et explore leur adsorption par rapport à des matériaux similaires tels que le gel de silice et les charbons actifs. Ces deux chapitres utilisent des isothermes d'adsorption déterminés expérimentalement de CO2, N2, O2 et Ar ainsi que la caractérisation pour déterminer les tendances d'adsorption dans les matériaux. Certaines conclusions majeures pour les aérogels de silice étaient que les modifications de surface courantes pour rendre le matériau plus résistant à l'adsorption d'eau ont un impact significatif sur l'adsorption de CO2 avec une différence d'environ 4 fois dans la capacité d'adsorption. Pour les aérogels de carbone, certaines conclusions majeures étaient que l'adsorption était de plus en plus dominée par la nature hétérogène de la surface à des pressions plus faibles et de plus en plus dominée par la taille des pores aux pressions plus élevées. Les deux chapitres discutent de l'adsorption d'air ainsi que des idées telles que l'influence de la conductivité thermique du gaz dans les pores en ce qui concerne l'adsorption.

Dans le domaine spatial, la contamination moléculaire est un problème important pouvant affecter considérablement la performance des instruments embarqués. Selon l’environnement thermique, certaines molécules polluantes provenant du dégazage sous vide des matériaux constitutifs des satellites viennent en effet se déposer sur les surfaces sensibles telles que les optiques et les différents détecteurs. Grâce à leur structure microporeuse organisée qui leurs confère de remarquables capacités d’adsorption, les zéolithes sont des solides de choix pour minimiser les risques de pollution. Les pastilles, billes et peintures zéolithiques offrent plus précisément l’avantage d’être directement intégrées dans la structure interne des satellites, sont légères et non pulvérulentes. C’est pourquoi l’objectif de cette thèse est d’étudier la mise en forme de poudre zéolithique. Les propriétés mécaniques et les propriétés d’adsorption des objets obtenus seront étudiées pour confirmer leur utilisation dans le domaine du spatial.Au cours de ce travail, trois mises en forme ont été développées : les pastilles, les billes et les peintures zéolithiques. Les pastilles zéolithiques ont présenté des propriétés mécaniques très intéressantes, contrairement aux billes zéolithiques qui peuvent engendrer une contamination particulaire lors de la mise en orbite du satellite (vibrations). Les capacités d’adsorption de ces deux mises en forme sont satisfaisantes : des molécules telles que le n-hexane, le cyclohexane et le 3-méthylpentane y ont été adsorbées. Enfin, la première formulation de peinture zéolithique a conduit à des capacités d’adsorption correctes (diminution de 20 % due à la présence de liant) avec une adhésion (test ISO 2409) acceptable. Cette dernière mise en forme est une des nombreuses perspectives des travaux réalisés au cours de cette thèse. / In low earth orbit, global performances of satellites can be affected by the contamination of critical surfaces as optical devices and detectors. On-orbit molecular contamination is due to outgassed organic pollutants emanating from spacecraft materials. One way to reduce and to eliminate this phenomenon is the use of molecular adsorbents. Among them, zeolites appear to be relevant materials for contaminants retaining. Unlike common powder materials, zeolites films can also avoid the secondary dust contamination due to particles breeding and can be easily inserted in the satellite structure. As a consequence, this work deals with the shaping of zeolitic powder.Three shapes were developed during this work: pellets, beads and paints. Zeolitic pellets showed very interesting mechanical properties, on the contrary to zeolitic beads which can beget a particulate contamination (vibrations). The adsorption capacities of these two shapes are good: molecules such as n-hexane, cyclohexane and 3-methylpentane were adsorbed. Finally, the first formulation of a zeolitic paint was developed: a loss of 20 % of the adsorption capacities was observed (presence of binder). The adhesion (ISO 2409 test) was acceptable. This last shape is one of the many perspectives of this work.

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.

Οι ζεόλιθοι είναι φυσικά ένυδρα αργιλοπυριτικά ορυκτά, με πολύ χρήσιμες ιδιότητες από πλευράς δομής και χημικής σύνθεσης, γεγονός που τους καθιστά κατάλληλους για πολλές χρήσεις, τόσο ως φυσικά ορυκτά όσο και ως τεχνητά. Μερικά από τα σημαντικότερα χαρακτηριστικά των ζεόλιθων είναι η μικρή πυκνότητα που παρουσιάζουν με μεγάλο όγκο κενών η σταθερή κρυσταλλική δομή τους και τα ομοιόμορφα σε μέγεθος κανάλια τους. Σε αυτά τα χαρακτηριστικά τους οφείλουν και την πληθώρα των ιδιοτήτων τους που τους καθιστά ιδιαίτερα χρήσιμους, όπως είναι η μεγάλη ιοντοανταλλακτική τους ικανότητα, καθώς και η ικανότητα προσρόφησης και κατάλυσης. Οι ζεόλιθοι εξαιτίας των μεγάλων κενών και των καναλιών που παρουσιάζει η δομή τους, χρησιμοποιούνται ως πληρωτικά στη χαρτοβιομηχανία, ως ελαφριά αδρανή σε τσιμέντα και σκυροδέματα, καθώς και ως συμπληρώματα διατροφής στην κτηνοτροφία. Επιπρόσθετα, η ικανότητά τους να ανταλλάσουν κατιόντα, βοηθά στον έλεγχο της περιβαλλοντικής ρύπανσης με διάφορες εφαρμογές, στην αποσκλύρυνση του σκληρού νερού, στο διαχωρισμό του οξυγόνου από το άζωτο στον αέρα, στη μετατροπή του πετρελαίου σε καταλύτες, σε λιπάσματα και βελτιωτικά εδαφών αλλά και σε ανθεκτικά απορροφητικά οξέως που χρησιμοποιούνται κατά την ξήρανση και τον καθαρισμό του φυσικού αερίου. Οι αφυδατωμένοι ζεόλιθοι χρησιμοποιούνται σε πληθώρα βιομηχανικών εφαρμογών, όπου η επιλογή του εκάστοτε ζεόλιθου προϋποθέτει τον έλεγχο των ανταλλάξιμων κατιόντων και της θερμοκρασίας. Επίσης, χρησιμοποιούνται για την αύξηση του αριθμού των οκτανίων της βενζίνης και το διαχωρισμό κορεσμένων από τους ακόρεστους υδρογονάνθρακες. Ζεόλιθοι χρησιμοποιούνται συχνά και σαν φορείς καταλυτών μεγάλης πτητικότητας, για την εκλεκτική προσρόφηση μετάλλων από διαλύματα, στη δέσμευση βαρέων μετάλλων από βιομηχανικά απόβλητα και τη συγκράτηση επικίνδυνων ραδιενεργών στοιχείων από πυρηνικά απόβλητα. Οι συνθετικοί ζεόλιθοι είναι προτιμότεροι από τους φυσικούς στις περισσότερες βιομηχανικές εφαρμογές, εξαιτίας της ενιαίας χημικής τους σύστασης και κρυσταλλικότητας, αλλά μειονεκτούν λόγω του υψηλού κόστους παραγωγής τους, ωθώντας στηνν αναγκαιότητα της αξιοποίησης των αποθεμάτων των φυσικών ζεόλιθων. Αποθέσεις ζεόλιθων στον Ελλαδικό χώρο απαντώνται σε βαθιά μη ηφαιστειακά ιζήματα των Ιόνιων νήσων, όπως στη Ζάκυνθο, στην Κεφαλονιά και τη Λευκάδα, αλλά και σε μεταμορφωμένα πυροκλαστικά πετρώματα στη Θράκη, στα νησιά Κίμωλος και Πολύαιγος, καθώς και στη Σάμο, τη Μήλο και τη Σαντορίνη. Αυτά τα κοιτάσματα δημιουργήθηκαν είτε από υδροθερμικές εξαλλοιώσεις με τη βοήθεια μετεωρικού ή/και θαλασσινού νερού, είτε από τη διαγένεση του ηφαιστειακού γυαλιού σε ανοιχτά υδρολογικά συστήματα, με την κυκλοφορία βασικών εδαφικών νερών, είτε σε περιβάλλοντα αλμυρών λιμνών με υψηλή αλκαλικότητα. Στην παρούσα πτυχιακή εργασία, μελετήθηκαν 24 δείγματα από περιοχές της πιο πρόσφατης ηφαιστειακής δραστηριότητας της νήσου Μήλου, οι οποίες παρατηρούνται γύρω από τα ηφαιστειακά κέντρα της Φυριπλάκας (νότια) και του Τράχηλα (βόρεια). Το νησί αυτό, αποτελείται κυρίως από ηφαιστειακά προϊόντα, με εναλλαγές πυροκλαστικών προϊόντων χερσαίας απόθεσης και τοφφιτών, αποτεθειμένων σε θαλάσσιο περιβάλλον. Κύριος στόχος της εν λόγω μελέτης είναι ο ορυκτολογικός και χημικός προσδιορισμός των εξαλλοιωμένων τόφφων της νήσου Μήλου, η ιοντοανταλλακτική ικανότητά τους, καθώς και ο προσδιορισμός του περιβάλλοντος σχηματισμού τους, με έμφαση στις ορυκτολογικές, ιστολογικές και χημικές τροποποιήσεις που υπέστησαν κατά τα στάδια εξαλλοίωσης τους. Οι ζεολιθοποιημένοι τόφφοι από τη νήσο Μήλο μελετήθηκαν ορυκτολογικά και ιστολογικά, μέσω μακροσκοπικής και μικροσκοπικής παρατήρησης, ενώ πραγματοποιήθηκε και ακτινογραφική μελέτη, τόσο των φυσικών δειγμάτων, όσο και του αργιλικού τους κλάσματος. Ακολούθως, ελέγχθηκαν χημικά και οι αναλύσεις τους επεξεργάσθηκαν, ενώ εφαρμόσθηκε και η μέθοδος Isocon, για την προσέγγιση της κινητικότητας των στοιχείων κατά την πορεία της εξαλλοίωσσής τους. Τέλος, προσδιορίστηκε και η ιοντοανταλλακτική ικανότητα σε επιλεγμένο αριθμό δειγμάτων. / Zeolites are natural hydrated aluminosilicate minerals with very useful properties in terms of structure and chemical composition, which makes them suitable for many uses, such as natural minerals and as artificial. Some of the important characteristics of the zeolites are sparsely presenting with large void volume of the stable crystalline structure and uniform in size their channels. In these characteristics are and the abundance of properties that make them particularly useful, as is the large ion exchange capacity and adsorption capacity and catalysis. Zeolites due to the large gaps and channels showing their structure, are used as filler in the paper industry as a lightweight aggregate in cement and concrete, as well as dietary supplements in animal husbandry. Additionally, the ability to exchange cations, helps control environmental pollution with various applications in aposklyrynsi of hard water, the separation of oxygen from nitrogen in the air, the conversion of oil catalysts, fertilizers and soil but also acid resistant absorbent used in the drying and cleaning of gas. Dehydrated zeolites used in numerous industrial applications, where the selection of the respective zeolite assumes control of exchangeable cations and temperature. Also used to increase the octane number of gasoline and the separation of the saturated unsaturated hydrocarbons. Zeolites are often used as carriers for catalysts and high volatility, for the selective adsorption of metals from solutions, the binding of heavy metals from industrial waste and containing hazardous radioactive elements from nuclear waste. Synthetic zeolites are preferred by physicists in most industrial applications, because of their uniform chemical composition and crystallinity, but handicapped by the high cost of production, pushing stinn need for the valuation of stocks of natural zeolites. Zeolites deposits in Greece are found in deep non-volcanic sediments of the Ionian islands, as in Zakynthos, Kefalonia and Lefkada, but in metamorphic pyroclastic rocks in Thrace, the islands of Kimolos and Polyaigos and Samos, Milos and Santorini . These deposits were created either by hydrothermal alteration with the help meteoric and / or seawater or diagenesis of volcanic glass in open hydrologic systems with the release of key soil water or in environments salt lakes with high alkalinity. In this thesis, studied 24 samples from areas of more recent volcanic activity of the island of Milos, observed around the volcanic centers Fyriplaka (south) and the neck (north). The island consists mostly of volcanic products, swings pyroclastic products of terrestrial deposition and toffiton, deposited in a marine environment. The main objective of this study is the mineralogical and chemical identification of the altered tuffs of the island of Milos, the ion exchange capacity, and the determination of the environment of their formation, with emphasis on the mineralogical, chemical and histological changes caused by the alteration stages. The zeolithopoiimenoi tuffs from the island of Milos studied mineralogy and histologically by macroscopic and microscopic observation, while held and radiographic study of both natural samples and their clay fraction. Subsequently tested chemicals and their analyzes were processed and applied the method Isocon, to approximate the mobility of elements during the course of their exalloiossis. Finally, determined and ion exchange capacity in a selected number of samples.

Ethylene and propylene are important chemical feedstocks for the production of polyethylene and polypropylene. Ethylene and propylene can be produced by various methods including steam cracking of liquefied natural gas (LNG), naphta or light olefin fractions. The methanol to olefin (MTO) process provides an alternative means of producing ethylene and propylene, where ZSM-5 is frequently used as catalyst due to its hydrophobicity, strong acidity, molecular sieve properties and low tendency towards coking, which makes ZSM-5 one the most popular zeolite catalysts in the industry. The oil crisis 1973 and the second oil crisis in 1978 caused the development of a commercial MTO process. Mobil Research and Development Corporation built a fixed-bed pilot plant to demonstrate the feasibility of the MTO as well as methanol-to-gasoline (MTG) process. When the oil price dropped again during the 1980’s, further developments of commercial processes were stopped for the time being. However, investigations on a bench scale are still pursued, and applications for patents are still submitted. During this study ZSM-5 was synthesized with a hydrothermal method, which produced agglomerated polycrystalline grains with characteristic ZSM-5 morphology and a Si/Al ratio of approximately 40. The synthesis time, synthesis temperature and aging time were varied while keeping all the other synthesis parameters constant in order to determine their influence on crystallite size. The synthesis time was varied between 12-72 hours, synthesis temperature was varied between 130-170°C and aging time between 30-90 minutes. Using SEM to determine crystal size, it was found that a variation in the aging time produced the largest crystallites (average of 21.6μm ± 10.8μm) while also having the largest influence on crystallite size followed by synthesis temperature (average of 13.1μm ± 4.9μm) and finally synthesis time (average of 5.7μm ± 0.4μm). In all cases XRD and SEM confirmed the formation of ZSM-5. To evaluate the as-synthesized ZSM-5 and compare it to a commercial ZSM-5 catalyst, Catalyst A using the MTO process, ZSM-5 was synthesized for 72 hours at 170°C with an aging time of 60 minutes before synthesis. The as-synthesized as well as Catalyst A’s agglomerated polycrystalline grains were sieved into three size fractions: smaller than 75μm, 75-150μm and 150-300μm. All six ZSM-5 fractions of ZSM-5 were used as catalysts for the MTO process in a fixed bed reactor at 400°C, atmospheric pressure and a 20wt% methanol to water feed. At 3.5 hours time on stream (TOS), the intermediate 75-150μm fraction had the highest light olefin selectivity for both the as-synthesized as well as Catalyst A, followed by the 150-300μm fraction and finally the smaller than 75μm fraction with the lowest light olefin selectivity. From this results it is clear that the as-synthesised ZSM-5 did not perform as well as Catalyst A. While the intercrystalline voids of the agglomerated ZSM-5 form second-order pores where self-diffusion is enhanced, the increased diffusional barriers created by the intercrystalline boundaries reduce the diffusion rate, promoting secondary reactions at the strong Brönsted acid sites thereby reducing ethylene and propylene selectivity. Coking reduces access to the Brönsted acid sites and plays a more influencial role for smaller crystallite sizes. Accordingly, the smaller than 75μm fraction had the lowest light olefin selectivity, while the 150-300μm fraction was probably least influenced by coking. The increased pathways for products and reagents in the 150-300μm fraction resulted in more secondary reactions taking place within this catalyst than the 75-150μm fraction explaining the superior performance of the 75-150μm fraction. Since the grain size determines the ratio of the external to the internal surface areas as well as the amount of intercrystalline boundaries in the catalyst, it follows that the catalytic activity and polycrystalline grain size ratio should actually be tailored when optimising the product distribution of the ZSM-5 catalysed MTO process. The as-synthesized ZSM-5 didn’t perform very well when compared to Catalyst A and modification of the synthesis method is recommended. / Thesis (MSc (Chemistry))--North-West University, Potchefstroom Campus, 2012.

Doctor of Philosophy / Department of Chemical Engineering / Jennifer L. Anthony / Zeolites and zeolite-like materials are a group of porous materials with many applications in industry including but not limited to detergent builders and catalyst in the oil refining and petrochemical industry, due to their unique properties such as uniform pore size, large surface area and ion-exchange capacity. Researchers are constantly seeking new methods to synthesize zeolites. Zeolites are commonly synthesized in water. Then in 2004, a new method called ionothermal synthesis was invented by Dr. Morris and his colleagues, using ionic liquids (ILs) and eutectic mixtures as the solvent. In contrast to water, ILs and eutectic mixtures have negligible vapor pressure, thus making the use of high-pressure vessel unnecessary. In addition, they have various structures which could render new structures to frameworks of zeolite. Furthermore, since the cations of some ILs have structures which are similar to common structure directing agents, they theoretically could be used both as solvent and structure directing agent in ionothermal synthesis, possibly simplifying the synthesis process. This project is aimed at investigating the behavior of precursors of zeolites in ionic liquids and the interaction between precursors and ionic liquids in ionothermal synthesis because these fundamental properties could be useful in the current and future synthesis of zeolites. First, solubilities of different precursors, including Syloid 63 silica particles, aluminium isopropoxide (Al(OiPr)3) and phosphoric acid (H3PO4) in ILs with different structures are reported. Parameters such as activity coefficient and Henry’s constant are calculated from the solubility result. Second, interaction between precursors and ILs are studied. It is found that the addition of ILs in Al(OiPr)3 could change the structure of Al(OiPr)3, especially with the presence of H3PO4. Both ILs’ structures and temperature are capable of influencing the structure change of Al(OiPr)3. Third, hydrochloric acid is used for the first time as the mineralizer to synthesize aluminophosphates in ILs and it could lead to both dense and porous materials. Regardless of the acid used, frameworks synthesized after several hours always undergo a dramatic change after further heating. A slightly longer alkyl chain of ILs could accelerate the formation of crystalline materials. Increasing concentration of precursors in the reaction gel could increase the yield, but the same framework is not retained. Researches have also been done on stability of ILs in the synthesis process and it is found that heat and the presence of H3PO4 could decompose ILs, but the decomposed amount is extremely small.

The objective of this work was to study the effect of supercritical water on coke formed on ZSM-5 during its use as a dodecane cracking catalyst. ZSM-5 coking was quantified at different reaction times, finding that the presence of supercritical water reduced coke formation by an order of magnitude or more. Coked samples were analyzed using several methods, including temperature programmed oxidation (TPO), attenuated total reflectance infrared (ATR-IR) spectroscopy, carbon-13 nuclear magnetic resonance (13C NMR), diffuse reflectance ultraviolet-visible spectroscopy (DR-UV-vis) and UV-Raman. Coked produced in the absence of SCW was formed by polycyclic aromatic hydrocarbons (PAHs) with more than 4 aromatic rings containing alkyl side chains. Coke produced in the presence of SCW was formed by aromatics with 1 to 3 aromatic rings. The characteristics of coke formed in the absence of water on ZSM-5 that had been pretreated in SCW were intermediate to those of coke formed on fresh ZSM-5 in the presence and absence of water, suggesting that the presence of water influences coke properties. It was also verified that SCW can decrease coke formation due to its effect on Bronsted acidity of the catalyst and ability to promote coke gasification. The effect of coke deposits produced in the presence and absence of SCW on the rate of ethanol dehydration, a model reaction studied under diffusion-controlled conditions, indicated that SCD/SWC coke deactivated less the catalyst than SCD coke.

Zeólitas tipo Y contendo terras raras, RE,Ca/NaY (RE = La, Ce, Nd, Eu, Gd), foram preparadas a partir da forma NaY (razão Si/Al = 2,4 ) por trocas iônicas sucessivas com soluções de cloreto de cálcio e cloreto de terras raras, -através de refluxo; e subseqüente filtragem a vácuo, secagem e tratamento térmico sob fluxo de nitrogênio. Após o tratamento térmico, os Íons aquosos trivalentes de terras raras sofrem hidrólise, formando hidroxilas catiônicas do tipo [RE. OH]2+ e prótons H+, tornando-se localizados nas cavidades e canais da zeólita. O próton reage com o oxigênio da rede cristalina, originando centros ácidos muito fortes. O tipo específico de terra rara trocado ionicamente influencia a acidez total, força e distribuição dos sítios ativos na zeólita. As composições químicas das celas unitárias das amostras foram determinadas por espectrometria de emissão atômica por plasma de argônio induzido (ICP-AES). A cristalinidade, após troca iônica e tratamento térmico, foi confirmada por espectroscopia na região do infravermelho (FT-IR) e difração de raios-X. A microssimetria do íon európio na zeólita Eu,Ca/NaY foi investigada por espectroscopia eletrônica de emissão na região do visível, sob excitação de radiação ultravioleta (396 nm). As propriedades ácidas das amostras RE, Ca/NaY foram estudadas por termogravimetria (TG) e calorimetria exploratória diferencial (DSC), usando n-butilamina como molécula sonda. Por TG, foi investigada a acidez total das amostras; enquanto que por DSC, utilizando o modelo cinético de Borchardt & Daniels, foi investigada a força ácida relativa das amostras. A presença dos centros ácidos de Brönsted e Lewis foi determinada por espectroscopia na região do infravermelho (1700-1300 cm-1) , usando piridina como molécula sonda. A atividade catalítica e seletividade das amostras foram avaliadas na reação química modelo de alquilação de benzeno com a olefina linear 1-dodeceno para formação de alquilbenzeno linear. A reação foi estudada na fase líquida, em um microrreator de batelada, à temperatura de 80°C. 0s produtos monoalquilados e os isômeros lineares de 1-dodeceno foram determinados por cromatografia em fase gasosa e espectrometria de massa (GC-MS). / The Y zeolites containing calcium and rare earth polivalent cations, RE,Ca/NaY (RE = La, Ce, Nd, Eu, Gd), were prepared by ion exchange, refluxing the NaY zeolite (Si/Al = 2,4) with calcium chloride and rare earth chloride solutions, followed by thermal treatment under nitrogen flow. The trivalent hydrated rare earth ions undergo hydrolysis, forming [RE.OH]2+ cation hydroxyls and protons H+, which react with oxygen in the lattice, generating strong acid sites. The rare earth elements influence the total acidity, strength and distribution of the active sites in the zeolite. The unit cell chemical compositions of the samples were determined by Inductively Coupled Plasma / Atomic Emission spectroscopy (ICP/AES). The crystallinity was confirmed by Fourier Transform Infrared Spectroscopy (FT-IR) and X-ray diffraction. The europium microsimetry in the Eu,Ca/NaY zeolite was investigated by emission electronic spectroscopy in the visible region, under ultra-violet excitation (396 nm). The acid properties of the RE,Ca/NaY samples were studied by Thermogravimetry (TG) and Differential Scanning Calorimetry (DSC), using n-butilamine as molecular probe. From TG curves, the total acidity was calculated, whereas the relative acid strength was determinated by DSC curves, using the Borchardt-Daniels kinetic model. The nature of Brönsted and Lewis acid sites was investigated by FT-IR, in the 1700 - 1300 cm-1 region, using pyridine as molecular probe. The catalytic activity and selectivity of the samples were evaluated on the alkylation of benzene with 1-dodecene model reaction, to form linear alkylbenzenes, in liquid phase, at 80°C using a bath reactor. The reactant conversion, extent of isomerization and product distribution were monitored by Gas Chromatography and Mass Spectrometry techniques (GC-MS).