Chemical Engineering Commons^™

Development Of Catalytic Technology For Producing Sustainable Energy, Syed Ali Z Gardezi

USF Tampa Graduate Theses and Dissertations

This dissertation explores catalyst technology for the production of renewable liquid fuels via thermo-chemical conversion of biomass derived syngas. Fischer-Tropsch synthesis is a process for converting syngas, i.e. a mixture of CO and H2, into energy rich long chain hydrocarbons and oxygenated compounds. This synthesis process involves a number of elementary reactions leading to an array of polymeric products. The economic operation of an FTS process lie in the interplay of both catalyst and reactor design. In relation to catalysis, the nature of chemisorbed species, and the fractional availability of active metal sites determines rate, conversion and yield. Similarly, reactor …

Kelvin Probe Electrode For Contactless Potential Measurement On Concrete-Properties And Applications, Michael Thomas Walsh

USF Tampa Graduate Theses and Dissertations

The practical feasibility of using a Kelvin Probe as a novel reference electrode in the measurement of both potential and polarization pulse response of reinforcing steel in concrete is demonstrated. Potential values measured using a KP reflect greater stability and repeatability than can typically be attained with conventional reference electrodes. Duplicate reinforced concrete beam test specimens with well-differentiated centrally corroding rebar segments were analyzed using both the Kelvin Probe (KP) and a conventional Saturated Calomel Electrode (SCE). Potential profile maps were developed using potential values recorded under static conditions with both the SCE and the KP. Nominal polarization resistance was …

Application And Characterization Of Self-Assembled Monolayers In Hybrid Electronic Systems, Michael Enoch Celesin

USF Tampa Graduate Theses and Dissertations

In this study, we explore ultra-thin insulators of organic and inorganic composition and their potential role as high-speed rectifiers. Typical applications for these structures include IR sensing, chemical detection, high speed logic circuits, and MEMS enhancements. While there are many elements in the functional group required to create a rectifying antenna (rectenna), the primary thrust of this work is on the rectifier element itself.

To achieve these research goals, a very good understanding of quantum tunneling was required to model the underlying phenomenon of charge conduction. The development of a multi-variable optimization routine for tunneling prediction was required. MATLAB was …

Synthesis Of Titanium Dioxide Photocatalyst With The Aid Of Supercritical Fluids, Haitao Li

USF Tampa Graduate Theses and Dissertations

Titanium Dioxide (TiO2) emerged as one of the most popular photocatalysts since 1970's. However, its photocatalytic activity requires UV irradiation due to its large band gap unless further functionalization or modifications are performed. Furthermore, recovery issue has always been a major drawback, if the more effective form nano particles are utilized.

The key objectives of this research were synthesizing new TiO2 based photocatalyst systems that are effective with both the UV and the visible light while utilizing novel superior environmentally friendly techniques enabling development of nano-structured photocatalysts that can be easily recovered. In this dissertation research, highly porous nano-structured TiO2/WO3/Fe3+ …

One Dimensional Stochastic Coating Growth Kinetics Of Peg 3400 Onto Ammonium Nitrate In A Fluidized Bed, Brandon Smeltzer

USF Tampa Graduate Theses and Dissertations

Fluidized beds represent a cost effective, scalable technology invaluable to the chemical processing community as part of the global scheme of particle design. However, despite wide spread use and multiple approaches (empirical and mechanistic) to modeling a fluidized bed coating process, operations must be done at different scales due to changes within the balance of phenomenological forces (e.g. gravity, buoyancy, drag, surface tension, viscosity, kinetic energy).

Ammonium nitrate is synthetic compound that has multiple applications such as fertilizer, rocket fuel, and self-cooling applications. Ammonium nitrate has five temperature dependent crystal structures that are accompanied by a change in density. The …

Structured Materials For Catalytic And Sensing Applications, Selma Hokenek

USF Tampa Graduate Theses and Dissertations

The optical and chemical properties of the materials used in catalytic and sensing applications directly determine the characteristics of the resultant catalyst or sensor. It is well known that a catalyst needs to have high activity, selectivity, and stability to be viable in an industrial setting. The hydrogenation activity of palladium catalysts is known to be excellent, but the industrial applications are limited by the cost of obtaining catalyst in amounts large enough to make their use economical. As a result, alloying palladium with a cheaper, more widely available metal while maintaining the high catalytic activity seen in monometallic catalysts …

Theoretical Studies Of Co Based Catalysts On Co Hydrogenation And Oxidation, Nianthrini Balakrishnan

USF Tampa Graduate Theses and Dissertations

CO hydrogenation and CO oxidation are two important processes addressing the energy and environmental issues of great interest. Both processes are carried out using metallic catalysts. The objective of this dissertation is to study the catalytic processes that govern these two reactions from a molecular perspective using quantum mechanical calculations. Density Functional Theory (DFT) has proven to be a valuable tool to study adsorption, dissociation, chain growth, reaction pathways etc., on well-defined surfaces. DFT was used to study the CO reduction reactions on promoted cobalt catalyst surfaces and CO oxidation mechanisms on cobalt surfaces.

CO hydrogenation via Fischer-Tropsch Synthesis (FTS) …

Innovative Desalination Systems Using Low-Grade Heat, Chennan Li

USF Tampa Graduate Theses and Dissertations

Water and energy crises have forced researchers to seek alternative water and energy sources. Seawater desalination can contribute towards meeting the increasing demand for fresh water using alternative energy sources like low-grade heat. Industrial waste heat, geothermal, solar thermal, could help to ease the energy crisis.

Unfortunately, the efficiency of the conventional power cycle becomes

uneconomically low with low-grade heat sources, while, at the same time, seawater desalination requires more energy than a conventional water treatment process. However, heat discarded from low-grade heat power cycles could be used as part of desalination energy sources with seawater being used as coolant …

Fermentation And Supercritical Extraction Studies Of Açaí Berry, Rosanna Iris Ayala

USF Tampa Graduate Theses and Dissertations

The açaí berry has grown in popularity for dieters and the health conscious. The berry contains high levels of antioxidants. The main anthocyanins are cyanidin-3-rutinoside and cyanidin-3-glucoside. The berries also contain vitamins and nutrients that help boost energy and alertness, and fatty acids that help maintain normal cholesterol levels. As a result of the health benefits of the constituents, the berries are chosen for obtaining the active ingredients by extraction.

The solids left over after extraction still contain nutrients and useful components. There is a possibility of fermenting this residual and creating an açaí berry wine. Açaí berry wine is …

Investigation And Synthesis Of Novel Graphene-Based Nanocomposites For Hydrogen Storage, Anthony Joseph D'Angelo

USF Tampa Graduate Theses and Dissertations

It is of great interest to develop and utilize a high surface area material with optimized hydrogen sorption properties. The need for a renewable energy source to replace automobile gasoline has become more critical in the past decade. Hydrogen is a viable fuel source for automobile usage; however, the question of how hydrogen will be safely and efficiently stored still remains. Critical factors for optimum hydrogen storage include ambient conditions and low activation temperature for adsorption and desorption phenomena. In order for optimum hydrogen adsorption to be achieved, the properties of (1) high surface area, (2) optimum hydrogen adsorption energy, …

Effect Of Platinum Particle Size On The Sulfur Deactivation Of Hydrogenation, Lyndsey Michelle Baldyga

USF Tampa Graduate Theses and Dissertations

A large concern of the fossil fuel and renewable energy industries is the sulfur poisoning of catalysts. In the case of noble metals, such as platinum, it is seen that there is a size trend associated with the level of activity in the presence of sulfur. Smaller nanoparticles could be more tolerant due to sulfur surface vacancies. On the other hand, larger particles could have less deactivation because the sulfur is more attracted to the smaller particles and the sulfur molecules bind stronger to these smaller particles.

The size effect of sulfur deactivation was investigated by testing four sizes of …

Novel Blends Of Sulfur-Tolerant Water-Gas Shift Catalysts For Biofuel Applications, Timothy Michael Roberge

USF Tampa Graduate Theses and Dissertations

As traditional sources of energy become depleted, significant research interest has gone into conversion of biomass into renewable fuels. Biomass-derived synthesis gas typically contains concentrations of approximately 30 to 600 ppm H2S in stream. H2S is a catalyst poison which adversely affects downstream processing of hydrogen for gas to liquid plants. The water-gas shift reaction is an integral part of converting CO and steam to H2 and CO2. Currently, all known water-gas shift catalysts deactivate in sulfur concentrations typical of biomass-derived synthesis gas. Novel catalysts are needed to remain active in the presence of sulfur concentrations in order to boost …

Catalytic Tri-Reforming Of Biomass-Derived Syngas To Produce Desired H2:Co Ratios For Fuel Applications, Devin Mason Walker

USF Tampa Graduate Theses and Dissertations

This study focuses on upgrading biomass derived syngas for the synthesis of liquid fuels using Fischer-Tropsch synthesis (FTS). The process includes novel gasification of biomass via a tri-reforming process which involves a synergetic combination of CO2 reforming, steam reforming, and partial oxidation of methane. Typical biomass-derived syngas H2:CO is 1:1 and contains tars that deactivate FT catalyst. This innovation allows for cost-effective one-step production of syngas in the required H2:CO of 2:1 with reduction of tars for use in the FTS. To maximize the performance of the tri-reforming catalyst, an attempt to control oxygen mobility, thermal stability, dispersion of metal, …

Smart Packaging: A Novel Technique For Localized Drug Delivery For Ovarian Cancer, Eva Christabel Williams

USF Tampa Graduate Theses and Dissertations

Localized drug delivery is emerging as an effective technique due to its ability to administer therapeutic concentrations and controlled release of drugs to cancer sites in the body. It also prevents the contact of harsh chemotherapy drugs to healthy regions in the body that otherwise would become exposed to current treatments.

This study reports on a model chemotherapy drug delivery system comprising non-ionic surfactant vesicles (niosomes) packaged within a temperature-sensitive chitosan network. This smart packaging, or package-within-a package system, provides two distinct advantages. First, the gel prevents circulation of the niosomes and maintains delivery in the vicinity of a tumor. …

Aggregation Of Sediment And Bacteria With Mucilage From The Opuntia Ficus-Indica Cactus, Audrey Lynn Buttice

USF Tampa Graduate Theses and Dissertations

Flocculants are commonly used in industrial settings where solid-liquid separations are desired including industrial and municipal wastewater management and potable water production facilities. Conventional flocculants include inorganic metal salts and synthetic organic polymers. The cost, availability, and harmful effects of the non-biodegradable nature of these flocculants have led to the widespread study of natural flocculants. Current natural flocculants being studied include polysaccharides cultivated from microbial extracellular matrix products and plant based materials. In this study, the mucilage of Opuntia ficus-indica cactus was evaluated as a natural flocculant for sediments and bacteria. The O. ficus-indica cactus is also known as the …

Precipitation Of Phosphate Minerals From Effluent Of Anaerobically Digested Swine Manure, Alex Y. Lin

USF Tampa Graduate Theses and Dissertations

Swine production represents approximately 40% of the world's meat production, and its wastes contain high concentrations of organic carbon, nitrogen (N), and phosphorus (P). Anaerobic digestion is an increasingly popular technology for treating animal wastes while simultaneously generating energy. Its propagation and ability to solubilize organic N and P make adding a struvite recovery process attractive. Recovering struvite (MgNH4PO4) from anaerobically digested swine waste can address global P shortages, meet P discharge guidelines, and produce slow-release fertilizer, which can be sold for revenue.

Anaerobic digesters were operated with at organic loading rates of 3.4-3.9 g volatile solids per liter per …

Design Of Colloidal Composite Catalysts For Co2 Photoreduction And For Co Oxidation, Bijith D. Mankidy

USF Tampa Graduate Theses and Dissertations

In this doctoral dissertation, novel colloidal routes were used to synthesize nanomaterials with unique features. We have studied the impact of nanoparticle size of catalyst, role of high surface area of a photocatalyst, and the effect of varying elemental composition of co-catalytic nanoparticles in combination with core-shell plasmonic nanoparticles. We have demonstrated how physical and chemical characteristics of nanomaterials with these unique features play a role in catalytic reactions, specifically the oxidation of CO and the photoreduction of CO2. The first objective of this doctoral dissertation involved the preparation of CoO nanoparticles with discrete nanoparticles sizes (1-14 nm) using a …

Shape-Shifting Surfaces For Rapid Release And Direct Stamping Of Organized Micro-Tissues, Samuel James Dupont

USF Tampa Graduate Theses and Dissertations

The primary aim of the research in this study is to develop a robust and simple platform for the in vitro organization of cells on surfaces which facilitate rapid cell release and allows for the direct stamping of highly organized micro-tissues. Current approaches towards this goal have been very successful but are lengthy and subject cells to harsh conditions for extended periods of time raising questions regarding cell health and maintenance of physiological state. To address these concerns a platform was developed to allow for rapid cell release by utilizing a release mechanism different from previous work.

Micron-scale structures comprised …

Volume-Phase Transitions In Responsive Photo-Cross-Linked Polymer Network Films, Leena Patra

USF Tampa Graduate Theses and Dissertations

The overall thrust of this project is to gain an insight into a class of surface-tethered cross-linked thin films of poly(N-alkylacrylamides) that display a lower critical solution temperature (LCST).The structure of the alkyl group and the modification of the amide groups determine the LCST and resultant volume-phase transition behavior. The aim of this study involves synthesis and characterization of thin films and to correlate the volume-transition behavior to the structure of the alkyl group. For better understanding the volume-transition behavior, the polymer films are perturbed by the Hofmeister salt series to examine trends between different alkyl groups. While most of …

Determination Of Isotherms Of Enantiomers On A Chiral Stationary Phase Using Supercritical Fluid Chromatography, Wade Newlin Mack Ii

USF Tampa Graduate Theses and Dissertations

Supercritical fluids provide a robust, tunable environment with favorable transport properties and enhanced solubility. Supercritical carbon dioxide is an environmentally friendly substance that has distinct advantages to traditional solvents used in large scale chemical processing. Ibuprofen is an enantiomeric drug that has been shown to fight prostate cancer and has been used as a mild Alzheimer's disease treatment in the S conformation. Purification of high value products with decreased hazardous material consumption is accomplished by employing supercritical fluid chromatography (SFC). Large scale, single enantiomer purification of pharmaceuticals is dependent on scale-up information. Equilibrium isotherms provide the necessary information to scale-up …

Determination Of Ibuprofen Isotherm Using Supercritical Fluid Chromatography, Loi Ho

USF Tampa Graduate Theses and Dissertations

Chromatography is widely used to determine physiochemical properties data including adsorption isotherm. In the separation of enantiomers through sorptive processes, supercritical fluids allow efficient and green alternatives to liquid solvent based systems. The isotherm information is vital in the development of operating policies and design of preparative chromatographic or moving bed separation schemes. Determination of sorption isotherms from experimental chromatographic elution data is automated and compared with different chromatogram model. Procedures were developed and validated for separation of R- and S- ibuprofen with supercritical 〖CO〗_2 and ethanol mixture as the mobile phase over a chiral stationary phase. The isotherms for …

Oxygen Diffusion Characterization Of Frp Composites Used In Concrete Repair And Rehabilitation, Chandra K. Khoe

USF Tampa Graduate Theses and Dissertations

Many independent studies have conclusively demonstrated that fiber reinforced polymers (FRP) slow down chloride-induced corrosion of steel in concrete. The mechanism for this slow down is not well understood but it has been hypothesized that FRP serves as a barrier to the ingress of chloride, moisture, and oxygen that sustain electrochemical corrosion of steel.

This dissertation presents results from an experimental study that determined the oxygen permeation rates of materials used in infrastructure repair. In the study, the oxygen permeation constants for epoxy, carbon and glass fiber laminates, concrete, epoxy-concrete and FRP-concrete systems were determined and a method developed to …

Catalytic Hydrodehalogenation And Hydrogenation Of Halogenated Aromatic Organic Contaminants For Application To Soil Remediation, Claire J. Osborn

USF Tampa Graduate Theses and Dissertations

The objective of this research was to aid in the development of a new method for removing and destroying soil contaminants. In particular, 1,2,4,5-tetrachlorobenzene (TeCB) was selected for this research. Hydrodehalogenation (HDH) was paired with hydrogenation for remedially destroying TeCB without generating a secondary waste stream in a single batch reactor. Palladium- and rhodium-catalyzed HDH and hydrogenation were applied in a batch reactor at room temperature and moderate hydrogen pressure. Cyclohexane was formed as an end product with benzene as an intermediate reactant.

An analytical method was developed to measure TeCB, benzene, and cyclohexane in a solution of water and …

Supercritical Fluid Aided Microencapsulation Of Dry Powders, Raquel Carvallo

USF Tampa Graduate Theses and Dissertations

Coating of fine particles to produce tailored surface properties is currently a key development for supercritical fluids applications, in different areas such as: pharmaceutical, nutraceutical, cosmetic, agrochemical, electronic and specialty chemistry industries. During the encapsulation process the particles surface can be designed with specific properties by spreading a thin film coating material over the surface of the particles.

Chitosan, a natural polymer, was used in this work as the encapsulant material. Chitosan is biocompatible, biodegradable to normal body constituents, safe, non-toxic, bacteriostatic, anticancerogen, and versatile polymer. These attributes are among the properties that make Chitosan an attractive component of pharmaceutical …

Cactus Mucilage-Assisted Heavy Metal Separation: Design And Implementation, Dawn Iona Fox

USF Tampa Graduate Theses and Dissertations

Natural contamination of groundwater by arsenic (As) has become a critical public health threat in many parts of the world. The well-known regions associated with As contamination of groundwater are Bangladesh and West Bengal, India where approximately 100 million people are exposed to high levels of arsenic by drinking arsenic-contaminated groundwater and about 35 million are already affected. Long-term drinking of arsenic-contaminated water leads to arsenicosis, which is characterized by cancers of the skin, organ disease and certain other types of cancer. Affected developing communities are at higher risk because they may not have access to conventional water treatment facilities. …

The Conversion Of Low-Grade Heat Into Power Using Supercritical Rankine Cycles, Huijuan Chen

USF Tampa Graduate Theses and Dissertations

Low-grade heat sources, here defined as below 300 ºC, are abundantly available as industrial waste heat, solar thermal, and geothermal, to name a few. However, they are under-exploited for conversion to power because of the low efficiency of conversion. The utilization of low-grade heat is advantageous for many reasons. Technologies that allow the efficient conversion of low-grade heat into mechanical or electrical power are very important to develop.

This work investigates the potential of supercritical Rankine cycles in the conversion of low-grade heat into power. The performance of supercritical Rankine cycles is studied using ChemCAD linked with customized excel macros …

Plasma Mediated Molecular Delivery, Richard J. Connolly

USF Tampa Graduate Theses and Dissertations

Non-viral delivery of plasmid DNA has traditionally relied upon physical forces applied directly to target tissues. These physical methods typically involve contact between an applicator and the target tissue and often cause transient patient discomfort. To overcome the contact-dependent limitations of such delivery methodologies, an atmospheric direct current plasma source was developed to deposit ionized gas molecules onto localized treatment sites. The deposition of charged species onto a treatment site can lead to the establishment of an electric field with strengths similar to those used for traditional electroporation. In vitro experiments proved that this technology could transiently permeabilize cell membranes …

The Virtual Hip: An Anatomically Accurate Finite Element Model Based On The Visible Human Dataset, Jonathan M. Ford

USF Tampa Graduate Theses and Dissertations

The purpose of this study is to determine if element decimation of a 3-D anatomical model affects the results of Finite Element Analysis (FEA). FEA has been increasingly applied to the biological and medical sciences. In order for an anatomical model to successfully run in FEA, the 3-D model’s complex geometry must be simplified, resulting in a loss of anatomical detail. The process of decimation reduces the number of elements within the structure and creates a simpler approximation of the model. Using the National Library of Medicine’s Visible Human Male dataset, a virtual 3-D representation of several structures of the …

Investigation Of Buildup Dose For Therapeutic Intensity Modulated Photon Beams In Radiation Therapy, Khosrow Javedan

USF Tampa Graduate Theses and Dissertations

Buildup dose of Mega Voltage (MV) photon beams can be a limiting factor in intensitymodulated radiation therapy (IMRT) treatments. Excessive doses can cause patient discomfort and treatment interruptions, while underdosing may lead to local failure.

Many factors which contribute to buildup dose, including the photon beam energy spectrum, scattered or contaminant radiation and their angular distribution, are not modeled well in commercial treatment planning systems. The accurate Monte Carlo method was employed in the studies to estimate the doses.

Buildup dose of 6MV photon beams was investigated for three fundamentally different IMRT modalities: between Helical TomoTherapy and traditional opposed tangential …

Synthesis, Characterization, And Self-Assembly Of Gold Nanorods And Nanoprisms, Kristina L. Tran

USF Tampa Graduate Theses and Dissertations

The unique properties of gold nanoparticles make them excellent candidates for applications in electronics, sensing, imaging, and photothermal therapy. Though abundant literature exists for isotropic gold nanoparticles, work on nanoparticles of different shapes has been gaining interest recently. Anisotropic gold nanoparticles, such as nanorods and nanoprisms, have tunable optical properties in the visible and near-infrared regions. Through synthesis and surface modification, the production of various shapes of these gold nanoparticles can be controlled to meet different applications.

Two different types of gold nanorods were used in this thesis. The first type was stabilized with cetyltrimethylammonium bromide (CTAB) and had aspect …