In dieser Arbeit werden die Ergebnisse mehrerer verschiedener Synthesemöglichkeiten für eine Optimierung der katalytischen Leistung durch Hierarchisierung zweier Molekularsiebe vorgestellt. Dabei wurde der ZSM-5 als Vertreter der Alumosilikate und der SAPO-34 (Silizium Aluminium-phosphat) ausgewählt, da diese als entsprechende MTH-Katalysatoren bereits wirtschaftliche Bedeutung erlangt haben. Die verschiedenen Möglichkeiten, ein solches hierarchisches Netzwerk zu generieren, werden dabei in Bezug auf die katalytische Leistung der jeweiligen Katalysatoren evaluiert und bewertet.

>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

In dieser Arbeit werden die Ergebnisse mehrerer verschiedener Synthesemöglichkeiten für eine Optimierung der katalytischen Leistung durch Hierarchisierung zweier Molekularsiebe vorgestellt. Dabei wurde der ZSM-5 als Vertreter der Alumosilikate und der SAPO-34 (Silizium Aluminium-phosphat) ausgewählt, da diese als entsprechende MTH-Katalysatoren bereits wirtschaftliche Bedeutung erlangt haben. Die verschiedenen Möglichkeiten, ein solches hierarchisches Netzwerk zu generieren, werden dabei in Bezug auf die katalytische Leistung der jeweiligen Katalysatoren evaluiert und bewertet.

Orientador: Prof. Dr. Wagner Alves Carvalho / Dissertação (mestrado) - Universidade Federal do ABC. Programa de Pós-Graduação em Ciência e Tecnologia/Química, 2016. / Zeólitas hierárquicas possuindo estrutura tipo MFI foram preparadas hidrotermicamente utilizando surfactantes como agentes direcionadores de estrutura, constituídos por grupos de amônio quaternário sintetizados neste trabalho. A zeólita preparada utilizando o agente polimérico apresentou uma morfologia tipo nanoesponja com poros de diâmetro elevado. Utilizando o agente direcionador de estrutura C22-6-6 com adição de agente nucleante originou uma zeólita de morfologia tipo nanoesponja, composta por uma rede desordenada tridimensional de camadas MFI com espessura de 2,5nm suportando umas as outras. Com o mesmo agente direcionar, preparou-se uma zeólita de morfologia unilamelar e um material sem adição de alumínio, denominado nanossilicato. Este último material foi submetido a três métodos pós-síntese para modificação da superfície, visando o aumento de acidez. O desempenho catalítico das zeólitas MFI hierárquica e convencional foi investigado na eterificação de glicerol com álcool terc-butílico em fase líquida e na desidratação da frutose em várias condições: fase aquosa, fase orgânica e extração in situ da fase aquosa. As zeólitas hierárquicas foram mais ativas do que as amostras microporosas em ambas as reações, o que pode ser atribuído aos sítios ácidos localizados nas superfícies externas, acessíveis para os reagentes volumosos. A maior seletividade para 5-hidroximetilfurfural foi obtida com nanossilicatos modificados utilizando extração in situ. / Hierarchical zeolites possessing MFI framework type were hydrothermally prepared using surfactants as structure-directing agents consisting of quaternary ammonium groups prepared in this work. The zeolite prepared using polymeric structure-directing agent presented a nanosponge-like morphology with larger pores. The structure-directing agent C22-6-6 was used to prepare materials with different morphologies. Using the seed-assisted synthesis method, a nanosponge-like morphology was obtained. This zeolite was composed of a three-dimensional disordered network of MFI layers with 2.5nm thickness supporting each other. Furthermore, a unilamelar nanosheet zeolite was also prepared, as well as a material without aluminum, called nanosilicate. This last one was submitted to three post synthesis methods for surface modification in order to increase acidity. Catalytic performance of the MFI zeolites, both hierarchical and conventional, was investigated in glycerol etherification with tert-butyl alcohol in liquid phase, and in fructose dehydration in various conditions: aquous phase, organic phase and in situ extraction. Hierarchical zeolites were more active than conventional samples in both reactions, which can be attributed to the acid sites located on the external surfaces accessible for the reaction of bulky reactants. The highest selectivity to 5-hydroxymethyfurfural were obtained with modified nanosilicates and in in situ extraction.

Doctor Educationis / The research focused on the synthesis, characterisation and activity of zeolite supported metal catalysts for the Friedel-Crafts alkylation of benzene with t-butyl chloride. Alkyl benzenes are traditionally produced via systems that employ the use of Lewis acids or strong mineral acids. There have been widespread concerns over these approaches based on their environmental impacts and separation difficulties. Recent approaches have endeavoured the much to use more environmentally eco-friendly systems and zeolites have proved to be versatile support materials. The use of zeolites has also shown to greatly improve product selectivity as well as easing separation constraints. However the adoption of zeolites on large scale Friedel-Crafts alkylation has been hampered by the high cost of zeolite production from commercial sources. On the other hand fly ash has been found to be a viable starting material for zeolite synthesis. Apart from that South Africa is faced with fly disposal challenges and there is continual accumulation of fly ash at the coal fired power stations, which provide about 77 % of the power produced in the country. In this light the use of fly ash will help to reduce the disposal constraints as well as providing a cheap starting material for zeolite synthesis. In this study the hierarchical Zeolite X has been successfully synthesised from fly ash via a hydrothermal treatment. The zeolite was then loaded with Fe/Mn via two approaches namely liquid phase ion exchange and incipient wetness impregnation. For comparison purposes seasoned commercial support materials namely HBEA and MCM- 41 were also loaded with the same metals and characterised with various techniques namely; HRSEM, EDS, HRTEM, XRD, SAED, ICP-OES and N2 adsorption analysis, It was found from the characterisation undertaken that the integrity of the respective supports was generally retained upon metal loading. Both the ICP-OES and the EDS proved that the desired metals were successfully introduced onto the zeolitic support materials. The calculated percentage metal loading for the catalysts prepared via incipient wetness impregnation was closely related to the actual values obtained from the ICP-OES analysis for both the monometallic and the bimetallic catalysts (Fe/Mn). It was observed that the amount of metal that can be introduced on a zeolite via liquid phase ion exchange is largely dependent on the cation exchange capacity of the zeolite Supported metal catalysts for FC alkylation Page v and of the catalysts prepared using 0.25 M Fe solution it was found that Zeolite X had the highest Fe wt% loading of 11.4 %, with the lowest loading of 2.2 % obtained with the MCM-41 supported catalyst. The XRD patterns for the both HBEA and the MCM-41 supported metal catalysts resembled the patterns of the respective prestine support materials except in the case of catalysts with anFe wt % of more than 10, which exhibited peaks due to the Fe2O3 crystallites. In the case of the hierarchical Zeolite X, the metal loaded support had a significant reduction in the XRD peak intensities. The prepared catalysts were tested for the alkylation of benzene with t-butyl chloride. The benzene was also used as the solvent. The alkylation reaction was carried out in a round bottomed flask under reflux conditions and stirring at a temperature of 45 oC over a period of 5 h. A total of 18 catalysts was tested and the highest percentage conversion of 100 % was obtained with the 10%FeH after a reaction time of 2 h. The general trend obtained with the majority of the catalysts was characterised with a rapid initial increase and then steady state was achieved. Generally after a reaction time of 3 h almost all the catalysts had reached steady state in terms of the percentage conversion obtained. The outcomes reflect that the inclusion of Mn does not enhance the conversion but rather decreases it. It was also found that the Mn was not active in the alkylation of benzene as shown by the inactivity of the 10%MnM, where 10% by weight Mn was loaded on MCM-41. However the other monometallic catalysts containing Mn supported on Zeolite X and HBEA were found to be active. The activity is attributed to the presence of Brønsted acid sites in these zeolites which are not present in MCM-41. The selectivity studies reflect that the inclusion of Mn does slightly improve the selectivity towards the formation of the monoalkylated product (t-butyl benzene). The highest selectivity of 91.1 % was obtained with the 10%FeMnM after a reaction time of 4 h. MCM-41 supported catalysts had a relatively higher selectivity compared to the other supports. Considering the Fe monometallic catalysts tested it generally can be said that the yield were in the order HBEA > MCM-41 > Zeolite X. It however should be noted that the percentage yield is calculated from the conversion and selectivity percentages, this implies that the factors affecting these parameters will consequently affect the percentage yield obtained. Supported metal catalysts for FC alkylation Page vi The alkylation reaction was found to be characterised by the formation of two intermediate products which could not be identified. These products were formed during the transient start up stages of the reaction and would disappear from the reaction mixture with longer reaction times, and after 3 h in almost all the reactions studied the intermediates were not detected in the reaction mixture. The main products found were the monoalkylated product (desired product) and the para isomer (1,4-t-di-butyl benzene). There were no other dialkylated isomers or trialkylated products detected. The formation of the para isomer was usually after a reaction time of 2 h in most reactions. The research managed to show that the hierarchical Zeolites X can be synthesised from fly ash and ion exchange and incipient wetness impregnation are appropriate approaches that can be used to introduce Fe/Mn onto the support materials studied. The catalysts prepared were active to varying degrees in the Friedel-Crafts alkylation of benzene with t-butylchloride, with the exception of the 10%MnM which was found to be inactive.