Conselho Nacional de Desenvolvimento Científico e Tecnológico / This work aims the synthesis and study of ZSM-5 catalysts for the conversion of ethanol to light olefins, especially, using an alternative and inexpensive route. The ethanol emerges as a renewable source for the production of olefins and the ZSM-5 catalyst has important characteristics for this type of reaction such as acidity, surface area and particle size. The synthesis was carried out in hydrothermal treatment at 170 °C. Were performed two conventional synthesis with templates, using n-Butylamine and tetrapropylammonium hydroxide (TPAOH), and an third and alternative route using a nucleating gel. The catalyst characterization was performed using several techniques (XRD, BET, XRF, SEM and TGA) and was observed the formation of the ZSM-5 structure in all the synthesis methods. The catalysts were evaluated in the ethanol to olefins (ETO) reaction, and was evaluated the influence of the reaction temperature (250 to 450 °C) and SAR (SiO2/Al2O2 ratio) in the selectivity for olefins. The products analyses were made with a gas chromatograph with a FID-type detector. The ethylene yield was above to 80 % for all catalysts, and some above 90 %. Lower SAR values provided higher yields for propylene, around to 9 %. The temperature, SAR and template used in the synthesis influenced in the selectivity. In addition, was evaluated the influence of the catalyst mass, dilution and also its modification with different metals. When the mass was increase, the yield for propylene increased. The catalyst dilution with common sand provided, in some concentrations, greater propylene formation. The nucleating gel method showed to be a viable alternative for ZSM-5 synthesis and its use in the ETO reaction. / Este trabalho relata o estudo da síntese e caracterização de catalisadores ZSM-5 para seu posterior uso na reação de conversão de etanol para olefinas, especialmente utilizando uma rota alternativa mais econômica. O etanol surge como uma fonte renovável para a produção de olefinas e o catalisador ZSM-5 possui importantes características para esse tipo de reação, tais como acidez, área superficial e tamanho de partícula. A síntese foi conduzida de maneira hidrotérmica a 170 °C. Foram realizadas duas sínteses convencionais com direcionadores de estrutura, utilizando n-butilamina e hidróxido de tetrapropilamônio (TPAOH), e uma terceira rota alternativa utilizando um gel nucleante. A caracterização dos compostos sintetizados foi realizada com diversas técnicas (DRX, BET, FRX, MEV e TGA) sendo observada a formação da estrutura de ZSM-5 em todas as técnicas de síntese utilizadas. Os catalisadores foram avaliados na reação de conversão de etanol à olefinas (ETO) e foi avaliada a influência da temperatura de reação (250 a 450 °C) e SAR (SiO2/Al2O3 ratio) na seletividade das olefinas. A análise dos produtos formados foi realizada em um cromatógrafo a gás com detector tipo FID. O rendimento para eteno foi superior a 80 % em todos os catalisadores, sendo para alguns acima de 90 %. Baixos valores de SAR proporcionaram maiores rendimentos para propeno, em torno de 9 %. A temperatura, o valor de SAR e os direcionadores empregados na síntese influenciaram na seletividade. Também, foi avaliada a influência da quantidade de massa do catalisador, a diluição e também a modificação com diferentes metais (Ga, La, In) e um não metal (P). Quando a massa foi aumentada, o rendimento para propeno aumentou consideravelmente. A diluição com areia comum, em algumas concentrações, proporcionou maior formação de propeno. O método de síntese via gel nucleante mostrou ser uma alternativa viável para a síntese de ZSM-5 e seu uso como catalisador na reação ETO.

Diese Arbeit befasst sich mit der katalytischen Umsetzung von oxygenierten Kohlenwasserstoffen in einem Strömungsrohrreaktor bei 500 °C an mikroporösem Alumosilicat ZSM-5, an dem mesoporösem Alumosilicat Al-MCM-41 sowie an deren Mischphasen. Anhand der katalytischen Untersuchungen ist es möglich, für verschiedene Anforderungen an das Produktspektrum Empfehlungen an die Eigenschaften des zu verwendeten Katalysatorsystems zu formulieren. Hierfür wurden Untersuchungen zum Einfluss relevanter Syntheseprozessparameter auf die Zusammensetzung von Al-MCM-41/ZSM-5-Mischphasen vorgenommen. Die Synthese solcher Mischphasen wurde über einen 'Zwei-Template/Ein-Schritt“-Ansatz durchgeführt, der es erlaubte, die an das Katalysatorsystem gestellten Anforderungen durch eine geeignete Wahl der Syntheseparameter zu genügen. Während der Synthese der Al-MCM-41/ZSM-5-Mischphasen beobachtet man drei sich gegenseitig beeinflussenden Vorgänge, die durch, in der wässrigen Syntheselösung vorliegende, alumosilicatische Komponenten miteinander verknüpft sind: Die Auflösung und anschließende Restrukturierung einer nicht-porösen amorphen Phase, die Auflösung und Restrukturierung einer mesoporösen Al-MCM-41-Phase und die Kristallisation einer mikroporösen ZSM-5-Phase. Durch die Erhöhung des Al-Anteils im Synthesegel werden die ZSM-5-Kristallisation verlangsamt und der Schwerpunkt des Gleichgewichts dieser drei Vorgänge für einen gegebenen Reaktionszeitpunkt in Richtung der Bildung der mesoporösen Al-MCM-41-Phase verlagert. Der Einfluss des, in das jeweilige Katalysatorsystem eingebauten Aluminiums auf die katalytische Umsetzung von Oxygenaten manifestiert sich für die beiden Alumosilicate ZSM¬ 5 und Al MCM-41 auf verschiedene Weise. Eine Erhöhung des Al-Anteils in einem mikroporösen ZSM-5-Katalysatorsystem begünstigt den Verlauf von bimolekularen Reaktionen. Dies äußert sich in einem verstärkten Auftreten von Paraffin-bildenden Raktionen wie die Wasserstoff-Transfer-Reaktionen und/oder die Carboniumionen-Spaltung sowie in einer Dominanz von Aromaten-bildenen Reaktionen wie die Cyclisierung mit anschließender Dehydrierung und Aromatisierung. Dieser Effekt kann bei einer Erhöhung des Al-Anteils in einem mesoporösen Al-MCM-41-Katalysatorsystem nur im geringen Maße beobachtet werden. Jedoch nimmt mit sinkendem Si/Al-Verhältnis in beiden Katalysatorsystemen der Anteil an Produkten mit drei oder vier Kohlenstoffatomen zu. Zudem kann dabei eine beginnende Unabhängigkeit des gebildeten Produktspektrums von der Kettenlänge und der funktionellen Gruppe des umgesetzten Oxygenats beobachtet werden.:Inhaltsverzeichnis 1 Einleitung und Problemstellung 1 2 Grundlagen 4 2.1 Hydrothermale Synthese von Alumosilicaten 4 2.1.1 WÄSSRIGE CHEMIE UND HYDROTHERMALE BEHANDLUNG VON ALUMOSILICATEN 4 2.1.2 STRUKTUR UND BILDUNGSMECHANISMUS VON AL-MCM-41 5 2.1.3 STRUKTUR UND BILDUNGSMECHANISMUS VON ZSM-5 6 2.2 Katalytische Spaltung von Kohlenwasserstoffen an Alumosilicaten 9 2.2.1 NATUR UND LOKALISIERUNG VON SÄUREZENTREN 9 2.2.2 KOHLENWASSERSTOFF-POOL-MECHANISMUS UND VERKOKUNG 10 3 Experimentelles Vorgehen und analytische Messverfahren 14 3.1 Syntheseroute zur Herstellung von Al MCM 41/ZSM 5-Mischphasen, Al MCM 41 und ZSM-5 14 3.1.1 AL MCM 41/ZSM 5 MISCHPHASEN 14 3.1.2 AL-MCM-41 17 3.1.3 ZSM-5 17 3.2 Datenerhebung und -auswertung relevanter physikalisch-chemischer und festkörperanalytischer Charakterisierungsmethoden 17 3.2.1 PULVER-RÖNTGENDIFFRAKTOMETRIE 17 3.2.2 N2-PHYSISORPTION 19 3.2.3 TEMPERATUR-PROGRAMMIERTE AMMONIAK-DESORPTION 21 3.2.4 ELEMENTARANALYSE 23 3.2.5 27AL MAS NMR 24 3.2.6 THERMOGRAVIMETRISCHE ANALYSE 25 3.3 Katalytische Austestung und Analyse der Messdaten 26 3.3.1 VERSUCHSDURCHFÜHRUNG 26 3.3.2 ANALYSE UND AUSWERTUNG KATALYTISCHER MESSDATEN 27 3.3.3 DURCHGEFÜHRTE KATALYTISCHE TESTMESSUNGEN 29 4 Untersuchungen zum Bildungsmechanismus von Al MCM 41/ZSM 5-Mischphasen 33 4.1 Mechanistische Deutung 33 4.1.1 VORBETRACHTUNG 33 4.1.2 REAKTIONSABLAUF 34 4.1.3 UNTERSUCHUNG DER MESOPOROSITÄT 39 4.1.4 MORPHOLOGISCHE BETRACHTUNG 43 4.2 Wechselwirkungen der „Beeinflussungsfaktoren“ 45 4.2.1 EFFEKT VERSCHIEDENER AUTOKLAV-TYPEN 45 4.2.2 EFFEKT DES AL-ANTEILS IM SYNTHESEGEL 48 4.2.3 SYMBIOTISCHE EINFLUSSNAHME VON ALUMINIUM UND TENSIDEN 50 5 Charakterisierung verwendeter Katalysatormaterialien 52 5.1 ZSM-5 52 5.2 Al-MCM-41 57 5.3 Physikalische Mischungen aus Al-MCM-41 und ZSM-5 60 6 Katalytisches Spalten von Oxygenaten an ZSM 5 64 6.1 Katalytisches Spalten von Alkohol-Oxygenaten an ZSM 5 in Abhängigkeit des Si/Al Verhältnisses 64 6.1.1 PRODUKTANALYSE ANHAND DER KOHLENSTOFFANZAHL IM PRODUKTMOLEKÜL 65 6.1.2 PRODUKTANALYSE ANHAND EINZELNER STOFFGRUPPEN 68 6.2 Katalytisches Spalten von Carbonyl-Oxygenaten an ZSM 5 in Abhängigkeit des Si/Al Verhältnisses 71 6.2.1 PRODUKTANALYSE ANHAND DER KOHLENSTOFFANZAHL IM PRODUKTMOLEKÜL 72 6.2.2 PRODUKTANALYSE ANHAND EINZELNER STOFFGRUPPEN 76 6.3 Ableitung eines Kohlenwasserstoff-Pool Mechanismus zur Beschreibung des katalytischen Spaltens von Oxygenaten an ZSM 5 80 6.3.1 VEREINHEITLICHUNG DES OXYGENAT FEEDS ÜBER DESSEN DEOXYGENIERUNG 81 6.3.2 ASSIMILATION KURZKETTIGER OLEFINE DURCH EINEN KATALYTISCH AKTIVEN BEREICH 83 6.3.3 EINFLUSS DES PORENSYSTEMS UND AL-ANTEILS IM KATALYSATORSYSTEMS 85 6.3.4 BESCHREIBUNG DER PRODUKTBILDUNG EINZELNER STOFFGRUPPEN IN ABHÄNGIGKEIT WESENTLICHER REAKTIONSBEDINGUNGEN 87 7 Katalytisches Spalten von Triacylglyceriden an Al MCM 41 und physikalischen Mischungen aus Al-MCM-41 und ZSM-5 92 7.1 Gegenüberstellung des katalytischen Spaltens von Ethyloctanoat an Al MCM 41 und ZSM 5 in Abhängigkeit des Si/Al Verhältnisses 92 7.2 Anwendung des Kohlenwasserstoff-Pool Mechanismus zur Beschreibung des katalytischen Spaltens von Triacylglyceriden an physikalischen Mischungen aus Al MCM-41 und ZSM-5 97 7.3 Synthese-Struktur-Wirkungsprinzip 103 8 Zusammenfassung und Ausblick 106 Literatur 112 Abbildungsverzeichnis 127 Tabellenverzeichnis 139 Abkürzungsverzeichnis 141 Anhang 142 Veröffentlichungen 165 Eidesstattliche Erklärung 168

Die Nutzung von Kraftstoffen auf der Basis von Biodiesel erlaubt es, konventionelle, etablierte Antriebstechniken mit Nachhaltigkeit zu kombinieren. Daher kann in den nächsten Jahren mit einer weiteren weltweiten Steigerung der Biodieselproduktion gerechnet werden. Damit verbunden ist jedoch auch ein Anstieg der anfallenden Menge an Glycerol, das bei der Herstellung von Biodiesel als Koppelprodukt entsteht. Da traditionelle Märkte für Glycerol kaum mehr Wachstum zeigen, müssen neue Wege zur effizienten Verwertung von Glycerol gefunden werden. Die vorliegende Arbeit beschäftigt sich mit der heterogen-katalysierten Umsetzung von Glycerol zu Acrolein. Unter Verwendung von ZSM-5-Katalysatorproben mit unterschiedlichem Si/Al-Verhältnis und phosphorsäure-modifizierten Katalysatorproben konnte die Existenz von Synergieeffekten zwischen den texturellen, strukturellen und aciden Eigenschaften in der heterogen-katalysierten Glyceroldehydratisierung zu Gunsten der Acroleinselektivität eindeutig nachgewiesen werden. Eine selektive Umsetzung von Glycerol zu Acrolein wird daher an solchen Katalysatorproben ermöglicht, die ausgewogene texturelle, strukturelle und acide Eigenschaften aufweisen.

The combustion of fossil fuels has for a long time been a problem from an environmental and sustainability point of view, especially when it comes to the emissions of atmospheric carbon dioxide. The environmental concern has for instance shifted the attention towards finding new sustainable alternatives for producing chemicals and fuels, as a substitute to today’s dependence on fossil based crude oil. Catalytic Fast Pyrolysis of biomass is an excellent way to produce valuable chemicals and fuels using renewable resources. However, the process has some drawbacks, for example rapid deactivation of catalysts due to coke formation. Little is known about the characteristics of the formation of catalytic coke from pyrolysis processes, which should be a vital concern in future industrial processes. This thesis is dedicated to investigate the chemical coke characteristics found on zeolitic catalysts. Four zeolites of the type ZSM-5 were chosen for this thesis to deduce any chemical differences in the coke: HZSM-5, Fe/ZSM-5, Ni/ZSM-5, and Fe-Ni/ZSM-5. The coke were characterized by TGA, GC/MS, and FTIR. The results show that Fe/ZSM-5 produced the highest amount of coke compared to the other zeolites, where HZSM-5 had the lowest amount of coke formation. The coke consisted mainly of aromatic and cyclic hydrocarbons, dominated by polycyclic aromatic hydrocarbons. The content of ketones and alcohols in the coke found on HZSM-5 was higher compared to the metal-doped zeolites, while the formation of naphthalenes was lower. The FTIR results also show that coke was mainly comprised of aromatic hydrocarbons. However, traces of alkanes and alkenes reveal that the coke may have a greater variety than the GC/MS analysis suggests. The results show interesting features when metals are introduced to the zeolitic structure, at least when it comes to coke formation. The metal-doping of zeolites certainly seems to alter the chemistry of the catalytic reactions, compared to the parent zeolite. The differences in the chemical characteristics found in the coke are certainly interesting, and it could mean that the chemistry of the bio-oil also varies depending on the metals chosen for the ZSM-5. The new properties that metals introduce to the parent catalyst may open up new possibilities in industrial catalytic processes, and allow industries to take more advantage of the great benefits that biomass has to offer. / Förbränning av fossila bränslen har under lång tid utgjort ett problem ur miljö- och hållbarhetssynpunkt, i synnerhet gällande utsläppen av koldioxid. En större miljömedvetenhet har gett upphov till sökandet efter nya råvaror för att framställa bränslen och kemikalier, utan att förlita sig på fossil råolja. Katalytisk pyrolys av biomassa är ett utmärkt sätt att framställa värdefulla kemikalier från förnybara källor. Processen står dock inför en del tekniska utmaningar, bland annat en snabb deaktivering av använda katalysatorer genom koksning. Målet med detta examensarbete är att undersöka den kemiska sammansättningen av koks, som bildats på zeolitkatalysatorerna. Mer specifikt, att försöka undersöka huruvida den kemiska sammansättningen av koks skiljer sig mellan katalysatorn HZSM-5 och metalldopad HZSM-5. Fyra katalysatorer valdes för detta examensarbete, nämligen HZSM-5, Fe/ZSM-5, Ni/ZSM-5 och Fe-Ni/ZSM-5. Kokset har analyserats genom termogravimetrisk analys (TGA), gaskromatograf kopplad med en masspektrometer (GC/MS), samt Fourier-transform-infraröd-spektroskopi (FTIR). Resultaten visar att Fe/ZSM-5 bildade en större mängd koks jämfört med de andra zeoliterna, varpå HZSM-5 hade lägst halt koks. Utöver detta bestod kokset till största del av aromatiska- och cykliska kolväten, speciellt polycykliska aromatiska kolväten. Innehållet av ketoner och alkoholer i kokset var störst för HZSM-5, medan bildandet av naftalenföreningar ökade för de metalldopade zeoliterna. FTIR-analysen gav även upphov till signaler som är signifikanta för både alkaner och alkener. Därför kan det innebära att kokset innehar en större kemisk variation än vad GC/MS-analysen påvisade. Resultaten visar intressanta egenskaper hos metallmodifierade zeoliter, i synnerhet gällande koksbildning. Det verkar som att de metalldopade zeoliterna påverkar de katalytiska reaktionerna som sker i katalysatorn, jämfört med den obehandlade katalysatorn. Skillnaderna i den kemiska sammansättningen hos kokset för de olika katalysatorerna är definitivt intressant och kan indikera att det även kan föreligga skillnader i den kemiska sammansättningen hos bio-olja, beroende på vilken metall ZSM-5 har behandlas med. De nya egenskaperna som metaller bidrar med till ZSM-5 kan öppna upp nya möjligheter i industriella katalytiska processer, vilket även kan medföra att industrier bättre kan ta tillvara på de fantastiska egenskaper biomassa innehar.

Hydrothermal synthesis of ZSM-5 is an often applied but incompletely understood procedure. In comparison to current research efforts that aim to produce complex micro-mesoporous catalysts for the conversion of biogenic and bulky hydrocarbons, this work focuses on the dependency between Si/Al ratio and zeolite morphology of microporous ZSM-5 to understand and to control the synthesis process. In two series of time dependent crystallization, kinetics were analyzed at Si/Al ratio 20 and 100 to optimize the crystallization time. Subsequently, zeolites with different Si/Al ratio were obtained and characterized. The results show a transition from a slow dissolutionrecrystallization process to a fast solid-state-transformation with increasing Si/Al ratio. This is followed by a switching morphology from clusters of small agglomerates to bigger spherical particles. Respective acid site density and zeolite morphology determine local residence time, hydride transfer behavior and finally selectivity towards aromatics and higher hydrocarbons during methanol conversion. This background should provide control of even more complex syntheses of porous catalysts.

ZSM-5 is an aluminosilicate zeolite with high Si/Al ratio with suitable properties for catalysis, ion exchange, adsorption and membrane applications. The main goal of this thesis was to study the growth of ZSM-5 zeolite crystals from inexpensive natural sources of silica and alumina, as well as n-butylamine (NBA) as a low-cost structure directing agent. The first objective of this work was to develop pathways to synthesize ZSM-5 crystals from kaolin clay or diatomaceous earth, two inexpensive natural sources of silica and alumina (Paper I). In the case of kaolin, a heat treatment was used in order to form amorphous metakaolinite. Subsequently, dealumination of the raw materials by acid leaching made it possible to reach appropriate Si/Al ratios and to reduce the amount of impurities. Finally, leached metakaolinite or diatomaceous earth was reacted with sodium hydroxide and NBA. After synthesis optimization, both sources of aluminosilicates were found to behave differently during the course of synthesis and to lead to slightly different reaction products. The final products exhibited Si/Al ratios in the range 10-20. The use of leached diatomaceous earth allowed to reach higher yield of ZSM-5 crystals within comparable synthesis times. However, low amounts of mordenite were inevitably formed as a by-product, which was related to the high calcium content of diatomaceous earth. Therefore, the rest of the thesis focused on the kaolin system. In order to study the growth mechanism of ZSM-5 from leached metakaolinite, a proper methodology to gain local compositional data by energy dispersive spectroscopy (EDS) on aluminosilicates was developed (Paper II). Zeolite A was used as a model system that could be ion-exchanged with various elements. In order to evaluate the reliability of the measurements, inductively coupled plasma-sector field mass spectrometry (ICP-SFMS) and EDS were compared. The EDS method developed in this work resulted in molar ratios very close to theoretical values and was therefore found more reliable than ICP-SFMS. Therefore, the method developed for zeolite A was applied in the rest of the thesis work to study the formation and growth of ZSM-5 crystals. The second part of this work focused on the kaolin system in order to understand the nucleation and growth processes of the ZSM-5 crystals. This system was heterogeneous, due to the formation of a gel upon heating of the synthesis mixture. First, the internal structure of the gel was investigated (Paper III). Second, a kinetic study was performed and compared with microstructural observations (Paper IV). Finally, the mechanisms leading to Al-zoning and dendritical growth of the zeolite crystals were investigated (Paper V). The characterization of the intermediate phases during the different stages of the hydrothermal synthesis were analyzed by different analytical techniques, such as inductively coupled plasma-sector field mass spectrometry (ICP-SFMS), dynamic light scattering (DLS), extreme high resolution-scanning electron microscopy (XHR-SEM), energy dispersive spectroscopy (EDS), high resolution-transmission electron microscopy (HR-TEM), X-ray diffraction (XRD) and nitrogen gas adsorption. These investigations led to several important conclusions: 1) The walls of the gel were shown for the first time to be inhomogeneous and to possess a biphasic internal structure consisting of a mesoporous skeleton of aluminosilicate nanoparticles embedded in a silicate-rich soluble matrix of soft matter. 2) The kinetic study and microstructural evidences indicated that the early crystals were fully embedded inside the gel phase and that crystal growth was retarded, as the formation of the gel occurred simultaneously with the early growth of the crystals. Hence, nucleation and growth appeared to be solution mediated.  3) Finally, the Al zoning of the crystals was related to the biphasic internal structure of the gel, since the silicate-rich matrix was preferentially consumed first. 4) The dendrites present at the surface of the crystals during most of the growth process were shown to be caused by the presence of a web of nanoparticles, most likely originating from the mesoporous skeleton inside the gel. In the future, these findings are expected to lead to optimized synthesis pathways of catalysts with homogeneous properties and to contribute to the development of poor regions in Bolivia.

This research aimed at improving p-xylene selectivity in toluene disproportionation over ZSM-5 zeolite by exploring the effect of crystal size and various post synthetic modification methods. A comprehensive study of the effect of different modifications on the physicochemical properties of ZSM-5 was investigated using X-ray diffraction (XRD), pyridine adsorption, Fourier transform infra-red (FTIR), 29Si magic-angle spinning nuclear magnetic resonance (MAS NMR), BET surface area by N2 adsorption, inductively coupled plasma (ICP) and scanning electron microscopy (SEM). The catalytic performance of each catalyst was studied in a fixed bed reactor at a temperature 475 °C, WHSV 3-83 h-1 and two different pressures (1 and 10 bar). ZSM-5 zeolites with different crystal sizes (5, 50 and 100 ÂÂμm) were synthesized in house and compared with the commercially obtained ZSM-5 having a crystal size of 0.5 ÂÂμm. The increase in crystal size improved p-xylene selectivity which was attributed to the diffusion constraints imposed by the longer diffusion path lengths of large crystals. The highest p-xylene selectivity (58 %) was achieved over ZSM-5 with the largest crystal size 100 ÂÂμm at the highest WHSV 83 h-1. However, it was accompanied by a low conversion (2 wt. %). ZSM-5 with crystal size of 5 ÂÂμm delivered the best results in terms of the combination of para-selectivity (40 %) and toluene conversion (15 wt. %). The p-xylene produced in the channels of ZSM-5 can quickly isomerise to o-xylene and m-xylene on the external unselective acid sites. Different post modification methods were applied in this study in attempt to suppress the fast isomerization reaction by deactivating the external acid sites. This was achieved to some extent by depositing an inert silica layer using different silica agents, amounts and number of modification cycles and as a result p-xylene selectivity was significantly improved (84 %), especially over large crystals 5 ÂÂμm. The decrease in Brà̧nsted acidity (FTIR) suggested the success of the silylation method. Furthermore, impregnation of lanthanum and phosphorus on ZSM-5 improved p-xylene selectivity (40 %). FTIR measurements showed a drastic drop in the number of Brà̧nsted and Lewis acid sites after loading phosphorus which led to a large reduction in toluene conversion. Lanthanum impregnation had less effect on conversion and increased selectivity with decreased Brà̧nsted sites and pore volume reduction showed by N2 adsorption suggesting some pore narrowing. There are several approaches that can be considered in future to further improve p-xylene selectivity. Improving the synthesis of large crystals to balance acidity and crystal size can lead to the enhancement of p-xylene selectivity. Also, performing toluene disproportionation on optimised pre-coked ZSM-5 large crystals at high pressure can help to maintain the conversion while increasing p-xylene selectivity. Another approach would be to apply silylation modification to extruded large crystals ZSM-5.

In this work, the steady-state performance of zeolite-based (Cu-ZSM-5) and vanadium-based honeycomb monolith catalysts was investigated in the selective catalytic reduction process (SCR) for NO removal using NH3. The aim was to delineate the effect of various parameters including pretreatment of the catalyst sample with H2, NH3-to-NO ratio, inlet oxygen concentration, and space velocity. The concentrations of the species (e.g. NO, NH3, and others) were determined using a Fourier Transform Infrared (FTIR) spectrometer. The temperature was varied from ambient (25 C) to 500 C. The investigation showed that all of the above parameters (except pre-treatment with H2) significantly affected the peak NO reduction, the temperature at which peak NO reduction occurred, and residual ammonia left at higher temperatures (also known as 'NH3 slip'). Depending upon the particular values of the parameters, a peak NO reduction of around 90% was obtained for both the catalysts. However, an accompanied generation of N2O and NO2 species was observed as well, being much higher for the vanadium-based catalyst than for the Cu-ZSM-5 catalyst. For both catalysts, the peak NO reduction decreased with an increase in space velocity, and did not change significantly with an increase in oxygen concentration. The temperatures at which peak NO reduction and complete NH3 removal occurred increased with an increase in space velocity but decreased with an increase in oxygen concentration. The presence of more ammonia at the inlet (i.e. higher NH3-to-NO ratio) improved the peak NO reduction but simultaneously resulted in an increase in residual ammonia. Pretreatment of the catalyst sample with H2 (performed only for the Cu-ZSM-5 catalyst) did not produce any perceivable difference in any of the results for the conditions of these experiments.

This thesis focus on the analysis of spin-lattice NMRD relaxation profilesmeasured in various complex systems such as proteins, zeolites and ionicliquids. Proton, deuterium and fluoride T1-NMRD relaxation profiles wereobtained from a fast-field cycling (FFC) instrument. It is found that alsopossible to obtain NMRD profiles from the molecular dynamics (MD)simulation trajectories. NMRD Profiles were analyzed by using differentrelaxation models, such as the Solomon-Bloembergen-Morgan (SBM) theoryand the Stochastic Liouville (SL) theory. Paper I described the hydration of protein PrxV obtained from a MDsimulation, and compared with the picture emerges from an analysis byusing a generally accepted relaxation model [appendix C]. The result showsthat the information from NMRD analysis is an averaged picture of watermolecules with similar relaxation times; and the MD simulations containsinformation of all types of interested water molecules with differentresidence times. In paper II NMRD profiles have been used to characterize the hydration ofthe oxygen-evolving complex in state S1 of photosystem II. NMRDexperiments were performed on both intact protein samples and Mndepletedsamples, and characteristic dispersion difference were foundbetween 0.03 MHz to 1 MHz; approximately. Both the SBM theory and theSL theory have been used to explain this dispersion difference, and it isfound that this is due to a paramagnetic enhancement of 1-2 water moleculesnearby ~10 Å from the spin center of the Mn4CaO5 cluster. The result showsthe reorientation of the molecular cluster is in μs time interval. Whencompare these two theories, the SL theory presented a better interpretationbecause parameters obtained from the SBM theory shows they didn’t fulfilthe presupposed perturbation criterion (the Kubo term). Paper III deals with the water dynamics in the restricted/confined spaces inthe zeolite samples (H-ZSM-5 and NH4-ZSM-5) and obtained by proton anddeuterium spin-lattice NMRD profiles. The results show that the spin-latticeNMRD can be used to characterize various zeolites. The temperature has aweak effect on the relaxation rate R1, but the change of different counter ionsmay change the hydration and the translational diffusion pores and givedifferent R1. Proton and fluoride NMRD profiles and MD simulations were both used tostudy the dynamics of BMIM[PF6] in paper IV. Results indicate the reorientation of the molecules are in the ns time regime, and the effectivecorrelation time obtained from 1H and 19F are the same. From the MDsimulation it is found the reorientation of [PF6]- ions is much faster (in ps)compare with BMIM+ ion which moves in the ns time range. With previous results, the FFC NMRD profiles are indeed very informativetools to study the molecular dynamics of complex systems. The MDsimulation can be used as a complementary method to obtain detailedinformation. By combine these two methods, it provide a more colorfulpicture in the study of protein hydration and liquid molecular dynamics.

Made available in DSpace on 2016-06-02T20:36:28Z (GMT). No. of bitstreams: 1 3358.pdf: 2280113 bytes, checksum: 836e1809b57b84adf512d641f8aa3180 (MD5) Previous issue date: 2010-09-27 / Financiadora de Estudos e Projetos / The current market demands make with what Brazilian agribusiness search improvements in processes and new materials to reduce waste, pollution and biological contamination. Mainly materials that more are easily degraded by the action of microorganisms or abiotic factors.It is known that the synthetic plastics are difficult of degrade and one alternative to decrease their use and hence the contamination of the environment is the introduction of biodegradable plastics such as thermoplastic starch (TPS). Thus, this study aimed to develop nanocomposites of TPS, seeking conditions for the incorporation of nanozeólitas (ZSM-5) that could confer properties related to control hydrophilicity. The work started in the construction of hydrothermal reactors for the standardization of zeolite. The synthesis gel was based on a molar ratio has been already studied (Al2O3: 60SiO2: 11TPAOH: 900H2O). The hydrothermal treatment was done in five different ways, varying temperatures (100, 150 and 200oC) and time (24, 48 and 72 hours). The five samples were characterized by X-ray diffraction, nitrogen physisorption, particle size analysis by light scattering and scanning electron microscopy at high resolution. The best condition of formation of zeolite phase was 200oC for 24 hours. This synthesis was repeated and characterized by four times to obtain 27g of nanozeólitas to be used to obtain the composite processing. The compositions of thermoplastic starch and nanozeólita were made in a torque rheometer with mass ratios of 0, 2, 4, 6, 8 and 10% ZSM-5 TPS, keeping fixed the final mass of the mixture, 45 g. Thermogravimetric analysis of films showed that the increased load of nanozeolites in the matrix polymer no caused change in the temperatures of the events that occur in the mass losses. The results of dynamic mechanical thermal analysis showed no significant variations in glass transition temperatures of the glycerol and starch, which were influenced by the increase of ratio glycerol / starch. The analysis of tensile mechanics showed that up to 6% zeolite added there is no impairment of mechanical properties of films, above this value occurs a lower elastic modulus of the composite and consequently an increase in the deformation of the material also caused by variations in the relationship between ratio glycerol and starch. Statistical analysis of variance for this experiment confirmed the previous supposition. The pervaporation water vapor showed that the increased load of zeolite in the polymer matrix facilitated the passage of water through the polymer matrix due to the presence of the channels characteristic of the zeolite. Statistical analysis of variance showed that the most significant change was the 10% zeolite added. Through these studies we can see that it is possible to incorporation of zeolite in thermoplastic starch using the same equipment used in processing of synthetic plastics. This study also showed that the incorporation of zeolite modified the hydrophilicity of the material facilitating the passage of water vapor by the matrix polymer by channels of zeolite. / As exigências do mercado atual fazem com que a agroindústria brasileira busque melhorias nos processos e novos materiais a fim de diminuir o desperdício, a poluição e a contaminação biológica. Principalmente materiais que sejam mais facilmente degradados por meio da ação de microorganismos ou fatores abióticos. Sabe-se que os plásticos sintéticos atuais são de difícil degradação e uma alternativa para a diminuição do seu uso e por conseqüência a contaminação do meio ambiente é a introdução de plásticos biodegradáveis tal como o amido termoplástico (TPS). Sendo assim, objetivou-se neste trabalho o desenvolvimento de nanocompósitos de TPS, buscando condições para a incorporação de nanozeólitas (ZSM-5) que pudessem conferir propriedades relacionadas ao controle de hidrofilicidade. O trabalho teve início na construção de reatores hidrotérmicos para a padronização da zeólita. O gel de síntese teve como base uma proporção molar já estudada (Al2O3:60SiO2:11TPAOH:900H2O). O tratamento hidrotérmico foi feito de cinco formas diferentes, variando temperatura (100, 150 e 200oC) e tempo (24, 48 e 72 horas). As cinco amostras foram caracterizadas por difração de raios X, fisissorção de nitrogênio, análise de tamanho de partículas por espalhamento de luz e microscopia eletrônica de varredura de alta resolução. A melhor condição de formação da fase zeolítica foi de 200oC por 24 horas. Esta síntese foi repetida e caracterizada por quatro vezes para a obtenção das 27g de nanozeólitas a serem utilizadas na obtenção do compósito polimérico. As composições de amido termoplástico e nanozeólita foram feitas em um reômetro de torque com proporções em massa de 0, 2, 4, 6, 8 e 10% de ZSM-5 em TPS, mantendo fixa a massa final da mistura em 45 g. As análises termogravimétricas dos filmes mostraram que o aumento da carga de nanozeólita na matriz polimérica não houve mudanças nas temperaturas dos eventos em que ocorrem as perdas de massa. Os resultados das análises térmicas dinâmico-mecânica mostraram que não houve variações significativas nas temperaturas de transições vítreas tanto do glicerol como do amido, que foram influenciadas pelo aumento da relação glicerol/amido. As análises de resistência à tração mecânica mostraram que até 6% de zeólita adicionada não há comprometimento das propriedades mecânicas dos filmes, já acima ocorre um abaixamento no modulo elástico do compósito e consequentemente um aumento na deformação do material causado também pela variação na relação entre glicerol e amido. A análise estatística de variância para esse experimento comprovou essa suposição. A pervaporação ao vapor de água mostrou que o aumento da carga de zeólita na matriz polimérica facilitou a passagem de água pela matriz polimérica, isto devido à presença dos canais característicos da zeólita. A análise estatística de variância mostrou que a variação mais significativa foi a de 10% de zeólita adicionada. Por meio desses estudos podese observar que é possível a incorporação de zeólita em amido termoplástico utilizando os mesmos equipamentos utilizados no processamento dos plásticos sintéticos. Esse estudo também mostrou que a incorporação da zeólita modificou a hidrofilicidade do material facilitando a passagem do vapor de água através dos canais da zeólita.