Zeolite catalysts of three types (H-ZSM-5, Fe-ZSM-5 and H-Beta) were tested in the catalytic co-conversion of rapeseed cake and safflower oil into bio-fuel. This low pressure process was carried out at the temperatures of 350 and 400 °C. The yields and compositions of the product mixtures depended on the catalyst nature and the process temperatures. The produced organic phases consisted mainly of hydrocarbons, fatty acids and nitriles. This mixture possessed improved characteristics (e.g. heating value, water content, density, viscosity, pH) compared with the bio-oils, making possible its application as a bio-fuel. The most effective catalyst, providing the highest yield of organic liquid phase, was the highly acidic/wide-pore H-Beta zeolite. The products obtained on this catalyst demonstrated the highest degree of deoxygenation and the higher HHV (Higher Heating Value). The aqueous liquid phase contained water-soluble carboxylic acids, phenols and heterocyclic compounds.

Indiana University-Purdue University Indianapolis (IUPUI) / Extrusion-based 3D printing is one of the emerging additive manufacturing technologies used for printing a range of materials from metal to ceramics. In this process, the required material is extruded from the extruder in the form of a slurry. Zeolite and MOFs are mainly used for CO2 adsorption in the form of pellets and beads due to their good adsorptive property. Researchers are developing monoliths of Zeolite and MOFs and fabricate them using traditional extrusion and implement them in the gas adsorption applications as an option for beads and pellets by developing a monolithic structure. Previous research on Zeolite 13X and 5A have shown good structural and physical properties in monolith form. In this study, we developed slurry of two molecular sieve Zeolite 3A and 4A monoliths powders, mixing it with bentonite clay, methyl cellulose, and PVA as a binder. The slurry preparation was carried out at room temperature. Once the 3D printed samples are dried at room temperature, a sintering process was performed to increase mechanical strength. To be used in real-time applications, the 3D printed Zeolite sample need to have sufficient mechanical strength. The BET surface area test showed good results for Zeolite 13X compared to available literature. The surface area calculated for 3D printed Zeolite 13X was 767m2/g and available literature showed 498 m2/g for 3D printed Zeolite 13X. The microhardness values of 3D printed Zeolite samples were measured using a Vicker hardness tester. The hardness value of the 3D - printed Zeolite samples increased from 8.3 ± 2 to 12.5 ± 3 HV0.05 for Zeolite 13X, 3.3 ± 1 to 7.3 ± 1 HV0.05 for Zeolite 3A, 4.3 ± 2 to 7.5 ± 2 HV0.05 for Zeolite 4A, 7.4 ± 1 to 14.0 ± 0.5 HV0.05 for Zeolite 5A respectively. The SEM, EDS and XRD analysis was performed for 3D printed samples before and after sintering to evaluate their structural properties. The SEM analysis reveals that all 3D printed Zeolite samples retained their microstructure after slurry preparation and also after the sintering process. The porous nature of 3D printed Zeolite walls was retained after the sintering process. The EDS analysis showed that the composition of 3D printed Zeolite samples remained somewhat similar with minor variation for before and after sintering. The framework structure of Zeolite Type X for Zeolite 13X and Zeolite Type A for Zeolite 3A, 4A, 5A were in good shape after sintering as standard peak intensity points were retained. Zn-MOF74 was synthesized using solvothermal synthesis which is a well-established synthesis process used for the synthesis of MOFs. We also developed slurry for Zn-MOF-74 using bentonite clay and PVA as binders and printed small parts using hand printing.

Hydrocracking is one of the most essential catalytic processes in the oil industry for the conversion of heavy fractions of petroleum (light and heavy vacuum gas oil, demetallized oil) and renewable hydrocarbon feedstocks to high-quality fuels. Hydrocracking relies on a bifunctional catalytic process that combines catalytic cracking and hydrogenation steps. In principle, hydrocracking is aimed to convert heavy and ultraheavy oils with maximum fuel selectivity and minimum formation of light gases and polyaromatic compounds, from this high activity and selectivity of the catalyst, is achieved by finding a good balance between its acidic and hydrogenation properties. For this study, platinum catalyst impregnated on alumina was applied for hydrogenation reaction, whereas cracking function was accomplished by ultrastable Y (USY) zeolite. The central objective of the thesis was to study the fundamental effect of extra framework aluminum (EFAl) species forming with the hydrothermal treatment of USY on hydrocracking of selected model compound – n-hexadecane. Three commercial USY zeolites with different SiO2/Al2O3 ratios were steamed until they reached down to the conversion curve of the reference USY sample physically mixed with 1% Pt supported on alumina in a 1:10 ratio. XRD patterns showed that the crystalline faujasite structure was kept after steaming. In the physisorption of argon, slight changes were observed in surface area and pore volumes which were correlated to the structural collapse of the zeolite framework. Dealumination of the zeolite framework was verified by 27Al MAS NMR. FTIR spectroscopy of pyridine adsorption and TPD of ammonia were employed to investigate the acidity of the samples. From the results, it was found that the concentration of Brønsted acid sites was the main contributor to the activity-acidity relationship in n-hexadecane hydrocracking. To gain more insight into the relationship, samples were subjected to n-hexane cracking. Turnover frequency analysis supported the proposal about hydrocracking reaction and also revealed the chemical influence of EFAl on Brønsted acidity observed in catalytic cracking of hexane.

Diminishing petroleum resources combined with concerns about global warming and dependence on fossil fuels are leading our society to search for renewable sources of energy. In this respect, lignocellulosic biomass has a tremendous potential as a renewable energy source, once we develop the economical processes converting biomass into useful fuels and chemicals. Catalytic fast pyrolysis (CFP) is a promising technology for production of gasoline range aromatics, including benzene, toluene, and xylenes (BTX), directly from raw solid biomass. In this single step process, solid biomass is fed into a catalytic reactor in which the biomass first thermally decomposes to form pyrolysis vapors. These pyrolysis vapors then enter the zeolite catalysts and are converted into the desired aromatics and olefins along with CO, CO2, H2O, and coke. The major challenge with the CFP process is controlling the complicated homogeneous and heterogeneous reaction chemistry. The focus of this thesis is to study the reaction chemistry, catalyst design, and process development for CFP to advance the CFP technology. To gain a fundamental understanding of the underlying chemistry of the process, we studied the reaction chemistry for CFP of glucose (i.e. biomass model compound). Glucose is thermally decomposed in a few seconds and produce dehydrated products, including anhydrosugars and furans. The dehydrated products then enter into the zeolite catalyst pore where they are converted into aromatics, CO, CO2, H2O and coke. The zeolite catalyzed step is far slower than the initial decomposition step (>2 min). Isotopic labeling studies revealed that the aromatics are formed from random hydrocarbon fragments composed of the dehydrated products. The major competing reaction to aromatic production is the formation of coke. The main coking reaction is the polymerization of the furan intermediates on the catalyst surface. CFP is a shape selective reaction where the product selectivity is related to the zeolite pore size and structure. The shape selectivity of the zeolite catalysts in the CFP of glucose was systematically studied with different zeolites. The aromatic yield is a function of the pore size and internal pore space of the zeolite catalyst. Medium pore zeolites with pore sizes in the range of 5.2 to 5.9 Å and moderate pore intersection size, such as ZSM-5 and ZSM-11 produced the highest aromatic yield and least amount of coke. The kinetic diameter estimation of the aromatic products and the reactants revealed that the majority of these molecules can fit inside the zeolite pores of the medium pore zeolites. The ZSM-5 catalyst, the best catalyst for aromatic production, was modified further to improve its catalytic performance. These modifications include: (1) adjusting the concentration of acid sites inside the zeolites catalyst; (2) incorporation of mesoporosity into the ZSM-5 framework to enhance its diffusion characteristics, and (3) addition of Ga to the ZSM-5. Mesoporous ZSM-5 showed high selectivity for heavier alkylated monoaromatics. Ga promoted ZSM-5 increased the aromatic yield over 40%. A process development unit was designed and built for continuous operation of the CFP process in a pilot scale. The effects of process variables such as temperature, biomass weight hourly space velocity, catalyst to biomass ratio, catalyst static bed height, and fluidization gas velocity were studied to optimize the reactor performance. It was demonstrated that CFP could produce liter quantities of aromatic products directly from solid biomass.

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