Chemical Engineering Commons^™

Theoretical Investigation Of Heterogeneous Catalysis At The Solid–Liquid Interface For The Conversion Of Lignocellulosic Biomass Model Molecules, Muhammad Faheem

Theses and Dissertations

Catalytic conversion of biomass-derived oxygenates to fuels and value-added chemicals is a promising strategy in the search for renewable and sustainable energy sources. Most relevant catalytic processes are carried out in an aqueous environment using supported transition metal catalysts. The reaction network consists of multiple series and parallel pathways leading to formation of hydrogen, alkanes, and lighter oxygenates. The final product distribution ultimately depends on the sequence and competition of C−C, C−O, C−H, and O−H bonds scissions. Ethylene glycol (EG) is the simplest model molecule of various biomass-derived polyols that has a C:O stoichiometry of 1:1 and contains all relevant …

Gas-Phase, Catalytic Hydrodeoxygenation Of Propanoic Acid Over Supported Group Viii Noble Metals, Yuliana K. Lugo José

Theses and Dissertations

Recent advances for the deoxygenation of biomass, have demonstrated that hydrodeoxygenation (HDO) is one of the most promising route for the upgrading pyrolysis bio-oils. Catalytic hydrodeoxygenation of pyrolysis bio-oil have shown to be an efficient and economical process, since the raw materials consist mainly of waste. Propanoic Acid (PAc) is considered as one of the main constituents of pyrolysis bio-oils. However, these carboxylic acids are extremely corrosive and difficult to deoxygenate. Therefore, much effort have been given to the development of novel catalytic techniques, to improve the activity, stability and selectivity for the HDO of carboxylic acids.

This dissertation explores …

Ultrathin Graphene Oxide Membranes/Coatings For Separations, Hang Li

Theses and Dissertations

Graphene oxide (GO) was utilized as a novel material for making ultrathin membranes for gas separation and for making functional coatings for nano-/ultra-filtration in oil/water separation. Fundamental separation mechanisms by ultrathin GO membranes/coatings and potential applications were explored. This work can be divided into three parts. In the first part, ultrathin GO membranes supported on flat and smooth anodic aluminum oxide (AAO) substrates, with thickness down to 1.8 nm, were prepared by a facile vacuum filtration method. The as-prepared GO membranes were then studied for single-gas permeation and hydrogen mixture separation. It was revealed that the separation mechanism for the …

Synthesis Of Graphitic Carbon Nanostructures And Use As Electrocatalyst For Oxygen Reduction Reaction, Daniel A. Moniot

Theses and Dissertations

Graphitic carbon nanostructure (GCN) was synthesized by a simple procedure using cobalt(II) gluconate as a precursor and used as a catalyst support for polymer electrolyte membrane (PEM) fuel cell cathode. A novel stabilization procedure was developed to enhance the thermal stability of the GCN support. Support stabilization resulted in well-defined crystalline graphitic hollow structures as confirmed by highresolution transmission electron microscope (HRTEM). The prepared GCNs are used as support for depositing platinum nanoparticles (size) by modified polyol process. Rotating ring disk electrode (RRDE) and fuel cell studies were carried out to evaluate the catalyst performance. Cycling studies (0.6-1.0 V vs. …

Synthesis, Characterization And Evaluation Of Ir-Based Bimetallic Catalysts, You Jung Song

Theses and Dissertations

This dissertation considers effective bimetallic preparation for supported Ir-based bimetallic catalysts and their catalytic activity. Since bimetallic catalysts exhibit significantly different catalytic and chemical properties than their corresponding monometallic components by providing enhanced selectivity, stability and /or activity, many monometallic catalysts in industrial processes have been replaced by bimetallic catalysts. However, conventional synthetic methods used to produce monometallic and bimetallic catalysts often result in wide particle size distributions and non-uniform materials which can be difficult to characterize on a fundamental level. Two alternate preparation methods, dendrimer templating and electroless deposition, are developed and compared with conventional incipient wetness method. In …

Polymer Nano-Dielectrics For High Density Energy Storage, Sayful Islam Md

Theses and Dissertations

Military and commercial users require next-generation polymer dielectric materials for pulse power and power conditioning applications with rise times less than 1 ms and AC power at frequencies ranging from kHz to MHz. These power density and rate capability requirements necessitate the use of dielectric capacitors that store energy via polarization of electrons in molecular scale dipoles. Multiphase polymer composites and all-polymer dielectrics could be new kinds of materials to meet this acute need for capacitors with compact size and high rate capability.

The polymer nanocomposite (PNC) approach to achieve high energy density employed a “colossal” dielectric constant material, calcium …

Measurement And Modeling Of Fire Behavior In Leaves And Sparse Shrubs, Dallan R. Prince

Theses and Dissertations

Wildland fuels and fire behavior have been the focus of numerous studies and models which provide operational support to firefighters. However, fuel and fire complexity in live shrubs has resulted in unexpected and sometimes aggressive fire behavior. The combustion of live fuels was studied and modeled, and the results were assimilated into a shrub-scale fire behavior model which assumes fire spread by flame-fuel overlap. Fire spread models have usually assumed that radiation heat transfer is responsible for driving fire spread, but that assumption is a topic of continuing debate, and appears to contradict some experimental observations. A convection-based shrub-scale fire …

Design Of A Light-Weight Low-Volume High Oxygen Storage Density Material, Nicholas Robert Schwartz

Theses and Dissertations

A compact, lightweight, dense and safe method for storing and supplying oxygen remains a large hurdle for closed-circuit self-contained breathing apparatus (SCBA) and respiratory protective equipment. No filter that can protect against airborne chemical, biological, radiological, and nuclear (CBRN) contaminants exists, which presents the need for an isolated oxygen source. Heavy and high maintenance oxygen cylinders are typically used. The most important criteria for a smart and effective CBRN protection device are safety, weight, size, and cost, level of maintenance, ease-of-use and reliability. This study focused on nanomaterials for high capacity gas storage. Nanocapillary arrays composed of anodic aluminum oxide …

Enhancement Of Mass Transfer And Electron Usage For Syngas Fermentation, James J. Orgill

Theses and Dissertations

Biofuel production via fermentation is produced primarily by fermentation of simple sugars. Besides the sugar fermentation route, there exists a promising alternative process that uses syngas (CO, H2, CO2) produced from biomass as building blocks for biofuels. Although syngas fermentation has many benefits, there are several challenges that still need to be addressed in order for syngas fermentation to become a viable process for producing biofuels on a large scale. One challenge is mass transfer limitations due to low solubilities of syngas species. The hollow fiber reactor (HFR) is one type of reactor that has the potential for achieving high …

Engineering Cell-Free Systems For Vaccine Development, Self-Assembling Nanoparticles And Codon Reassignment Applications, Mark T. Smith

Theses and Dissertations

This dissertation reports on the technology of cell-free protein synthesis (CFPS) including 1) stabilized lyophilized cell-free systems and 2) enhanced heterogeneous cell extracts. This work further considers applications of CFPS systems in 1) rapid vaccine development, 2) functional virus-based nanoparticles, 3) site-specific protein immobilization, and 4) expanding the language of biology using unnatural amino acids. CFPS technology is a versatile protein production platform that has many features unavailable in in vivo expression systems. The primary benefit cell-free systems provide is the direct access to the reaction environment, which is no longer hindered by the presence of a cell-wall. The “openness" …

A New Software Tool To Environmentally And Economically Evaluate Solvent Recovery In The Pharmaceutical Industry, Eduardo Cavanagh

Theses and Dissertations

The environmental impact reduction and operating costs savings associated with the purification and reuse of solvent waste in the manufacture of active pharmaceutical ingredients (API's) were investigated. A software toolbox has been developed that combines Aspen Plus(R) process simulation with SimaPro(R) and Ecosolvent life cycle assessment (LCA) databases. The feasibility of a relatively small flexible skid capable of recovering multiple solvent waste streams was evaluated. Fractional distillation and pervaporation were considered to separate binary solvent waste mixtures. Optimum distillation reflux ratio and feed stage were determined to maximize the environmental impact reductions and operating cost savings. The optimum reflux ratio …

Volume Swing Frequency Response Method For Determining Mass Transfer Mechanisms In Microporous Adsorbents, Mohammad Iftekhar Hossain

Theses and Dissertations

Because of their numerous important applications in industrial catalytic, separation, and purification processes, miroporous materials have attracted considerable attention. Understanding the dynamic behavior of various gases in these porous materials is a critical step in designing, developing and effective operation of such kind of industrial processes. Frequency response (FR) methods have proven to be one of the best recently developed techniques and have been widely used to investigate kinetics behavior of various gas-solid systems due to their ability to discriminate among different rate limiting mechanisms. The current work has been focusing on the development of a volume swing frequency response …

Synthesis And Reactivity Of Hy Zeolite-Supported Rhodium Complexes, Artem D. Vityuk

Theses and Dissertations

The growing interest in the design of heterogeneous analogs of highly active and selective homogeneous catalysts prompted researchers to invest significant efforts in understanding of synthetic pathways, structure, and reactivity of supported single-site metal complexes. Synthesis of catalytically active organometallic species on solid supports with properties resembling those of their homogeneous counterparts could offer the opportunities to perform efficiently the solution organic reactions by utilizing flow instead of batch reactors. In this regard, rhodium carbonyl complexes and their derivatives are viewed as very attractive candidates for heterogenization due to their extensive application as catalysts for variety of industrially important reactions. …

Electrochemical, Interfacial, And Surface Studies Of The Conversion Of Carbon Dioxide To Liquid Fuels On Tin Electrodes, Jingjie Wu

Theses and Dissertations

The electrochemical reduction of carbon dioxide (CO2) into liquid fuels especially coupling with the intermittent renewable electricity offers a promising means of storing electricity in chemical form, which reduces the dependence on fossil fuels and mitigates the negative impact of anthropogenic CO2 emissions on the planet. Although converting CO2 to fuels is not in itself a new concept, the field has not substantially advanced in the last 30 years primarily because of the challenge of discovery of structural electrocatalysts and the development of membrane architectures for efficient collection of reactants and separation of products. An efficient catalyst for the electrochemical …

High Fidelity Chemistry And Radiation Modeling For Oxy-Combustion Scenarios, Hassan A. Abdul Sater

Theses and Dissertations

To account for the thermal and chemical effects associated with the high CO₂ concentrations in an oxy-combustion atmosphere, several refined gas-phase chemistry and radiative property models have been formulated for laminar to highly turbulent systems. This thesis examines the accuracies of several chemistry and radiative property models employed in computational fluid dynamic (CFD) simulations of laminar to transitional oxy-methane diffusion flames by comparing their predictions against experimental data. Literature review about chemistry and radiation modeling in oxy-combustion atmospheres considered turbulent systems where the predictions are impacted by the interplay and accuracies of the turbulence, radiation and chemistry models. Thus, …

Toward Polymer Coating With Easy Ice Release, Chenyu Wang

Theses and Dissertations

Minimizing adhesion of ice has been the subject of extensive studies for applications such aircraft wings, wind turbine blades spacecraft, power transmission wires, while a growing interest concerns coatings for aerospace applications. The work described here describes progress for coatings and ice release test method development over the last few years. Major achievements include: (1) New Rigid Adherent-Resistant Elastomers (RARE), (2) A new Epoxied Cylinder (EC) adhesion test, (3) Validation of an ice release test, and (4) Study of ice adhesion strength on coating thickness for a PDMS elastomer. Rigid Adhesion-Resistance Elastomers (RARE) are comprised of 3F 1 terminated with …

Development Of A Pressure Swing Adsorption Process For Co2 Capture From Flue Gas Using Solid Amine Sorbents, Anahita Abdollahi Govar

Theses and Dissertations

Solid amines are comprised of adsorbent materials, like silica gel, that contain amine based organic compounds, either physically or chemically, attached within their pores. The major characteristic of these sorbents that makes them interesting for CO₂ capture from flue gas is that unlike zeolites they are not negatively affected by the presence of water. The current work has been focusing on the development of a novel PSA cycle for CO₂ capture from flue gas using a solid-amine sorbent composed of PEI physically immobilized on a commercial silica substrate. The goal was to achieve > 90% recovery and > 95 vol. …

A Dynamic Optimization Framework With Model Predictive Control Elements For Long Term Planning Of Capacity Investments In A District Energy System, Jose Luis Mojica Velazquez

Theses and Dissertations

The capacity expansion of a district heating system is studied with the objective of evaluating the investment decision timing and type of capacity expansion. District energy is an energy generation system that provides energy, such as heat and electricity, generated at central locations and distributed to the surrounding area. The study develops an optimization framework to find the optimal investment schedule over a 30 year horizon with the options of investing in traditional heating sources (boilers) or a next-generation combined heat and power (CHP) plant that can provide heat and electricity. In district energy systems, the investment decision on the …

A Kinetic Study Of Aqueous Calcium Carbonate, Derek Daniel Harris

Theses and Dissertations

Amorphous calcium carbonate (ACC) precipitation is modeled using particle nucleation, growth, and aggregation. The particles are tracked in terms of their radial size and particle density using direct quadrature method of moments (DQMOM). Four separate nucleation models are implemented and are compared to experimental data. In discord with a recent study, it is shown that classical nucleation, coupled with equilibrium chemistry, is in good agreement with experimental data. Novel nucleation mechanisms are presented which fit the experimental data with slightly greater accuracy. Using equilibrium chemistry it is shown that the equilibrium value of ACC is pKeq = 7.74 at 24C, …

Molecular Modeling Of Dna For A Mechanistic Understanding Of Hybridization, Terry Jacob Schmitt

Theses and Dissertations

DNA microarrays are a potentially disruptive technology in the medical field, but their use in such settings is limited by poor reliability. Microarrays work on the principle of hybridization and can only be as reliable as this process is robust, yet little is known at the molecular level about how the surface affects the hybridization process. This work uses advanced molecular simulation techniques and an experimentally-parameterized coarse-grain model to determine the mechanism by which hybridization occurs on surfaces and to identify key factors that influence the accuracy of DNA microarrays. Comparing behavior in the bulk and on the surface showed, …

Novel Liposomes For Targeted Delivery Of Drugs And Plasmids, Marjan Javadi

Theses and Dissertations

People receiving chemotherapy not only suffer from side effects of therapeutics but also must buy expensive drugs. Targeted drug and gene delivery directed to specific tumor-cells is one way to reduce the side effect of drugs and use less amount of therapeutics. In this research, two novel liposomal nanocarriers were developed. This nanocarrier, called an eLiposome, is basically one or more emulsion droplets inside a liposome. Emulsion droplets are made of perfluorocarbons which usually have a high vapor pressure. Calcein (as a model drug) and Paclitaxel were used to demonstrate drug delivery, and plasmids and siRNA were used to exemplify …

Cryogenic Carbon Capture Using A Desublimating Spray Tower, Bradley J. Nielson

Theses and Dissertations

Global warming is becoming ever increasing concern in our society. As such the likelihood of a carbon tax in the US is becoming increasingly likely. A carbon tax will be expensive enough that coal-based power plants will either have to install carbon capture technology or close. The two front runner technologies for carbon capture are amine scrubbing, and oxyfuel combustion. The downside is that both of these technologies increase power generation cost in a new plant by about 80% and have up to a 30% parasitic load, which reduces the cycle efficiency, that is, the power production per unit fuel …

Aqueous Henry's Law Constants, Infinite Dilution Activity Coefficients, And Water Solubility: Critically Evaluated Database, Experimental Analysis, And Prediction Methods, Sarah Ann Brockbank

Theses and Dissertations

A database containing Henry's law constants, infinite dilution activity coefficients and solubility data of industrially important chemicals in aqueous systems has been compiled. These properties are important in predicting the fate and transport of chemicals in the environment. The structure of this database is compatible with the existing DIPPR® 801 database and DIADEM interface, and the compounds included are a subset of the compounds found in the DIPPR® 801 database. Thermodynamic relationships, chemical family trends, and predicted values were carefully considered when designating recommended values. Henry's law constants and infinite dilution activity coefficients were measured for toluene, 1-butanol, anisole, 1,2-difluorobenzene, …

The Effect Of Carbon Additives On The Microstructure And Performance Of Alkaline Battery Cathodes, Douglas Robert Nevers

Theses and Dissertations

This thesis describes research to understand the relationships between materials, microstructure, transport processes, and battery performance for primary alkaline battery cathodes. Specifically, the effect of various carbon additives, with different physical properties, on electronic transport or conductivity within battery cathodes was investigated. Generally, the electronic conductivity increases with carbon additives that have higher aspect ratios, smaller particle diameters, higher surface areas, and lower bulk densities. Other favorable carbon aspects include more aggregated and elongated carbon domains which permit good particleto-particle contacts. Of the various carbon additives investigated, graphene nanopowder was the best performer. This graphene nanopowder had the smallest particle …

Application Of One Dimensional Turbulence (Odt) To Model Fire Spread Through Biomass Fuel Bed, Abinash Paudel

Theses and Dissertations

Each year fires destroy millions of acres of woodland, lives, and property, and significantly contribute to air pollution. Increased knowledge of the physics and properties of the flame propagation is necessary to broaden the fundamental understanding and modeling capabilities of fires. Modeling flame propagation in fires is challenging because of the various modes of heat transfer with diverse fuels, multi-scale turbulence, and complex chemical kinetics. Standard physical models of turbulence like RANS and LES have been used to understand the flame behavior, but these models are limited by computational cost and their inability to resolve sub-grid scales. Application of several …

The Effects Of Mismatches And Probe Tethering Configurations On The Stability Of Dna Duplexes On Surfaces, Kyle Evan Pratt

Theses and Dissertations

DNA microarrays are chip-based, analysis tools which can perform hundreds of thousands of parallel assays to determine the identity of genes or gene expression levels present in a sample. They have been identified as a key technology in genomic sciences and emergent medical techniques; however, despite their abundant use in research laboratories, microarrays have not been used in the clinical setting to the fullest potential due to the difficulty of obtaining reproducible results. Microarrays work on the principle of DNA hybridization, and can only be as accurate as this process is robust. Fundamental, molecular-level understanding of hybridization on surfaces is …

Poly(N-Isopropylacrylamide)-Based Scaffolds For Tissue Engineering Applications, Pamela Kubinski

Theses and Dissertations

The primary goal of this work is to investigate the potential of poly(Nisopropylacrylamide)- based scaffolds in tissue engineering applications, specifically spinal injury and nucleus pulposus replacement. Poly(N-isopropylacrylamide), denoted PNIPAAm, is a synthetic polymer with hydrophilic properties at room temperature, but above 32C the chains become hydrophobic and entangle to form physical crosslinks. This thermoresponsive property enables PNIPAAm to be implanted as a free-flowing solution at room temperature and collapse into a gel in physiological conditions. However, as a homopolymer, the hydrophobicity of PNIPAAm in vivo causes the hydrogel to expel water and exhibit inelastic properties that do not mimic those …

Comfort And Compatibility Of Silicone Hydrogel Contact Lenses, Ngai Keung Tam

Theses and Dissertations

Silicone Hydrogel (SiHy) contact lenses are highly successful compared to previous soft lenses; they were developed to provide superior oxygen permeability. However, the hydrophobic natures of the silicone segments enhance lipid sorption which may diminish the lens surface wettability, clarity and comfort. While lens and lens care product are designed to remove lipid deposition, there is lack of experimental evidence to evaluate the actual performances with respect to lipid removal. An in vitro model using an artificial tear fluid containing radiolabeled lipids was employed in this thesis research to evaluate the efficacy of different multi-purpose lens care solutions in removing …

Foundational Work In Bioelectrochemical Anaerobic Reactor Design With Electron Mediators, Christopher D. Hoeger

Theses and Dissertations

Bioelectrical reactors (BER) have potential to be utilized in a wide variety of industrial applications. This work explores the kinetics involved with reduction of electron mediators (anthraquinone disulfonate and methyl viologen) in bioelectrical reactors. It also discusses on possible application of BER technology to produce ethanol from CO2 and electricity. It is established that Clostridium ragdahlei is capable of sustaining life and product formation with CO2 as the only carbon source. This means it is theoretically possible to utilize CO2 as he source of carbon and electricity as the source of reducing equivalents for bacterial growth and product formation. A …

Immobilized Viologen Polymer For Use In Direct Carbohydrate Fuel Cells, Yining Pan

Theses and Dissertations

Glucose and other carbohydrates are some of the most abundant renewable energy sources in the world. The oxidation of carbohydrates in a fuel cell allows their chemical energy to be converted directly into electrical energy. Viologen has been indentified and shows promising ability as an electron-transfer catalyst or mediator for carbohydrate oxidation in an alkaline carbohydrate fuel cell. Building on the previous results, the objective of this work was to develop an immobilization chemistry of viologen onto an electrode and to investigate the catalytic activity for carbohydrate oxidation in direct carbohydrate fuel cells.The immobilization was achieved by electropolymerizing a novel …