Thesis (M.Ch.E.)--University of Delaware, 2005. / Principal faculty advisors: Jingguang Chen, Raul F. Lobo, Dept. of Chemical Engineering. Includes bibliographical references.

Master of Science / Department of Chemical Engineering / Jennifer L. Anthony / Zeolite refers to a microporous material, which is also called a molecular sieve. There are three major industrial applications of zeolites: adsorbents, ion exchangers, and catalysts; and many other minor applications including: sensors, agriculture, medicine, veterinary, hydrogen storage, fuel cells, microreactors, membrane reactors, and racemic separations. Today, zeolite is not limited to aluminosilicate. Researchers are attempting to use other species (such as B, Ga, Ge, Ti, and Zn) to replace aluminum in zeolites framework to accomplish particular applications. In 1991, the first zincosilicate zeolite was synthesized by Annen et al.. Currently, only four zincosilicate zeolites have been synthesized. Theoretically, zincosilicate should balance divalent cations better than aluminosilicate zeolites to provide a stronger acid site especially for hydrogen cracking reactions. Large pore VET type VPI-8 (Li₁.₉₁₄Zn₁.₉₁₄Si₁₅.₀₈₆O₃₄) is the most thermal stable of all the zincosilicate zeolites and has low chemicals cost, however, a high crystallinity VPI-8 required prohibitively long synthesis times or seeded synthesis procedures. In this work, a seed-free short time synthesis zincosilicate zeolite VPI-8 is presented. Methane, also known as natural gas, had become the largest abundant carbon reserve today, more than the amount of the fossil fuel including conventional gas, oil, and coal. Unlike fossil fuel, methane can be recycled from landfill. Methane could be used to produce useful and/or expensive chemicals via syngas conversion to fuel, paraffin, methanol, alcohol, and dimethoxyethane. In addition to pathways via a syngas intermediate, methane could react directly to ethylene, formaldehyde, and aromatics. Because syngas preparation and compression usually expends 60-70% of the capital cost and consumes almost all the energy of operation, more and more researchers are exploring direct methane activation. However, the high stability of methane is one of the limitations, and coking is another limitation. In this work, methane dehydroaromatization (MDA) over zincosilicate zeolite Li-VPI-8 and ion exchanged Ni/Li-VPI-8 are investigated, due to the stronger acid site in zincosilicate than aluminosilicate zeolites. This is the first time to study using zincosilicate as catalyst, capitalizing on the more efficient synthesis methods demonstrated in this work.

Orientador: Gilson Herbert Magalhães Dias / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-13T19:09:25Z (GMT). No. of bitstreams: 1 Forner_Ricardo_D.pdf: 4146958 bytes, checksum: e310cb4a554e926b949b24daf9b0a2a9 (MD5) Previous issue date: 2008 / Resumo: Esta tese teve como objetivo o estudo dos efeitos estéricos e eletrônicos dos zeólitos faujasita HY, LiY, NaY e CsY na estrutura, reatividade e comportamento térmico do organometálico [MnCp(CO)3]ocluído. As diversas formas alcalinas do zeólito Y foram preparadas por troca iônica no zeólito Na56Y comercial e os estudos das interações, do comportamento térmico e da reatividade do complexo ocluído nos zeólitos foram feitos por espectroscopia de infravermelho com transformada de Fourier (FTIR) em um sistema especialmente construído para essa finalidade. O organometálico [MnCp(CO)3] adsorvido nos zeólitos apresentou, no mínimo, cinco bandas nos espectros FTIR, que foram atribuídas a diferentes sítios de ancoramentos localizados na superfície e na supercavidade. A decomposição do convidado ocluído ocorre com velocidades maiores nos sítios de ancoramento que possuem interações cátion-carbonila mais fracas. Os espectros obtidos para a oclusão do organometálico em zeólitos parcialmente hidratados mostraram que as interações carbonilas-cátions no zeólito parcialmente hidratado são tão intensas quanto às interações do convidado no hospedeiro desidratado. Os cálculos computacionais, que simularam as interações entre o zeólito e o organometálico, forneceram informações sobre energias de interações, comprimentos e ângulos de ligação. Os espectros simulados exibiram bandas de estiramentos de carbonilas próximas às bandas dos espectros obtidos experimentalmente / Abstract: This thesis aimed to study the steric and electronic effects of faujasita zeolites HY, LiY, NaY and CsY on the structure, reactivity and thermal behavior of [MnCp(CO)3] organometallic compound occluded. Various alkaline forms of zeolite Y were prepared by ion exchange in the zeolite Na56Y. Study of the interactions, the thermal behavior and reactivity of the organometallic compound occluded in zeolites were done using FTIR spectroscopy in a system especially constructed for this purpose. The FTIR spectra of [MnCp(CO)3] compound adsorbed in zeolites displays at least 5 bands that were attributed to different anchoring sites located on the surface and in the supercages. The decomposition of the occluded guest was faster in the anchoring sites where the interactions cation-carbonyl were weaker. The occluded organometallic spectra in partially hydrated zeolites have showed the same strength for carbonyl-cation and water-cation interactions. The computational calculations, that have simulated the interactions of the organometallic with zeólito, provided information on interaction energy, lengths and angles of bonds. The simulated spectra have showed carbonyl stretching bands in similar way to experimental spectra / Doutorado / Quimica Inorganica / Doutor em Ciencias Quimicas

M. Tech. / Gold (Au) mining in South Africa resulted in vast volumes of hazardous waste being generated. Poor management of most of the tailings dams has resulted in the release of acid mine drainage, which caused stream water and soil contamination with their run-offs. The consequence of mine closure has not only been observed in large-scale land degradation, but also in widespread pollution of surface water and groundwater in the Wonderfonteinspruit Catchment Area (WCA). Thus, clean-up methods must be developed in order to remove heavy metals from contaminated water bodies in this area. The efficacy of algae, zeolite and zeolite functionalized with humic acid in reducing the concentration of the heavy metals iron (Fe3+), zinc (Zn2+), manganese (Mn2+) and nickel (Ni2+) to acceptable levels in WCA was investigated in this study. It is also envisaged that the heavy metals to be removed from contaminated water can be useful in various industries. A sampling exercise was undertaken with the aim of identifying the heavy metals that contaminate the water in the catchment, as well as identify the priority heavy metals for laboratory sorption tests. Batch experiments were conducted to study the adsorption behavior of natural zeolite clinoptilolite and algae Desmodesmus sp. with respect to Fe3+, Mn2+, Ni2+, and Zn2+. The data was analysed using the Langmuir and Freundlich isotherms. Two kinetic models namely, pseudo-first order and pseudo second order were also tested to fit the data. It was found that the concentration of Fe3+, Mn2+, Ni2+ and Zn2+ was 115 mg/L, 121 mg/L, 26.5 mg/L and 6.9 mg/L from the sampled water bodies in the WCA, respectively. The Langmuir isotherm was found to correlate the adsorption of Fe3+, Mn2+, Ni2+, and Zn2+ better, with the adsorption capacity of 11.9 mg/g, 1.2 mg/g, 1.3 mg/g, and 14.7 mg/g, for the functionalized zeolite (FZ), respectively. The algae system gave adsorption capacities of 1.523 mg/g, 144 mg/g and 71.94 mg/g for Fe3+, Mn2+ and Ni2+; respectively. Pseudo second-order equation was found to be the best fit for the adsorption of heavy metals by unfunctionalized zeolite (UFZ) and the algae system. Zeolite functionalization with humic acid increased its uptake ability. The best results for kinetic study was obtained in concentration 120 ppm for Fe3+ and Mn2+, whilst for Ni2+ was at 20 mg/L , which is about the same concentrations found in contaminated water in the WCA (Fe3+ 115 mg/L, Mn2+121 mg/L and Ni2+ 26.5 mg/L).

>Magister Scientiae - MSc / The use of diesel engines in vehicles and heavy machinery throughout the world has been slowly increasing in the past few decades. This has led to high demand for diesel and gasoline with high octane number. Diesel and gasoline are in high demand due to its qualities as fuels containing low or no sulfur and nitrogen compounds, making them environmentally friendly and the anti- knocking properties respectively. With these reasons and more, researchers have been studying processes like the catalytic oligomerization of olefins to produce synthetic fuels with augmented qualities and properties. The effectiveness of the process will depend on the quality of the catalyst.

With demand for gasoline and diesel expected to decline in the near future, crude-tochemicals technologies have the potential to become the most important processes in the petrochemical industry. This trend has triggered intense research to maximize the production of light olefins and aromatics at the expense of fuels, which calls for disruptive processes able to transform crude to chemicals in an efficient and environmentally friendly way. Simultaneously, the production of high-demand chemical commodities such as olefins, aromatics and gasoline from alternative feedstocks such as methanol has been central to research in both academia and industry. In both conversions, catalyst composition and formulation play a key role. In principle, shaping and optimal compositional formulation are major challenges in the successful industrial application of heterogeneous catalysts. Herein, we evaluate the application of the spray-drying shaping technique to manufacture spherical zeolite-based catalysts and their applicability in the direct crude-to-chemicals and the methanol-to-hydrocarbons processes. A thorough study of the effect of formulated fluid catalytic cracking catalyst composition on the one-step cracking of Arabian light crude oil was studied in the present thesis. Our results demonstrate that over a 35wt.% yield to light olefins can be achieved on spray-dried catalysts containing 1:1 mixtures of ZSM-5 and FAU zeolites. On the other hand, the nature of the selected clay, one of the key components in formulated catalysts, has a significant influence in modifying the final acidity of the composite, which, when applied in methanol to hydrocarbons, results in the propagation of either the alkene or arene cycles. The present PhD thesis also has been dedicated to the study of optimal conditions for the highly selective and stable production of aromatics during methanol to aromatics at high pressure. High selectivity to aromatics (~50%) can be achieved on a commercial high silica ZSM-5 at 400° and 30 bar total pressure. The high partial pressure of primary olefins and the promoted methanol-induced hydrogen transfer pathway result in an exponential increase in aromatization, while the high partial pressure of steam generated via dehydration of methanol leads to in situ coke removal and, therefore, to a slower deactivation of the zeolite.

Zeolite-supported transition metal catalysts, which couple the unique size- and shape-selectivity arising from the well-defined microporous structure of zeolites with the inherent high activity of metal species, have demonstrated remarkable performance in numerous catalytic reactions. Conventionally, such catalysts are prepared by loading metal species in the micropores of zeolites in the form of clusters (each containing only several atoms). Despite their high catalytic activity, the ultra-small clusters are usually highly mobile, and tend to migrate from the micropores to the crystal surfaces of zeolite during the reaction, where they agglomerate and deactivate. In this dissertation, we attempted to solve this issue by encapsulating metal nanoparticles (NPs) in zeolite crystals, based on the following considerations: (i) compared to clusters, nanoparticles have similar catalytic activity but much less mobility; and (ii) as long as the active sites are inside the zeolite crystals (not necessarily in the micropores that are too small to accommodate nanoparticles), they can exhibit selectivity associated with the zeolite structure. In the first chapter, we gave a general introduction to zeolites and zeolite supported catalysts, focusing on the preparation of hierarchical zeolites that are the main catalyst support materials used in the research projects of this dissertation. In the second chapter, we encapsulated highly dispersed Pd NPs (~2.6 nm) in zeolite ZSM-5 crystals, and used the obtained catalyst (Pd@SG-ZSM-5) for the hydrogenation of cinnamaldehyde. The confinement effect gave rise to an interesting catalytic behavior: compared with the traditional supported Pd catalyst prepared by impregnation, Pd@SG-ZSM-5 showed a 2.5-fold enhancement in the selectivity of hydrocinnamaldehyde (73% vs. 30%). Liquid adsorption combined with infrared spectroscopy characterization revealed that Pd@SG-ZSM-5 catalyst adsorbs much less reactant and product molecules than traditional catalyst, thereby suppressing the formation of by-products and leading to high selectivity. In chapter three, we developed a new method to encapsulate in situ produced molybdenum carbide (MoCx) in zeolite ZSM-5 for the methane dehydroaromatization (MDA) reaction. In this method, the structure-directing agent used to synthesize hierarchical zeolite ZSM-5 was utilized to reduce molybdenum precursor through a calcination process in an inert atmosphere. The zeolite subsequently underwent a secondary growth process to achieve encapsulation. The catalytic behavior of the as prepared catalyst in MDA consolidate our previous conclusion that MoCx particles outside the microporous channels can also act as the active sites for MDA, whereas it is traditionally viewed that only MoCx clusters inside the micropores are active sites. In addition, the encapsulation strategy allowed us to design experiments to answer one open question related to MDA, namely whether the Brønsted acid (BA) sites of the zeolite play a catalytic role in the conversion of methane to aromatics or only promote the dispersion of the Mo species. We encapsulated MoCx particles, which had proven to be active sites, in pure siliceous zeolite (Silicalite-1) that does not contain BA sites. The catalyst did not exhibit MDA activity even when aromatic compounds were introduced into the system by pre-adsorption or co-feeding, indicating that the BA sites are responsible for the oligomerization/cyclization step during MDA. Finally, in chapter five, we summarized the dissertation and gave our perspectives and outlooks on the further development of encapsulated catalysts based on zeolites.

No description available.

Today, zeolites play a considerable role in many industrial fields, especially in heterogeneous catalysis. Well-defined microporous structure combined with acidity provides exceptional size and shape selectivity, making zeolites indispensable in petrochemistry. However, the micropores can cause diffusion limitations and, in turn, a drop in reaction rate and selectivity. Hence, the development of modification methodologies on zeolite textural properties is one of the attention-grabbing research topics nowadays. For example, to overcome transport limitations in zeolites, the particle size can be reduced, or a system of larger auxiliary pores can be introduced [1]. One of the most promising methods for introducing secondary pores on a large scale is desilication since it is low-cost, versatile, and easy [2]. Despite its simplicity, the desilication mechanism is still a matter of discussion. In detail, it is not well-understood: 1. The influence of different species on mesopore formation kinetics 2. How aluminum is assembled back into the zeolite 3. Which types of aluminum species form throughout the treatment. The present study tries to answer these questions by relating ex-situ and in-situ NMR. The proposed ex-situ 29Si MAS NMR approach allows monitoring the development of mesoporosity and silicon extraction by analyzing Q3 and Q4 changes. The combination of ex-situ with in-situ 29Si MAS NMR study showed that the limiting step of Si extraction is the transformation of Q3 into Q2. 27Al MAS NMR combined with MQMAS showed the formation of new aluminum species after desilication. It was shown that some of the Al framework T-sites might dissolve during alkaline treatment. In-situ 27Al NMR indicates redistribution of dissolved aluminum upon desilication.

No description available.