Chemical Engineering Commons^™

Thermochemistry And Kinetic Analysis On Radicals Of Acetaldehyde + O2, Allyl Radical + O2 And Diethyl And Chlorodiethyl Sulfides, Jongwoo Lee

Dissertations

Thermochemical properties for reactants, intermediates, products and transition states important in the radicals of acetaldehyde + O₂ and allyl radical + O₂ reaction systems are analyzed with density functional and ab initic calculations, to evaluate the reaction paths and kinetics in oxidation and pyrolysis. Ketene is one important product resulting from acetaldehyde oxidation; thus thermochemistry plus isomerization and conversion reactions of ketene are also analyzed. Enthalpies of formation are determined using isodesmic reaction analysis at the CBSQ composite and density functional levels. Entropies and heat capacities are determined using geometric parameters and vibration frequencies obtained at the HF/6-31G(d') …

A Reactive Melt Modification Of Polyethylene Terephthalate, Rahul Ramesh Dhavalikar

Dissertations

This work investigates the structural and chemorheological modification of polyethylene terephthalate in the melt phase with low molecular weight multifunctional glycidyl compounds as reactive additives. Polyethylene terephthalate undergoes chain extension and/or branching reactions with the additives that result in modified rheological properties suitable for certain polymer processing operations such as extrusion blow molding or extrusion foaming to low densities.

Among five different low MW difunctional and trifunctional epoxy compounds, triglycidyl isocyanurate is shown to be an efficient reactive melt modifier for commercially available polyethylene terephthalate polymers. Its stability at the polyethylene terephthalate melt temperatures is confirmed offline through thermogravimetric and …

Study Of Vapor/Gas Permeation Using Thin Immobilized Liquid Membrane, Gordana Obuskovic

Dissertations

To improve liquid membrane selectivity and stability for removal of vapor and gases from a gas stream, a thin immobilized liquid membrane (ILM) has been studied. Low vapor pressure liquid solvent/solutions were immobilized in part of the micropores of a hydrophilic, hydrophobic or ceramic hollow fiber substrate. To prepare such thin ILMs, three approaches were used: evaporation of the a volatile solvent; acrylic acid-grafted hollow fibers providing a thin hydrophilic layer; pressurization technique.

For removal of volatile organic compound (VOC), a thin ILM of silicone oil incorporated in the micropores of a hydrophobic hollow fiber with a silicone rubber coating …

Synthesis And Enzymatic Resolution Of Amino Acid Esters In "Green" Solvents -- Ionic Liquids, Hua Zhao

Dissertations

Chiral separation has attracted tremendous attention in pharmaceutical and chemical fields, especially in the area of chiral drug development. Chiral amino acids are among the most important intermediates in the asymmetric synthesis of modem drugs. This research has developed an effective method for obtaining optically pure amino acids by enzymatic resolution using a "green" solvent, named an ionic liquid.

Ionic liquids, a new type of "green" solvents, have been used in many organic reactions and other chemical processes (such as liquid-liquid extraction) with improved performance. This is mainly due to their favorable properties for chemical applications, such as low vapor …

The Development Of H Homogeneous Nucleation Rate Model For Thermoplastic Foams Based On A Molecular Partition Function And Fickian Diffusion, Ronald G. Gabbard

Dissertations

An improved homogeneous nucleation rate model for thermoplastic foams has been developed. This model does not rely on experimentally determined parameters and only uses pure component physical property data and a binary diffusion coefficient. This model, like those derived from classical nucleation theory, is made up of two parts, one that determines the size of the energy barrier in the nucleation process and one that estimates the forward rate of the process. A statistical-mechanical approach was used to create an energy term that is based on a molecular partition function. In this approach, the bulk phase (polymer and blowing, agent …

Process Control Of A Laboratory Combustor Using Neural Networks, Thana Slanvetpan

Dissertations

Active feedback and feedforward-feedback control systems based on static-trained feedforward multi-layer-perceptron (FMLP) neural networks were designed and demonstrated, by experiment and simulation, for selected species from a laboratory two stage combustor. These virtual controllers functioned through a Visual Basic platform. A proportional neural network controller (PNNC) was developed for a monotonic control problem - the variation of outlet oxygen level with overall equivalence ratio (Φ₀). The FMLP neural network maps the control variable to the manipulated variable. This information is in turn transferred to a proportional controller, through the variable control bias value. The proposed feedback control methodology …

Application Of Chemical Kinetic Modeling To Improve Design And Performance Criteria For A Practical Incineration System, Charles A. Bass Jr.

Dissertations

In this study, detailed thermo-chemical kinetics with networked ideal reactor model were applied to simulate a practical combustion system -the Secondary Combustion Chamber (SCC) of the Rotary Kiln incineration Simulator (RKIS) at the EPA facility at Research Triangle Park, NC. The networked ideal model was developed using analysis of reactor geometry, temperature profile measurements, and SO₂ tracer data provided by EPA. A computer simulation of the networked model was developed using the CHEMKIN H library. A parallel effort considered the effects of non-ideal mixing on detailed thermo-kinetic, simulations. Specifically, an alternate approach was developed to solve the Partially Stirred …

Elementary, Pressure Dependent Model For Combustion Of C1, C2 And Nitrogen Containing Hydrocarbons : Operation Of A Pilot Scale Incinerator And Model Comparison, Chad Sheng

Dissertations

A 140000 BTU/hr pilot scale incinerator has been constructed, tested and run; and an online sampling train capable of taking in situ data has been established. The continuous on-line analytical instruments include a CO analyzer, an NO/NOx analyzer and an 02 analyzer. In addition, two gas chromatographs with flame ionization detector are used to determine CH4, C2H2 + C2H4 and total hydrocarbon concentrations. Typical operating conditions are at an average 02 concentration of 6 - 8 %. The NO concentration ranged from 100 - 200 ppm. Approximately I ppm of CH.4 is also present at steady state operations.

The kinetic …

Evolutionary Polymorphic Neural Networks In Chemical Engineering Modeling, Li Gao

Dissertations

Evolutionary Polymorphic Neural Network (EPNN) is a novel approach to modeling chemical, biochemical and physical processes. This approach has its basis in modern artificial intelligence, especially neural networks and evolutionary computing. EPNN can perform networked symbolic regressions for input-output data, while providing information about both the structure and complexity of a process during its own evolution.

In this work three different processes are modeled: 1. A dynamic neutralization process. 2. An aqueous two-phase system. 3. Reduction of a biodegradation model. In all three cases, EPNN shows better or at least equal performances over published data than traditional thermodynamics /transport or …

Modeling And Experimental Validation Of A Single-Feed Semi-Batch Precipitation Process, Ernesto Uehara-Nagamine

Dissertations

Crystallization is a widely practiced unit operation throughout the chemical and pharmaceutical process industries. Despite its widespread application, crystallization still suffers a disproportionate number of process difficulties due to the complexity of the steps involved in the process. In particular, the final characteristics of the product are strongly affected by the mixing conditions during the process. The development of a validated modeling approach would be highly valuable for the successful prediction of the crystal characteristics under differing mixing conditions.

In the present work, the single-feed semi-batch precipitation process of barium sulfate in a stirred tank was experimentally studied and numerically …

An Investigation Of Centrifugal Blood-Cell Separation, Timothy Edward Roche

Dissertations

This dissertation investigated the centrifugal, batch separation of whole blood into subpopulations of red blood cells (erythrocytes) and white blood cells (leukocytes). Separations took place in a custom-built centrifuge (using a seal-less, anti-twisting feed/withdrawal system) containing, a 25-ml capacity separation chamber. The blood separation chamber had dart-shaped geometry in the radial plane and a constant depth in the axial direction. Separation experiments were performed on whole bovine blood at varying hematocrit, centrifuge speed, and batch duration. A small, companion study of whole human blood separation runs also were conducted; they concentrated on batch duration effect and achieved superior separations.

A …

An Experimental Study Of Dry Particle Coating : Devices, Operating Parameters And Applications, Michelle Ramlakhan Mohan

Dissertations

Dry particle coating, which mechanically coats fine guest particles onto the surfaces of larger host particles, without binders or solvents, is investigated. Several systems of host and guest particles are coated in different devices to study various aspects of dry particle coating. The devices used are Magnetically Assisted Impaction Coating (MAIC) device, Mechanofusion, and the Hybridizer.

MAIC is used to coat fine SiO₂ guest particles onto the surface of larger cornstarch and cellulose host particles. This is done to simultaneously improve the flowability of the host particles, as well as reduce their hydrophilicity. Dry particle coating is used to …

Immobilized Liquid Membranes For Facilitated Transport And Gas Separation, Anjaneya Sarma Kovvali

Dissertations

Separation and purification of gas mixtures is a major area of activity in chemical engineering. Gas separation using facilitated transport membranes has been the subject of considerable research for many years. Immobilized liquid membranes (ILMs) are an important class of facilitated transport membranes. Despite their potential to provide superior performance, they could not achieve commercial success so far due to their instability. Recent research addressed the issue of stability of ILMs by replacing water as the solvent successfully with glycerol. In the present thesis, the relevance of glycerol as an ideal solvent for developing stable ILMs is demonstrated using the …

Microporous Polymeric Membranes Via Melt Processing, Chaiya Chandavasu

Dissertations

Novel ultraporous and microporous membranes from immiscible polymer blends were produced via melt processing and post-extrusion treatments. Polystyrene (PS)/polypropylene (PP) and poly(ethylene terephthalate) (PET)/polypropylene (PP) blend systems with different rheological properties were studied. The blends were first compounded in an intermeshing co-rotating twin-screw extruder and subsequently extruded through a sheet die to obtain the precursor films. These were post treated by uniaxial or biaxial deformation (100-500%) with respect to original dimensions to induce a microporous structure. The porosity is induced by drawing the precursor film at a temperature below the glass transition temperature (T_g) of the minor …

Turbulent Mixing And Chemical Reaction In Baffled Stirred Tank Reactors : A Comparison Between Experiments And A Novel Micromixing-Based Computational Fluid Dynamics Model, Otute Akiti

Dissertations

The optimization of reaction processes to maximize the yield of a desired product while minimizing the formation of undesired by-products is one of the most important steps in process development for drug manufacturing or fine chemical production. In many situations the kinetics of product formation can be quite complex and involve a number of intermediate steps as well as parallel and serial reactions. This renders the systems sensitive to the operating conditions. Often, upon scale-up, a decrease in the yield of the desired product is experienced, while more undesired by-products are produced. A large number of interrelated variables influence the …

Endotoxin Removal From Protein Solutions By Immobilized Metal Ion Affinity Chromatography, Yun Kang

Dissertations

In the biotechnology/pharmaceutical industry, the removal of endotoxins from final protein product has always been a challenge. A novel method for endotoxin removal from protein solutions, immobilized metal (ion) affinity chromatography (IMAC) has been developed in this study. Fe³⁺ was charged to a chelating gel that contains iminodiacetic acid (IDA). The IDA- Fe³⁺ IMAC column was exploited to remove endotoxin from protein solutions. This method involves the adsorption of the endotoxin on IMAC column. More than 99% endotoxin is removed and protein yield is higher than 90%. IDA-Fe³⁺ IMAC has proved to be an economical and efficient …

Fluidization And Soot Filtration In A Rotating Fluidized Bed, Gui-Hua Qian

Dissertations

A horizontal rotating fluidized bed (RFB) has been investigated for the removal of soot from diesel engine exhaust. This requires necessitating an understanding of the nature of fluidization, particle mixing and filtration in the RFB.

In an RFB, particles are subject to a centrifugal force which can be much larger than the force of gravity. Therefore the Geldart classification for conventional fluidized beds must be modified for rotating fluidized beds. A theoretical analysis shows that group A particles (minimum bubbling velocity U_mb > minimum fluidization velocity U_mf can shift to group B U_mb = U_mf and group …

An Integrated Membrane-Based Chromatographic Process For Biomolecule Isolation And Purification, Xiaoping Dai

Dissertations

Biomolecules obtained from fermentation and cell-culture processes are present in low concentrations in a complex medium/broth. For intracellular products, cells are first harvested. Subsequently, cell lysis and homogenization are undertaken to produce a homogenate. The biomolecules are next separated from the cell debris by lysate clarification. For extracellular products, the biomolecules are separated from the whole cells by clarification. The overall yield is reduced with each additional step. As the cost of bioseparation process accounts for 50-80% of the final product cost, innovations in and improvement of bio-downstream processing are greatly needed.

In this research, a cyclic process integrating a …

The Impact And Fate Of Aqueous Sodium Nitrate On Hydrocarbon Flames, Ann Marie Flynn

Dissertations

This study examined the impact and fate of sodium (fed as an aqueous nitrate solution) in fuel-rich methane/air and methane/methyl chloride/air flames as a function of equivalence ratios that experienced diffusion of air from the surroundings. The flames were stabilized on a slotted, uncooled burner. The data set was divided into profiles of relative sodium atom concentrations, temperatures, and selected stable species concentrations. The flames were simulated using a modified version of the Sandia FORTRAN program for modeling steady laminar one-dimensional premixed flames complete with detailed mechanisms. The results showed that maximum sodium atom concentration in the flame is decreased …

In-Line Measurement Of Solibility Of Physical Blowing Agents In Thermoplastic Melts As Related To Extrusion Foaming, Qiang Zhang

Dissertations

A novel in-line method for measuring physical blowing agent solubility in thermoplastic melts in extrusion foaming equipment has been developed in this study. This method uses video microscopy in connection with a foaming extruder (single or twin-screw) to generate solubility data by observing the onset of gas bubble formation/dissolution. This method offers a number of advantages over the existing conventional methods. It can be easily used to obtain solubility data for many foamable thermoplastic-physical blowing agent systems at high pressure and temperature near actual foaming conditions. Data generated using this method could be directly used to characterize and control a …

Chemical Reactions And Mass Transport In Emulsion Liquid Membrane, Huifang Fan

Dissertations

Emulsion liquid membrane (ELM) systems are an important technique for wastewater cleanup. For this purpose, emulsion globules are dispersed in wastewater (external phase), each emulsion globule consisting of many tiny aqueous droplets (internal phase) enclosed in oil (membrane phase). Hazardous chemicals in the wastewater are transported into the internal droplets by mass transfer mechanisms.

Since Li first invented an ELM system in the 1960s, much research effort has been devoted to experimentally finding the optimal conditions for ELM recovery of various chemicals. Such studies would have benefited greatly from the guidance of mathematical models, especially those that provide analytical predictions. …

Removal Of Volatile Organic Compound (Voc) Vapors In Biotrickling Filters : Process Modeling And Validation With Chlorinated Aromatic Compounds, Christos J. Mpanias

Dissertations

This study dealt with the removal of vapors of volatile organic compounds from airstreams in biotrickling filters (BTFs). A detailed general model was developed for describing the process under steady-state conditions. The model accounts for mass transfer between phases (air, liquid, biofilm) and biodegradation of pollutants in the biofilm. It also accounts for potential kinetic interactions among pollutants as well as potential process limitations by oxygen availability.

The general model was experimentally validated using mono-chlorobenzene (m-CB) and ortho-dichlorobenzene (o-DCB) as model compounds either alone or in mixture with each other. Before BTF experiments were undertaken, a systematic kinetic study was …

Modelling Of In-Situ Bioremediation With Emphasis On Inhibitory Kinetics And Biomass Growth, Dilip Kumar Mandal

Dissertations

This thesis was motivated by the need for better engineering tools to predict the extent of contaminant plume migration in the saturated zone. The principal result was a mathematical model analogous to a catalytic packed-bed reactor, in which the subsurface was considered to be composed (conceptually) of soil aggregates (the "catalyst" particles, in which biodegradation, diffusion, and sorption take place), and a mobile phase (groundwater) passing around the aggregates, in which convection, axial diffusion, and mass transfer from the aggregates take place.

The modelling emphasis was on a more detailed exposition of the biokinetics of the system (including an inhibitory …

Molecular Modelling Studies Of Acetylcholinesterase, Charilaos E. Linaras

Dissertations

The controversial role of electrostatic interactions in the process of steering of acetylcholine into the active site of acetylcholinesterases was investigated in this study. A novel methodology was implemented to simulate the process of recognition of acetylcholine by Torpedo Californica and both wild type and charge neutralized mutated Human AChE. The obtained results suggest the important role of coulombic interactions in the steering process. The steering process of selected irreversible AChE inhibitors was also simulated supporting the role of electrostatic interactions in the recognition process.

A novel methodology was also employed to model the covalent adducts of Torpedo Californica and …

Membrane-Based Reactors For Ozonolysis Of Organic Pollutants In Aqueous And Gaseous Streams, Purushottam V. Shanbhag

Dissertations

Many gaseous and aqueous waste streams contain multiple organic pollutants at low concentration levels. It is not economical to recover and reuse these compounds; it would be advantageous to destroy them efficiently within the waste stream. This work employed ozone, a powerful oxidizing agent, in concert with a compact membrane-based phase-contacting device. Three types of membrane devices were studied: two of them (the single-phase membrane ozonator and the two-phase membrane ozonator) treated organic pollutants in wastewater, while the third (the integrated absorption-oxidation membrane ozonator) removed volatile organic compounds (VOCs) from a gaseous waste stream.

In the single-phase membrane ozonator, the …

A Controlled Release Technique Using Microporous Membranes, Stephanie Farrell

Dissertations

A novel controlled release device based on aqueous-organic partitioning is described. The device comprises a reservoir, bounded by a microporous or porous membrane in the form of a hollow fiber or flat film. The reservoir liquid phase and the pore liquid phase are immiscible. The agent partitions between the phases at the aqueous-organic interface of the reservoir and the pore mouth, and then diffuses through the membrane pore liquid into a surrounding aqueous solution. The partition coefficient significantly influences the rate of release of the agent by reducing the driving force for diffusion across the fluid-filled membrane pore. The performance …

Vapor-Liquid Phase Equilibria Of Nonideal Fluids With A Ge-Eos Model, Socrates Ioannidis

Dissertations

This study dealt with the prediction and correlation of vapor-liquid equilibria behavior of nonideal fluids. The thermodynamic formalism of the G^E-EoS models, which combines the two traditional methods γ-Φ and Φ-Φ used so far for low and high pressure phase equilibria correlations respectively, has been combined with the 1FG^E model, based on one-fluid theory, to produce a more consistent approach to the phase equilibrium problem.

In the first part of our study we examine the predictive abilities of our model for vapor-liquid equilibria of highly nonideal fluids. The results establish the fact that the Huron-Vidal mixing rule …

Reaction Kinetics Of Methanol And Mtbe Oxidation And Pyrolysis, Wen-Chiun Ing

Dissertations

This study presents experimental data on the decomposition of methanol in several different reaction environments - fuel lean to stoichiometric at a temperature range of 873 and 1073 K and a pressure range of I and 5 atm. Methane fuel is also added in several of the systems studied in order to provide experimental data to understand the methanol addition effect on the methane oxidation.

Computer codes: ThermCal, ThermSrt and ThermCvt have been developed for the thermal property calculations of stable molecules by the Benson group additivity method and of radicals by the NJIT hydrogen bond increment method.

Pressure dependent …

Emulsion Liquid Membrane Removal Of Arsenic And Strontium From Wastewater : An Experimental And Theoretical Study, Ding-Wei Zhou

Dissertations

The emulsion liquid membrane (ELM) technique has been successfully applied on the removal of arsenic (As) from metallurgical wastewater and the removal of strontium (Sr) horn radioactive wastewater. This study consisted of experimental work and mathematical modeling.

Extraction of arsenic by an emulsion liquid membrane was firstly investigated. The liquid membrane used was composed of 2-ethylhexyl alcohol (2EHA) as the extractant, ECA436OJ as the surfactant, and Exxsol D-8O solvent (or heptane) the diluent. The sulfuric acid and sodium hydroxide solutions were use I as the external and internal phases, respectively. The arsenic removal efficiency reached 92% within 15 minutes in …

An Investigation Of The Mechanism Of Advanced Oxidation Processes (Aop) Involving Free Radicals And Charged Species., Yaw-Kuen Lin

Dissertations

Hydrogen peroxide is a key component in Advanced Oxidation Processes (AOP). Its decomposition at different pH conditions has been studied and some interesting results were observed. When the pH value of hydrogen peroxide solution is less than 9, its rate of decomposition is independent of pH. On the other hand, in the pH range of 9-12.6, its rate of decomposition increases as pH increases, and goes through a maximum value then suddenly decreases with respect to pH. A reaction kinetic model with three rate constants in the form of beta probability function was used to describe the experimental data of …