Engineering Commons^™

Role Of Bed Design Characteristics On The Effective Thermal Conductivity Of A Structured Adsorbent, Pravin Bosco Charles Antony Amalraj

Theses and Dissertations

This work evaluates the role of different design variables on the effective thermal conduction of a structured adsorbent bed for its possible application in a temperature swing adsorption (TSA) process. The structured adsorbent bed is represented by eight parallel layers of intercalated smooth and corrugated foils of a metal support coated with 13X zeolite resulting in the formation of parallel triangular channels. The variables investigated include the thickness of the adsorbent coating, thickness of the metal, nature of contacts between smooth and corrugated foils, type of metal, presence and magnitude of an air gap between the foils, difference in alignment …

Combinatorial Study Of Oxidation Catalysts: Uncovering Synthesis-Structure-Activity Relationships, Kathleen B. Mingle

Theses and Dissertations

High throughput experimentation (HTE) in catalysis has proven useful in expediting materials discovery via parallelized synthesis, characterization, and testing of candidate materials. However, even in a high-throughput manner, the combinatorial explosion of relevant parameters far exceeds our ability to study. To further complicate the problem, a large time investment and great deal of characterization is often required to build an in-depth understanding of catalytic materials. It follows that the field of heterogeneous catalysis is rich with examples of catalytic systems that have been developed using trial and error efforts for which a lot is known but context is lacking. Techniques …

Hydrodeoxygenation Of Acetic Acid Using Monometallic And Bimetallic Catalysts Supported On Carbon, José Luis Contreras Mora

Theses and Dissertations

Heterogeneous catalytic hydrodeoxygenation (HDO) of biomass-derived feeds is a deoxygenation process that is of highly interest. Carboxylic acids are one of the main components of bio-oils and acetic acid is one of the most abundant of these carboxylic acids. This acid is rich in oxygen, therefore a lot of research to produce fuel and other valuable chemicals such as ethanol is of interest.

This dissertation explores the gas-phase catalytic HDO of AA over catalysts supported on activated carbon (Cp-97). Temperature-dependent conversion and selectivity were studied at 1 atm from 200-400⁰C with an AA concentration of 1.1% and 20% …

Development Of Bimetallic Catalysts For Dry Reforming Of Methane And Hydrogenation Of Succinic Acid, Jayson Michael Keels

Theses and Dissertations

Advances in natural gas recovery have greatly impacted the global economy; the abundant supply of gas has revealed new opportunities and challenges in a wide range of markets within the fuels and chemicals industries. One such opportunity exists with the overabundance of gas from remote wells that is flared or emitted because of the high costs associated with transportation of a chemical with such a high molar volume. A possible solution is an on-site process to convert gas to higher value chemicals that are liquid at standard conditions, and can more easily be transported. As a first step, CO2 from …

Stabilization Of Silicon And Germanium Based High Capacity Anodes For Lithium Ion Batteries, Kuber Mishra

Theses and Dissertations

Lithium-ion batteries (LIBs) have been the driver of the widespread application of portable electronics. As the electronic devices have been more powerful and versatile, the pressing demand for higher energy density batteries have led the extensive explorations of novel materials for high capacity electrodes. Despite several breakthroughs in literature, the current state of art LIBs still uses the battery chemistry developed in early 1990s.The keys challenges for switching to other high capacity electrodes have been high cost, non-linear scalability and poorer electrochemical performance. This dissertation focusses on development of high capacity electrodes in order to increase the energy density of …

Fundamental Aspects Of A Novel Technology For Abatement Of Indoor Allergens, Odell Lendor Glenn Jr.

Theses and Dissertations

The overall goal of this research was to develop a novel approach to reduce the potency of certain asthma triggers, namely, proteins produced by pests or pets in indoor environments. The broad hypothesis of the research was that naturally occurring essential oils will demonstrate enhanced denaturing ability. In any indoor environment, allergens are bound to dry dust particles. In this work, the effectiveness of using dry ice and CO2 with potential for essential oils on dry allergenic proteins through CFD modeling and ELISA methods were evaluated.

There are three objectives central to this work. The first objective was to apply …

Understanding Early Amyloid-Ss Aggregation To Engineer Polyacid-Functionalized Nanoparticles As An Inhibitor Design Platform, Nicholas Vander Munnik

Theses and Dissertations

Alzheimer’s disease (AD) is characterized by the presence of amyloid-ß (Aß) protein aggregates in the brains of those afflicted. This protein aggregates via a complex pathway to progress from monomers to soluble oligomers and ultimately insoluble fibrils. Due to the dynamic nature of aggregation, it has proven exceedingly difficult to determine the precise interactions that lead to the formation of transient oligomers. A statistical thermodynamic model has been developed to elucidate these interactions. Aß was simulated using fully-atomistic replica exchange molecular dynamics. We use an ensemble of 5 × 105 configurations taken from these simulations as input for a self-consistent …

Design, Synthesis, And Characterization Of Monometallic And Bimetallic Catalysts, Sonia Eskandari

Theses and Dissertations

Supported catalysts are used extensively in a variety of heterogeneously catalyzed reactions for industrial processes. Techniques for preparing supported noble metal catalysts are typically chosen to achieve high metal dispersions in order to obtain high activity for a given metal loading. Enhancing the catalytic performance of heterogeneous catalysts can be done by increasing active site count as well as modification of the physico-chemical characteristics of the catalyst material. For supported metal nanoparticles this can be achieved by decreasing particle size, thus increasing dispersion or metal utilization on the surface of the particles, while modification of metal properties can be attained …

Selective Deposition Of Platinum By Strong Electrostatic Adsorption Onto Cobalt- And Iron-Based Catalysts For Fischer-Tropsch Synthesis, Fahad A. Almalki

Theses and Dissertations

Cobalt and iron based catalysts are commercially predominant for Fischer-Tropsch synthesis, Co-based catalysts for their stability, activity, and inactivity for the water gas shift reaction and Fe-based catalysts for their cheap cost, high light-olefins and alcohols selectivity, and tolerance to H2/CO ratio. These catalysts are structure sensitive with lower activity at nanoparticle sizes smaller than 6-8 nm. Co-based catalysts exhibit high activity, low CH4 selectivity, and high C5+ selectivity, while Fe-based catalysts are more selective to low-molecular-weight hydrocarbons such as olefins and alcohols. The reducibility of cobalt and iron is another important factor which may be key for improving their …

Dynamic Simulation Of A Solar Powered Hybrid Sulfur Process For Hydrogen Production, Satwick Boddu

Theses and Dissertations

The Hybrid Sulfur process is a thermo-electrochemical cycle used to produce hydrogen from water. The process requires a high temperature energy source for H2SO4 decomposition with temperature reaching 800°C. This step is followed by SO2 - depolarized water electrolysis. Using solar energy as the high temperature energy source allows for efficient environmentally friendly production of hydrogen. This method is an alternative to traditional photovoltaic electrolysis for hydrogen production. Making the process economically competitive is a major challenge. Operating the process with changes in the availability of solar energy also increases process complexity. The dependence of the process on solar energy …

A Novel Supercritical Co2-Based Decellularization Method For Maintaining Scaffold Hydration And Mechanical Properties, Michael A. Matthews, Tarek Shazly, Rachel M. Handleton, Dominic M. Casali

Faculty Publications

Decellularized tissues are commonly utilized as tissue engineering scaffolds. Decellularization by extended exposure to aqueous detergents can damage the microstructure or deposit cytotoxic residue. Supercritical carbon dioxide (scCO2) has been proposed for decellularization, but reportedly causes dehydration and scaffold embrittlement.

Presented herein is a novel decellularization method that preserves matrix hydration state and mechanical properties. Over 97% of the water in porcine aorta is maintained by presaturating scCO2 with water; however, complete decellularization was not attained by any process utilizing only scCO2. Instead, a novel hybrid method is presented that combines a brief (48 h) exposure of tissue to aqueous …

Modeling Battery Performance Due To Volume Change In Porous Electrodes Due To Intercalation, Taylor R. Garrick

Theses and Dissertations

The demand for energy continues to increase as the economies of developing countries become more modern and show an increased need for a reliable energy infrastructure in order to meet the increased demand associated with a large and more mobile population. An increased demand puts a strain on all sectors, however it is specifically noticeable in the transportation sector where a significant portion of the fuel utilized for transportation comes from petroleum and other fossil fuels. Recently, using alternative forms of energy for transportation has become reality, and in turn, using electricity as a transportation fuel has gained significant momentum, …

Determination And Validation Of High-Pressure Equilibrium Adsorption Isotherms Via A Volumetric System, Hind Jihad Kadhim Shabbani

Theses and Dissertations

Adsorption equilibrium isotherms for N2, CO2, and CH4 on zeolite 13X were investigated at three different temperatures (25.5, 50.5 and 75.5 ̊ C) and a pressure range of (0-6.89475) MPa for CH4 and N2 and in the range of (0-4.82633) MPa for CO2 using built in volumetric apparatus. The results were validated using with a volumetric system (ASAP) at the same temperatures and a pressure up to (160-110) KPa respectively. The experimental results were correlated using three process Langmuir (TPLM). The correlated isotherms were then used to calculate the isosteric heat of adsorption for the three gases on 13X. The …

Supercritical Carbon Dioxide Treatment Of Natural Biomaterials For Tissue Engineering Applications, Dominic M. Casali

Theses and Dissertations

The number of people requiring an organ transplant in the United States has increased considerably over the past 25 years, but the number of organ donations has stagnated; over 8,000 people now die annually while awaiting a transplant or become too sick to receive one. Tissue engineering (TE), the design and production of artificial tissues and organs in vitro, has been proposed to alleviate this problem. Though synthetic polymers offer tunable mechanical and biochemical properties, natural biomaterials have recently garnered attention in TE for their high degree of biocompatibility and ability to direct cell proliferation and constructive tissue remodeling. Yet …

Pollutant Formation In Oxy-Coal Combustion, Nujhat Choudhury

Theses and Dissertations

With the increasing levels of carbon dioxide (CO2) in the atmosphere, researchers are driven to seek cleaner combustion techniques to burn coal for power generation. Oxy-coal combustion is a promising technique to cut down CO2 emissions. This technology requires the introduction of a pure oxygen (O2) stream and a recycled flue gas stream into the boiler instead of air. Flue gas stream generated from the system will be low in volume and highly concentrated in CO2. Thus, the capture and sequestration process will be facilitated. But, one of the concerns of adopting this technology is the altered chemistry of pollutants …

Stilbenes: Therapeutic Interventions Targeting Amyloid Β Protein Aggregation In Alzheimer’S Disease, Yiying Wang

Theses and Dissertations

Alzheimer’s disease (AD) is the most common form of dementia and accounts for 60-80 % of all dementia cases. In the United States, AD is ranked as the 6th leading cause of death and it is the only one among the top 10 that cannot be prevented, treated or even slowed. All FDA approved drugs focus on attenuating the symptoms for a limited time by regulating neurotransmitters without any intervention with the underlying disease process. A major player in the initiation and development of this debilitating disorder is the misfolding and subsequent aggregating of amyloid-β (Aβ) peptide. This aggregation process …

Theoretical Investigation Of The Catalytic Hydrodeoxygenation Of Levulinic Acid Over Ru (0001) Catalyst Surface, Osman Mamun

Theses and Dissertations

Due to the rapidly declining fossil fuel reserves and the onset of global climate change, the development of active, selective, and stable catalytic materials for the efficient production of biomass derived platform chemicals, i.e., levulinic acid (LA), succinic acid (SA), γ-valerolactone (GVL) etc., is receiving considerable attention in order to produce second generation biofuels and commodity chemicals. Though solid lignocellulosic biomass is significantly cheaper than petroleum; however, the available technology is the significant barrier for large scale utilization of biomass for the production of biofuels. The development of biomass conversion technology requires, 1) identification of potential biomass chemicals that can …

Co2 Capture From Flue Gas By A Psa Process Using A Novel Structured Adsorbent, Nima Mohammadi

Theses and Dissertations

First adsorption equilibrium isotherms for N2, O2, Ar and CO2 on zeolite 13X were measured at three temperatures (25, 50, 75 °C) and pressures up to 110 kPa with a volumetric method and validated by also measuring the same isotherms with a gravimetric system.

Then a comprehensive 2-D mathematical model was developed to study the fundamentals of adsorption processes in parallel channel structured adsorbents. The results clearly indicated that under studied circumstances the plug flow condition can be assumed and therefore the system is not subject to premature breakthrough.

The pressure drop of corrugated structured adsorbents with narrow triangular channels …

Rational Synthesis Of Catalysts For Biomass Conversion, Qiuli Liu

Theses and Dissertations

With climate change due to global warming, the production of hydrocarbon fuels and chemicals from renewable biomass resource has become more pressing in recent decades. The biggest challenge in biomass conversion is to develop active, selective and stable catalysts for particular applications. The objective of this research is to optimize catalytic performance for hydrodeoxygenation (HDO) and hydrogenation reactions by enhancing the stability of the support, tuning metal particle size, and controlling surface composition.

The high content of water in bio-oil and the aqueous environment of the upgrading process requires a hydrothermally stable catalyst. The hydrothermal stability has been effectively improved …

Development Of Novel Catalysts For Air Pollution Control, Chao Wang

Theses and Dissertations

The development of economy strongly related with increased consumption of fossil fuels, which causes severe air pollution issue. With more and more strict environmental regulations implemented all over the world, robust and efficient emission control technologies need to be innovated and applied to overcome the pollution challenge. This dissertation focuses on utilizing heterogeneous catalysis to eliminate carbon monoxide (CO), hydrocarbons (CH_x) and nitric oxides (NO_x) emissions produced from fossil fuel combustion.

The first type of catalyst is Pd supported on Mn-Ce solid solution. It achieves 100% CO conversion at room temperature. The high activity is attributed …

Structural, Interfacial, And Electrochemical Properties Of Pr2nio4+Δ – Based Electrodes For Solid Oxide Fuel Cells, Emir Dogdibegovic

Theses and Dissertations

Currently, the electrochemical performance and performance durability of solid oxide fuel cells (SOFCs) are limited by cathode materials. The high polarization resistance and phase instability of the cathode are two major challenges to hinder the commercialization of SOFC systems. Two families of oxides are presently known as potential cathode materials for SOFCs: (1) the perovskite family of oxides with a general formula of ABO₃, and (2) the Ruddlesden-Popper (RP) family of oxides (e.g. nickelates) with a general formula of A₂BO₄. The electron-hole conduction in these materials occurs simultaneously with oxygen ion conduction based on …

Ultrathin Graphene Oxide Membranes For Water Purification: Fundamentals & Potential Applications, Weiwei Xu

Theses and Dissertations

To develop ultrathin GO membranes with both high permeation rate and excellent selectivity, it is essential to understand the interlayer nanostructure and its influence on water purification performance. We purposely deposited GO at a fast rate and at a rate ~12 times slower to control the interlayer nanostructure of the resulting membranes. The d-spacing difference between proposed thermodynamically favored interlayer structure which formed at slow deposition rate and another relative randomly packed interlayer structure formed at fast deposition rate were corroborated by XRD, organic vapor deposition, and AFM. Molecular dynamics simulations further confirmed that, in type I structure, functionalized patches …

Statistical Mechanics Of Lipid-Liquid Crystal Systems: From Fundamentals To Sensing Applications, Donya Ohadi Kabir Maghsudlu

Theses and Dissertations

Understanding the thermodynamics of small systems has a well-established history. The non-intuitive behavior of the intensive properties of small systems comprised of less than a few hundred particles has important implications in many areas of engineering and materials science. Nevertheless, many open questions about the thermophysical properties of systems not in the thermodynamic limit remain unanswered. In the first part of this work, we explore the consequences of the coupling of two small subsystems that together make up a larger isolated system through the use of statistical mechanics and molecular dynamics simulations of Lennard-Jones particles in two dimensions. The results …

Adsorption Reversibility Of So2, No2, And No On 13x And 5a Zeolites, Peter Fairchild

Theses and Dissertations

The adsorption reversibility of gasses that are typically found in flue gas for coal based power plants, such as SO2, NO2, and NO, onto 13X and 5A zeolites was presently investigated. The four individual gas mixtures containing these species consisted of 74 ppm NO (balance He), 74 ppm NO2 (balance He), 42 ppm SO2 (balance He), and 500 ppm SO2 (balance N2), which were also consistent with the values that are found in flue gas. Another gas, 15.03 mol% CO2 (balance N2), was also used in this work to evaluate the role of exposing SO2 to the zeolite on their …

Characterization, Synthesis And Stabilization Of Au Based Bimetallic Catalysis For The Hydrochlorination Of Acetylene, Kerry Charles O'Connell

Theses and Dissertations

Polyvinyl chloride (PVC) is the third most-produced plastic polymer world-wide by volume after polypropylene and polyethylene. Vinyl chloride monomer, which is polymerized into PVC, is produced via mercuric chloride catalysts that deactivate as mercury sublimes into the atmosphere from the catalyst surface, resulting in substantial environmental concerns.

In an effort to rationally synthesize non-mercuric catalysts, strong electrostatic adsorption (SEA) was used to prepare highly dispersed and active gold nanoparticles over low point of zero charge (PZC) carbon to increase the active metal surface area. The use of <1.5nm gold clusters did not lead to large increases in activity as there was an increased degree of particle coalescence during reaction for activated carbon supported samples. A pronounced support effect was observed in which oxide supports completely prevented Au sintering, but was virtually inactive. This suggests that the active site for the hydrochlorination reaction involves the carbon surface.

The stabilization of carbon supported gold nanoparticles in the HCl-rich reaction environment was …

Polyphenols As Natural, Dual-Action Therapeutics For Alzheimer's Disease, Kayla M. Pate

Theses and Dissertations

Alzheimer’s disease (AD), the most common form of dementia, is characterized by extracellular plaques in the brain created when monomeric amyloid-β (Aβ) protein aggregates into fibrillar structures. Soluble Aβ aggregates, including oligomers, that form along the reaction pathway are believed to be the primary pathogenic species and have been shown to increase the production of reactive oxygen species (ROS). This upregulation of ROS is one suggested contributing factor of Aβ aggregate cytotoxicity and has proven capable of mediating cell signaling associated with Aβ aggregate-induced cellular responses.

Polyphenols have been suggested as a complimentary AD therapeutic based on epidemiological evidence that …

Pvdf Membranes With Stable, Ultrathin Graphene Oxide (Go) Functional Coatings For Antifouling Oil/Water Separation Under Cross-Flow Condition, Lei Wang

Theses and Dissertations

Oil/water separation plays an important role in industrial wastewater treatment and environment protection. For the treatment of oily wastewater, especially for removing oil droplets with sizes in the micrometer range, ultrafiltration (UF) membrane technology is considered the most efficient method due to its high separation efficiency and relatively simple operational process. However, caused by the deposition of the oil droplets onto the membrane surface and into the membrane pores, the fouling of UF membranes shortens their service time and degrades their separation performance in practical applications.

In this work, graphene oxide (GO) was utilized as a novel coating material to …

Development Of Pressure Swing Adsorption (Psa) Processor Co2 Capture From Flue Gas, Md. Atikur Rahman

Theses and Dissertations

Reducing the anthropogenic CO2 emissions and lowering the concentration of greenhouse gases in the atmosphere has become one of the most important environmental issues of recent times. To this end, the development of a cost effective pressure swing adsorption (PSA) process, utilizing commercially available 13X zeolite as the adsorbent, is underway to remove and concentrate CO2 in the flue gas of a coal-fired power plant. This systematic development effort has been carried out so far at the bench scale. It has included the following studies that defined and validated this PSA process both experimentally and via a PSA process model. …

Ultrathin Microporous Metal Oxide Coatings: Preparation By Molecular Layer Deposition, Characterization And Application, Zhuonan Song

Theses and Dissertations

Molecular layer deposition (MLD), a gas phase deposition technique, was applied to deposit conformal organic-inorganic hybrid coatings by conducting a series of sequential, self-limiting surface reactions on substrates with exquisite thickness control at the sub-nanometer level. Obtained organic-inorganic hybrid coatings can subsequently be converted into porous coatings by removing the organic compound. Potential of functional coatings and membranes prepared by MLD was explored for applications from adsorptive separation, water purification, to gas storage.

We demonstrated a new concept, pore misalignment, to continuously fine tune the molecular-sieving “gate” of 5A zeolite by adjusting the external porous Al2O3 MLD coating thickness. For …

Uncertainty Quantification In Computational Catalysis, Eric Alan Walker

Theses and Dissertations

This dissertation augments the field of computational catalysis with uncertainty quantification. An efficient tool to describe the energetics and structure of atomistic systems is density functional theory (DFT). DFT may be used to understand how catalysts work although DFT is inexact in nature due to approximations necessary for computational tractability. These approximations in DFT cause uncertainty in microkinetic model results for catalytic systems. Therefore, reliable model results gained from DFT include a quantification of uncertainty. The case study to examine a systematic framework for uncertainty quantification is water-gas shift (WGS CO+H2O⇌CO2+H2) reaction by Pt/TiO2 catalyst.

Uncertainties are represented with probabilities …