Chemical Engineering Commons^™

Quantifying And Elucidating The Effect Of Co2 On The Thermodynamics, Kinetics And Charge Transport Of Aemfcs, Yiwei Zheng

Theses and Dissertations

Anion exchange membrane fuel cells (AEMFCs) have shown significant promise to provide clean, sustainable energy for grid and transportation applications – and at a lower theoretical cost than more established proton exchange membrane fuel cells (PEMFCs). Adding to the excitement around AEMFCs is the extremely high peak power that can now be obtained (> 3 W cm-2) and continuously improving durability (1000+ h), which has made the future deployment of AEMFCs in real-world applications a serious consideration. For some applications (e.g. automotive), the most critical remaining practical issue with AEMFCs is understanding and mitigating the effects of atmospheric CO2 (in …

Improving Boron For Combustion Applications, Kerri-Lee Annique Chintersingh

Dissertations

Boron has received much attention as a potential additive to explosives and propellants due to its high theoretical gravimetric and volumetric heating values. The challenge, however, is that boron particles tend to agglomerate, have lengthy ignition delays and very low combustion rates. Prior research indicates that boron’s long ignition delays are due to its inhibiting naturally occurring oxide layer, impeding the diffusion of reactants for oxidation. For combustion, current studies report that boron particles have two consecutive stages, but the actual reaction mechanism is poorly understood. Despite many years of relevant research, quantitative combustion data on micron-sized boron particles are …

Influence Of Frictional Or Rotational Kinetic Energy On Wellbore-Fluid/Temperature Profiles During Drilling Operations, Ahmed Q. Al Saedi, Ralph E. Flori, C. Shah Kabir

Geosciences and Geological and Petroleum Engineering Faculty Research & Creative Works

Temperature-profile distributions in a wellbore during drilling operations might take different forms when applying the energy balance in the overall system. For steady-state conditions, wherein the wellbore is considered a closed system, adding any source of additional energy to this system can influence the predicted temperature profiles. This study presents a new analytical model to investigate the influence of rotational energy arising from the drillstring operation on the wellbore-temperature behavior.

A significant part of the drilling operation is rotation of the drillstring. Depending on the drilling rig, various equipment provides this kind of energy, such as the rotary table or …

Elucidation Of The Catalytic Partial Oxidation Of Methane Utilizing The One-Of-A-Kind Catalytic Shock Tube Technique, Robyn E. Smith

Dissertations and Theses

The mechanism for the catalytic partial oxidation of methane has been debated in scientific literature for over 20 years. This is a seemingly simple reaction producing CO, CO₂, H₂ and H₂O through either partial oxidation followed by complete oxidation or complete oxidation followed by reforming steps. What is happening when the reaction is allowed to occur in an environment absent of transport limitations, absent of temperature gradients and temperature changes, absent of boundary layers must be understood and, until now, has yet to be achieved in one experimental technique.

A novel method using a one …

Pyrolysis Kinetics Of Live And Dead Wildland Vegetation From The Southern United States, Elham Amini, Mohammad-Saeed Safdari, David R. Weise, Thomas H. Fletcher

Faculty Publications

The fundamental combustion behavior of live wildland vegetation is not fully understood. Since the combustion process during wildland fire starts with pyrolysis, there is a need for better understanding of pyrolysis to develop improved wildland fire models. The kinetics of pyrolysis of live and dead wildland vegetation has not been explored in detail. In this study, the pyrolysis kinetics were determined for 14 different plant species (live and dead) which are all native to the forests in the southern United States. Pyrolysis experiments were carried out in a Thermogravimetric analyzer (TGA) under inert conditions at 5 different heating rates ranged …

Homogeneous Reaction Kinetics Of Carbohydrates With Viologen Catalysts For Biofuel Cell Applications, Hilary Bingham

Theses and Dissertations

Energy usage is continually on the rise and significant efforts are being extended to provide more renewable energy. One area of exploration is the development of fuel cells, which includes biofuel cells that can extract energy from carbohydrates obtained from biomass. Recently, viologen catalysts have been shown to enhance reaction rates of energy extraction and improve carbohydrate conversion efficiencies. However, characterizing the effects of process parameters such as pH, reactant concentrations, and carbohydrate exposure time to buffer solutions with a rigorous model is lacking. This thesis characterizes the homogeneous reaction between carbohydrates and a methyl viologen catalyst to provide insights …

Kinetic Modelling And Experimental Studies For The Effects Of Fe2+ Ions On Xylan Hydrolysis With Dilute-Acid Pretreatment And Subsequent Enzymatic Hydrolysis, Hui Wei, Xiaowen Chen, Joseph Shekiro, Erik Kuhn, Wei Wang, Yun Ji, Evguenii Kozliak, Michael E. Himmel, Melvin P. Tucker

Chemical Engineering Faculty Publications

High-temperature (150–170 °C) pretreatment of lignocellulosic biomass with mineral acids is well established for xylan breakdown. Fe²⁺ is known to be a cocatalyst of this process although kinetics of its action remains unknown. The present work addresses the effect of ferrous ion concentration on sugar yield and degradation product formation from corn stover for the entire two-step treatment, including the subsequent enzymatic cellulose hydrolysis. The feedstock was impregnated with 0.5% acid and 0.75 mM iron cocatalyst, which was found to be optimal in preliminary experiments. The detailed kinetic data of acid pretreatment, with and without iron, was satisfactorily modelled …

Reaction Kinetics Of The Hydrogenation Of Phenol In A Tubular Reactor, Michael Selzer

Williams Honors College, Honors Research Projects

The reaction kinetic parameters for the hydrogenation of phenol to cyclohexanone are determined for the liquid phase reaction with the palladium catalyst supported on an electrospun PVDF membrane. Runs of the reactor were completed at catalyst loadings of 40, 50, and 60 g/m², and tube diameters of 0.187 in and 0.25 in with a runtime of ten hours. One-dimensional and two-dimensional models of the experimental setup were developed. Fitting data to the one-dimensional model found that the pre-exponential factor was 2.50 x 10⁴, the activation energy was 7.69 kJ/mol, and the order with respect to phenol …

Using Agricultural Wastes To Treat Lead-Contaminated Water In Western Australia, Hanie Hashtroudi

Theses: Doctorates and Masters

Aqueous solutions are becoming increasingly contaminated in all parts of the world (2015). Heavy metals are toxic contaminants that are mainly distributed in urban stormwater run-off and industrial wastewaters as a result of some mining operations, electronic assembly planting, battery manufacturing, and etching operations (Kadirvelu et al. 2001). Pb (II) is a heavy metal that causes significant damage in the human body. Drinking lead-contaminated water even at low concentrations may cause lifethreatening conditions such as cancer, kidney damage, brain damage, and liver problems (El-Said 2010). Therefore, it is necessary to remove lead from aqueous solutions.

Several conventional physical, chemical, and …

Abiotic- And Biotic-Formation Of Manganese Oxides And Their Fate In Environmental Systems, Haesung Jung

McKelvey School of Engineering Graduate Student Theses & Dissertations

Manganese (hydr)oxide (Mn (hydr)oxide) minerals are ubiquitous in aquatic and terrestrial environments. These minerals have high surface areas and are highly sorptive and redox active. From decades of accumulated knowledge about natural redox cycling, we have found that Mn (hydr)oxides play critical roles as electron donors and acceptors in elemental geochemical cycling and biological metabolisms in nature. Thus, Mn (hydr)oxides have garnered increasing interest to understand natural systems. Considering the variety of redox reactions with Mn (hydr)oxides in nature, it is also expected that there should be diverse pathways to form Mn (hydr)oxides through abiotic and biotic processes. Previous studies …

Development And Validation Of A Kinetic Model For Enzymatic Hydrolysis Using Candida Rugosa Lipase, Ammar Jamie, Ali Alshami, Zuhair O. Maliabari, Muataz A. Ateih

Chemical Engineering Faculty Publications

Biochemical processing involving enzymatic catalysis of hydrolysis reactions of oils and fats must overcome significant technological barriers before the full benefits of the technology can be realized. Owing to their selectivity and mild reaction conditions, lipases are becoming increasingly important as biocatalysts provided that their kinetics and optimum reaction conditions are well-understood. In this study we report on the development and validation of a kinetic model for the degradation of oils using Candida rugosa lipase, from which a better understanding of the influence of different reaction conditions on hydrolysis kinetics is elucidated. Variations of reaction temperature, mixing speed, enzyme loading …

Modeling Effects Of Annealing On Coal Char Reactivity To O2 And Co2, Based On Preparation Conditions, Troy Michael Holland, Sham Bhat, Peter Marcy, James Gattiker, Joel D. Kress, Thomas H. Fletcher

Faculty Publications

Oxy-fired coal combustion is a promising potential carbon capture technology. Predictive computational fluid dynamics (CFD) simulations are valuable tools in evaluating and deploying oxyfuel and other carbon capture technologies, either as retrofit technologies or for new construction. However, accurate predictive combustor simulations require physically realistic submodels with low computational requirements. A recent sensitivity analysis of a detailed char conversion model (Char Conversion Kinetics (CCK)) found thermal annealing to be an extremely sensitive submodel. In the present work, further analysis of the previous annealing model revealed significant disagreement with numerous datasets from experiments performed after that annealing model was developed. The …

Comprehensive Model Of Single Particle Pulverized Coal Combustion Extended To Oxy-Coal Conditions, Troy Michael Holland, Thomas H. Fletcher

Faculty Publications

Oxy-fired coal combustion is a promising potential carbon capture technology. Predictive CFD simulations are valuable tools in evaluating and deploying oxy-fuel and other carbon capture technologies either as retrofit technologies or for new construction. However, accurate predictive simulations require physically realistic submodels with low computational requirements. In particular, comprehensive char oxidation and gasification models have been developed that describe multiple reaction and diffusion processes. This work extends a comprehensive char conversion code (CCK), which treats surface oxidation and gasification reactions as well as processes such as film diffusion, pore diffusion, ash encapsulation, and annealing. In this work several submodels in …

Low-Temperature Artificial Maturation Studies Of Type Ii And Type Iii Kerogens: Implications For Biogenic Gas Production, Albert Willy Nguena Kamga

Chemistry & Biochemistry Theses & Dissertations

Ancient organic matter (OM) in shales and coals, known mainly as Type II and Type III OM are known to produce both biogenic, thermogenic gas and oil. In this dissertation, mild artificial maturation, via closed system pyrolysis, is employed to determine the thermal reactivity of Type II and Type III OM beyond diagenesis. We select three Type II kerogens: i) Type II kerogen isolated from recent cores (3.3 Ma, Ro = 0.28) recovered from an upwelling basin in Namibia, Africa referred to as ODP Sediment, ii) Type II-S isolated from sediments (150 Ma, Ro = 0.38) recovered from an outcrop …

Experimental And Theoretical Investigation Of Sustainable Fast Pyrolysis Biofuels From Woody Biomass, Bethany Jean Klemetsrud

Dissertations, Master's Theses and Master's Reports

Biofuels are an important advancement in alternative energy that can provide substantial environmental benefits compared to their conventional fossil fuel counterparts Said benefits are usually measured using life cycle assessments. However, it is not well understood yet how different methodological choices such as system boundaries, biomass feedstocks, conversion pathways, geographical data, etc. affect the conclusions drawn from biofuels LCA. This research shows large variability in life cycle assessment results and limits comparison across different biofuel pathways due to methodological choices set forth by policy and certification schemes. Advanced biofuels have not reached large scale production due to a limited understanding …

Global Sensitivity Analysis For A Comprehensive Char Conversion Model In Oxy-Fuel Conditions, Troy Michael Holland, Thomas H. Fletcher

Faculty Publications

Oxy-fired coal combustion is a promising potential carbon capture technology. Predictive CFD simulations are valuable tools in evaluating and deploying oxy-fuel and other carbon capture technologies either as retrofit technologies or for new construction. However, accurate predictive simulations require physically realistic submodels with low computational requirements. In particular, comprehensive char oxidation and gasification models have been developed that describe multiple reaction and diffusion processes. This work focuses on the sensitivity of a recent comprehensive char conversion code named CCK, which treats surface oxidation and gasification reactions as well as the processes such as film diffusion, pore diffusion, ash encapsulation, and …

Oxidation Process Of H 2 O /Uv For Cod Reduction Of Wastewater From Soybean Tofu Production, Komala Pontas, Abrar Muslim

Makara Journal of Technology

Chemical Oxygen Demand (COD) reduction of wastewater from soybean tofu production was studied by conducting advanced oxidation process (AOP) using hydrogen peroxide with UV radiation catalysts in a closed cylindrical glass reactor. The hydroxyl radical (*OH) concentration from H2O2 decomposition was modeled, and exponential trends were found for the *OH concentration over radiation time and operation temperature. As a result, it was found that the maximal *OH concentration was 0.209 mol L-1 at 240 minutes and 50 °C. The *OH concentration exponentially increased following rise in operation temperature. The H2O2/UV AOP application reduced COD concentration to approximately 42.41% from 10,545 …

Interfacial Engineering Of Biomass Hydrolysis By Cellulase Enzymes And Mechanistic Modeling Of Hydrolysis Of Cellulose Substrates, Ravinder Kumar Garlapalli

Theses and Dissertations--Chemical and Materials Engineering

Lignocellulosic biomass is a sustainable and renewable energy resource that can be converted to fuels and other commodity chemicals, but this conversion is currently limited by its recalcitrance to enzymatic degradation. Because of this recalcitrance, the major challenges in the commercialization of enzymatic hydrolysis processes are the relatively low hydrolysis rates, limited cellulose conversion under some conditions, and high cost of enzymes.

Enzymatic hydrolysis is influenced by the structure of the biomass after pretreatment and the mode of enzyme action, but has also been shown to be enhanced by surfactant additives. The objective of this work was to elucidate the …

Preparation Of Active, Stable Supported Iron Catalysts And Deactivation By Carbon Of Cobalt Catalysts For Fischer-Tropsch Synthesis, Kamyar Keyvanloo

Theses and Dissertations

The first half of this dissertation reports the development of supported Fe FT catalysts including the effects of various, carefully chosen preparation methods on the performance of alumina-supported iron/copper/potassium (FeCuK/Al2O3); it was determined that non-aqueous slurry impregnation and co-impregnation yielded catalysts with activities as high as any reported in the literature. Furthermore, the effects of support properties including pore size, hydroxyl group concentration, and support stabilizer were investigated for FeCuK/Al2O3 catalysts containing 20 or 40% Fe. For the first time, we report the performance of a supported Fe FT catalyst that is not only more active and stable than any …

Evaluation Of Environmental Materials As Thermal Witness Materials, Shashank Vummidi Lakshman

Dissertations

New and complex energetic materials are under development for achieving tunable pyrotechnical events for applications such as neutralization of biological weapons, bunker busters and many others. To guide the development of hybrid materials, the pyrotechnical environment they produce requires higher degree of characterization i.e. good description of spatial and temporal temperature distribution.

Temperature measurements in pyrotechnical events are especially challenging, where the temperature of the environment rises more than 2000 K on microseconds to few milliseconds time scale. These environments produce high thermal stress where traditional sensors like thermocouples, optical pyrometers struggle to describe the dynamic changes in the environment. …

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 …

Modeling Of Kinetically Limited Growth Rate For Solution-Synthesized Germanium Nanocrystals, Nicholas Shoop

Chemical and Biological Engineering ETDs

Solution synthesis is a common method of generating semiconductor nanocrystals. For solution synthesis, many studies have assumed that the growth rate is diffusion-limited with an unphysically low diffusion constant. In this thesis, a model is developed that considers both diffusion and surface kinetics. The diffusion coefficient of Ge monomers through the solvent, octadecene, at elevated synthesis temperatures is estimated to be on the order of 10-5 to 10-4 cm2/sec, while the mass transfer boundary layer thickness is estimated to be on the order of a few nanometers, similar to the nanocrystal size. These two realistic conditions strongly suggest that the …

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 …

Kinetic Analysis Of Thiol Oxidation To Study The Effects Of Fluorinated Groups On Metal Phthalocyanine Catalysts, Nellone Eze Reid

Dissertations

The oxidation of thiol (RSH) to disulfide (RSSR) is important biologically and industrially. Corrosive and malodorous thiols exist as contaminants in wastewater discharge from mining facilities, pulp and paper mills, tanneries, and oil refineries. The elimination of thiols from petroleum products is necessary for even cleaner fuels. Thiols in gas products can also inhibit catalyst activity for some downstream processes.

Experiments and mechanistic kinetic studies were conducted for the aerobic oxidation of 2-mercaptoethanol (2-ME) and 4-fluorobenzenethiol (4-FBT) catalyzed by cobalt phthalocyanines: H₁₆PcCo, F₁₆PcCo, and F₆₄PcCo, each exhibiting a metal center subject to increasing Lewis …

Kinetic Modeling Of Self-Hydrolysis Of Aqueous Nabh4 Solutions By Model-Based Isoconversional Method, Rajasree Retnamma, A. Q. Novais, C. M. Rangel, Lin Yu, Michael A. Matthews

Faculty Publications

The present work reports the kinetic modeling of self-hydrolysis of non-buffered, non-stabilized NaBH4 solutions by model-based isoconversional method. The overall kinetics is described by a „reaction-order‟ model in a practical operating window of 10-20 wt% NaBH4 solutions at 25-80 C and 0-50% conversions. The apparent activation energy and pre-exponential factor are interrelated through a kinetic compensation effect (KCE). The apparent reaction order remains constant at a given temperature irrespective of extent of conversion and decreases with increase in temperature. It decreases from firstorder to 0.26 with increase in temperature from 25 to 80 C. The apparent activation energy is found …

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 …

Reaction Mechanisms Of Hydrocarbon And Mercury Systems In The Atmosphere And In Combustion: A Theoretical Study Of Thermochemical And Kinetic Properties, Itsaso Auzmendi Murua

Dissertations

The continuing increase in the world population and the rapidly changing lifestyle and education of this population projects significant increases in energy requirements. Global warming is a worldwide major concern with a very serious potential stress on our climate threatening major changes to the environment. It is, without question, of major importance to improve the efficiency and optimize the current available combustion processes and fuel sources, to develop alternative fuels and to reduce the emissions of toxic pollutants.

The objective of this dissertation is to present thermochemical, kinetic and modeling results on two reference fuels (the land vehicle fuel isooctane …

Kinetics Of Lipid Extraction From Microalgae, Brian Mcconnell

Honors Theses and Capstones

No abstract provided.

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 …

Capacity Fade Model For Spinel Limn2O4 Electrode, Yiling Dai, Long Cai, Ralph E. White

Faculty Publications

A mathematical model for the capacity fade of a LiMn₂O₄ (LMO) electrode is developed in this paper by including the acid attack on the active material and the solid electrolyte interphase (SEI) film formation on the LMO particle surface. The acid generated by the LiPF₆ and the solvent decompositions are coupled to the manganese (Mn) dissolution. The decrease of the Li ion diffusion coefficient is involved as another contribution to the capacity fade, which is caused by the passive film formation on the active material surface. The effects of cell practical operation/fabrication conditions and kinetics of …