Chemical Engineering Commons^™

Performance Enhancement And Modeling Of Thermochemical Conversion Of Herbaceous And Hardwood Biomass Via Gasification With Integrated Sustainability Evaluation, Sanal Kumar Ap Mr

Theses and Dissertations

This thesis investigates the thermochemical conversion of three biomass feedstocks, namely Prosopis juliflora (PJ), Oryza sativa rice husk (RH), and Sesamum indicum stalk residue (SR), through experimental, simulation, and environmental analyses to evaluate their suitability for sustainable energy production. Thermogravimetric analysis (TGA) was conducted under inert conditions at multiple heating rates to study the thermal degradation and kinetic behavior of the biomasses.

Activation energy was evaluated using Kissinger, Flynn–Wall–Ozawa (FWO), Kissinger–Akahira–Sunose (KAS), Friedman, and Coats–Redfern methods. The results indicated that SR exhibited the highest thermal stability, followed by RH and PJ. Experimental gasification studies were carried out in a throatless …

Control Of Pore Nucleation And Rearrangement Kinetics During Aluminium Anodizing In Phosphoric Acid Electrolyte, Ilya V. Roslyakov, Nikita A. Shirin, Dmitry M. Tsymbarenko, Sergei N. Pavlov, Sergey E. Kushnir, Nikolay V. Lyskov, Kirill S. Napolskii

Journal of Electrochemistry

Anodic aluminium oxide (AAO) porous films with an interpore distance of several hundred nanometers are of great interest due to their unique interaction with visible and near-infrared light, and high thermal stability up to 1500 °C. These porous films are prepared by aluminium anodizing at high voltages in weak acids, leading to a slow kinetics of initial stages of porous structure formation. Here, we propose an approach to accelerate AAO formation in electrolytes based on weak acids such as phosphoric acid. Aluminium foils, pre-patterned using first anodizing under different conditions and subsequent selective dissolution of a sacrificial AAO layer, were …

Applications For The Quasi-Atomic Orbital And Constrained Density Functional Theory Methods On Catalytic Reactions, Alvaro David Loaiza Orduz

LSU Doctoral Dissertations

Selective activation of C–O, C–H, and C–C bonds underpins biomass upgrading, alkane functionalization, and CO₂ conversion. Despite their importance, the electronic factors governing catalytic performance remain incompletely understood, and many industrial processes still rely on empirical trends or material-specific observations. This dissertation addresses this gap by applying density functional theory (DFT), thermodynamic decomposition, and electronic-structure analysis to identify unifying principles of reactivity across transition-metal phosphides, vanadate oxides, copper-based electrocatalysts, and mixed IrO₂–RuO₂ layers. This work examines how charge transfer, orbital localization, and ligand-induced perturbations control reaction pathways in diverse catalytic systems. C–O bond scission in 2-methyltetrahydrofuran (MTHF) and methanol was …

Mechanistic Modelling And Parameter Estimation Of Heterogeneous Catalytic Synthesis Of Green Fuel, Rasheed U. Owolabi, Obinna P. Anele, Mohammed A. Usman

Mansoura Engineering Journal

Investigation of the kinetics and mechanistic modelling of biodiesel synthesis through the reaction of castor oil with methanol under catalyzed conditions was carried out in this study. The reaction mechanisms of the Eley-Rideal, Langmuir-Hinshelwood-Hougen-Watson, and Hattori type were employed to identify the rate-determining or controlling step of the reaction. Thirteen rate expressions were developed for reactant adsorption, product desorption, and surface chemical reactions. The experimental data from Sanchez-Cantu et al. were used to validate the models, and the best-fitting model and parameter estimation were evaluated using SAS and MATLAB software. From the results, the Eley-Rideal mechanism with glycerol desorption as …

Improving The Stability And Selectivity Of Methane Dry Reforming Catalysis Through Active Site And Process Tuning, Jonathan Lucas

LSU Doctoral Dissertations

Dry reforming of methane (DRM) is a potential industrial solution to greenhouse emissions whereby CH₄ and CO₂ are reacted on a transition metal catalyst to produce syngas, a feed stock for higher value chemical products. Ni can be used as the catalyst for DRM replacing the high cost and low abundance noble metals (Pt, Pd, Rh). However, the harsh process conditions of DRM (T > 700°C, P of 1-10 bar) readily deactivate Ni through coking and sintering. Ni supported on reducible oxides, specifically CeO₂ and CeO₂-ZrO₂ (CZO), have been widely studied to combat the rapid …

Community Diversity And Makeup Affect The Capacity For Bioconversion Of Chemically Deconstructed Pet Plastic Waste Into Biomass, Hunter Stoddard

Dissertations, Master's Theses and Master's Reports

Plastic waste management is an issue worldwide, particularly for locations with challenging logistics, such as remote locations, those impacted by natural disasters, and regions with armed conflict. These locations also struggle with food logistics and malnutrition. It is possible to tackle both issues by combining chemical deconstruction to depolymerize plastic waste with microbial conversion of the liquid product into biomass that can be used as an edible protein powder. The focus of this work is on the bioconversion of products from the chemical deconstruction of polyethylene terephthalate (PET) using ammonium hydroxide. Microbial communities have previously been shown to utilize the …

Determination Of Binary Co2/H2 Adsorption Isotherms And Kinetics Over Porous Organic Cage Cc3 Via Zero-Length Column Technique, Jimmy D.L. Moreno, Kyle Newport, Ali A. Rownaghi, Fateme Rezaei

Chemical and Biochemical Engineering Faculty Research & Creative Works

Understanding the dynamics of mixed-gas adsorption is essential for industrial-scale adsorptive separations. Also, obtaining binary adsorption isotherms is essential to gain a better understanding of adsorbate-adsorbent interactions in multicomponent gas mixtures. Porous organic cages (POCs) are highly porous, crystalline materials, with a small average pore window that make them promising candidates for separation applications. In this work, we utilized zero-length column (ZLC) technique to not only determine the kinetics of CO₂/H₂ separation over CC3 but also obtain the binary adsorption isotherms. The ultra crystalline diffusivities of 1.49 x 10^–4 and 8.31 x 10^–5 cm^{2 …}

A Computational Investigation Into Thermo-Kinetic Parameters Governing The Decomposition Of Bio-Oil Model Compounds, Ali Huseein Aljefri

Thesis/ Dissertation Defenses

Among notable products from thermal degradation of biomass are simple oxygen-containing aromatics. These compounds typically appear in high loads in collected bio-oil derived from biomass. As such, it is important to comprehend the decomposition chemistry of this category of compounds. This thesis takes on board a general approach to report thermo-kinetic parameters that govern decomposition of a selected set of bio-oil model compounds in two distinct systems: firstly radical-derived pathways in the gas phase and secondly thermal degradation in their condensed media. The first is attained through accurate density functional calculations while the second is accomplished through the use of …

A Computational Investigation Into Thermo-Kinetic Parameters Governing The Decomposition Of Bio-Oil Model Compounds, Ali Huseein Aljefri

Theses

Among notable products from thermal degradation of biomass are simple oxygen-containing aromatics. These compounds typically appear in high loads in collected bio-oil derived from biomass. As such, it is important to comprehend the decomposition chemistry of this category of compounds. This thesis takes on board a general approach to report thermo-kinetic parameters that govern decomposition of a selected set of bio-oil model compounds in two distinct systems: firstly radical-derived pathways in the gas phase and secondly thermal degradation in their condensed media. The first is attained through accurate density functional calculations while the second is accomplished through the use of …

Direct Blue 86 Textile Dye Removal From Aqueous Solution Using Rice Husk-Based Adsorbent, M. Zulbahari M. Zua, Muhammad Raza Ul Mustafa, Mohamed Hasnain Isa, Teh Sabariah Binti Abd Manan, Naimah Ibrahim, Rozeana Hj Md Juani, Wida Susanty Hj Suhaili, Asmaal Muizz Sallehhin Bin Hj Mohammad Sultan, Zuliana Binti Hj Nayan

ASEAN Journal on Science and Technology for Development

Adsorption by activated carbon is an effective method of dye removal. However, due to high production and regeneration costs of activated carbon, various studies on low-cost adsorbents have been conducted. Agricultural waste such as rice husk (RH) is seen to be a good adsorbent for dye removal. Moreover, rice husk is readily available. In this study, rice husk-based adsorbents were prepared by chemical and thermal treatments. Standard curve (colour vs absorbance) for Direct Blue 86 (DB 86) was prepared to determine the concentration of dye before and after adsorption. The adsorption potential of the adsorbent for textile dye DB 86 …

Development And The Use Of A New Kinetically Limited Linear Driving Force Model For Diffusion-Based Adsorptive Separations, Sulaimon Adedayo Adegunju

Theses and Dissertations

A new kinetically limited linear driving force (KLLDF) model, in terms of a modified extended Langmuir (EL) isotherm, was developed. This KLLDF model augments the equilibrium driving force in the linear driving force (LDF) model in such a way that the equilibrium loading of each component in the LDF model depends on the actual, kinetically limited, loading of the other components in a gas mixture, not their partial pressures. In contrast, the LDF model assumes the presence of a slower diffusing adsorbate in a gas mixture affects the equilibrium of a faster diffusing adsorbate in a pore structure via its …

Microalgae Immobilization With Filamentous Fungi: Process Development For Sustainable Food Systems, Suvro Talukdar

Theses and Dissertations--Biosystems and Agricultural Engineering

Demand for sustainable food sources has increased because of the rapid growth of the world's population.  In this study, microalgae cells of Haematococcus pluvialis were immobilized using the edible fungal strain Aspergillus awamori for potential food applications. The study investigated the impact of fungal loading, pellet geometry, and initial microalgae cell concentration on the immobilization performance and product characteristics. It was found that higher fungal loading and larger fungal pellets contributed to increased immobilization performance while increased initial microalgae concentration inhibited the process. Larger fungal pellets had decreased biomass density, which led to decreased surface concentration of immobilized microalgae but …

Carbon Dioxide And Steam Gasification Of Biochar: A Study On Mitigating Greenhouse Gas Emissions And Producing Syngas For Downline Synthesis Of Renewable Hydrocarbon Fuel, Parth Patel

College of Graduate Studies: Theses & Dissertations

This research explores the potential of mitigating CO₂ emissions from fossil fuel consumption and providing an alternative renewable source of energy by gasifying biochar with carbon dioxide (CO₂) and steam (H₂O). The utilization of captured carbon dioxide and wastewater in industrial sectors is considered to further contribute to the advancements in energy-efficient and low-emission technological solutions. This research evaluated the performance and kinetic parameters of biochar gasification through CO₂ and H₂O gasification using a stainless-steel fixed bed reactor. The operating parameters including biochar mass, reactor temperature, and inlet flow rate were varied. …

Understanding The Kinetics And Mechanisms Of The Desired And Undesired Reactions During Electrochemical Hydrogenation And Hydrogenolysis Of Furfural On Copper In Acidic Media, Andrew S. May

Dissertations and Theses

The decarbonization of the chemical industry would have an immense impact on lowering greenhouse gas emissions and assisting in mitigating global warming. To achieve this there is a growing interest in implementing renewable feedstocks like biomass and coupling of chemical processes with renewable energy. Furfural is a biomass derived species that has been identified as a platform molecule. Electrochemical processes are more easily coupled with renewable electricity and can be used to valorize biomass derived species such as furfural. The installation of electrochemical processes is hindered by a smaller knowledge base compared to thermochemical processes. This dissertation investigates the electrochemical …

Microwave-Assisted Ammonia Synthesis Over Cs-Ru/Ceo2 Catalyst, Alazar Kesete Araia

Graduate Theses, Dissertations, and Problem Reports (ETD)

Ammonia synthesis is one of the greatest innovations of the 20^th century with extensive applications from fertilizers to intermediates for nitrogen-containing chemicals and pharmaceuticals. Annually, more than 242 million tons of ammonia is produced globally, supporting approximately 27% of the world’s population. One of the fast-growing applications for ammonia is as H₂ energy carrier due to its high energy storage capacity, considered to be a decarbonized energy source. The low volumetric energy density and incompressibility makes Hydrogen a non-preferable energy carrier; an alternative carrier becomes a requirement. Ammonia possesses unique property as an energy-dense carrier to store and …

Modeling And Performance Analysis Of Deb Based Hydrogen Getters, John A. Matteson

Chemical and Biological Engineering ETDs

Hydrogen getter materials are used to irreversibly absorb hydrogen gas in sealed environments. The DEB based getter system, despite finding widespread use in this application, still posses challenges with respect to experimental performance analysis and fundamental understanding of reaction mechanism. The second chapter of this report addresses the experimental challenges of this getter system by demonstrating the utility and experimental strengths of a custom magnetic suspension balance (MSB) based gravimetric sorption system. This apparatus enables performance evaluation in process relevant conditions including dilute mixed gas environments which our results indicate is necessary for accurate performance evaluation of getter systems. Chapter …

Aryl Sulfonic Acid Catalysts: Effect Of Pendant Group Structure On Activity In Hydrolysis Of Polyethylene Terephthalate, Hossein Abedsoltan, Maria R. Coleman

Chemical and Biochemical Engineering Faculty Research & Creative Works

A series of aryl sulfonic acids were tested as catalysts for acid hydrolysis occurring at the surface of poly(ethylene) terephthalate (PET) particles. Specifically, p-toluene sulfonic acid monohydrate (PTSA), 2-naphthalenesulfonic acid (2-NSA), and 1,5-naphthalenedisulfonic acid tetrahydrate (1,5-NDSA) were chosen to provide sulfonic acid active groups and varying hydrophobic functionality. The effect of catalyst concentration and reaction temperature on PET hydrolysis rate was studied. The aryl sulfonic acid catalysts exhibited much higher rates of PET hydrolysis than the mineral acid, H₂SO₄. At 150°C and 4 M catalyst, the time required to achieve more than 90% TPA yield was …

Kinetics Of Carboxymethylation Reaction Of Cellulose Samples With Different Degree Of Crystallinity, Ilkhom Goyibnazarov, Sherzod Yuldoshov, Abdushukhur Sarimsokov

CHEMISTRY AND CHEMICAL ENGINEERING

No abstract provided.

Koh-Based Modified Solvay Process: Optimization And Kinetics Studies, Aya Abdel-Hamid Mourad

Dissertations

While desalination of seawater is important for meeting the water demand, the technology produces large volumes of reject brine and CO₂, causing environmental pollution. Solvay process (based on ammonia, NH₃) and modified Solvay process (based on calcium oxide, CaO) try to manage these wastes. However, more attention is needed to overcome different limitations of these processes such as, alkaline solubility, operating temperature, maintaining high pH value, and low sodium (Na⁺) removal efficiency, which does not exceed 35%. The aim of this work is to introduce an alternative alkaline, namely potassium hydroxide (KOH) and investigate …

Impact Of Clay Stabilizer On The Methane Desorption Kinetics And Isotherms Of Longmaxi Shale, China, Zhong Hua Liu, Jia Chun Wang, Baojun Bai, Yan Ling Wang

Geosciences and Geological and Petroleum Engineering Faculty Research & Creative Works

Knowing methane desorption characteristics is essential to define the contribution of adsorbed gas to gas well production. To evaluate the synthetic effect of a clay stabilizer solution on methane desorption kinetics and isotherms pertaining to Longmaxi shale, an experimental setup was designed based on the volumetric method. The objective was to conduct experiments on methane adsorption and desorption kinetics and isotherms before and after clay stabilizer treatments. The experimental data were a good fit for both the intraparticle diffusion model and the Freundlich isotherm model. We analyzed the effect of the clay stabilizer on desorption kinetics and isotherms. Results show …

Fluorine-Based Inorganic Oxidizers For Use In Metal-Based Reactive Materials, Siva Kumar Valluri

Dissertations

This work explores inorganic fluorides as oxidizers for fuel-rich reactive materials. A preliminary assessment of metal fluorides accounting for their enthalpy of formation points to bismuth (III) fluoride, BiF3 and cobalt (II) fluoride, CoF2 as oxidizers of interest. Initially, composite powders of aluminum with chosen fluorides at 50-50 wt. % are prepared by arrested reactive milling. Despite an increase in reactivity and lowtemperature ignition, the prepared composite powders are insensitive to initiation by electro-static discharge (ESD), making them attractive alternative to analogous thermites having very high ESD sensitivity. In air, the composite powder particles burn faster than reference aluminum particles …

Kinetics Study Of The Hydrodeoxygenation Of Xylitol Over A ReoX-Pd/Ceo2 Catalyst, Blake Macqueen, Michael Royko, Bradie S. Crandall, Andreas Heyden, Yomaira J. Pagán-Torres, Jochen A. Lauterbach

Faculty Publications

In this study, we elucidate the reaction kinetics for the simultaneous hydrodeoxygenation of xylitol to 1,2-dideoxypentitol and 1,2,5-pentanetriol over a ReOx-Pd/CeO2 (2.0 weight% Re, 0.30 weight% Pd) catalyst. The reaction was determined to be a zero-order reaction with respect to xylitol. The activation energy was elucidated through an Arrhenius relationship as well as non-Arrhenius kinetics. The Arrhenius relationship was investigated at 150–170◦ C and a constant H2 pressure of 10 bar resulting in an activation energy of 48.7 ± 10.5 kJ/mol. The investigation of non-Arrhenius kinetics was conducted at 120–170◦ C and a sub-Arrhenius relation was elucidated with activation energy …

Pore Microstructure Impacts On Lithium Ion Transport And Rate Capability Of Thick Sintered Electrodes, Ziyang Nie, Rohan Parai, Chen Cai, Charles Michaelis, Jacob M. Lamanna, Daniel S. Hussey, David L. Jacobson, Dipankar Ghosh, Gary M. Koenig Jr.

Mechanical & Aerospace Engineering Faculty Publications

Increasing electrode thickness is one route to improve the energy density of lithium-ion battery cells. However, restricted Li⁺ transport in the electrolyte phase through the porous microstructure of thick electrodes limits the ability to achieve high current densities and rates of charge/discharge with these high energy cells. In this work, processing routes to mitigate transport restrictions were pursued. The electrodes used were comprised of only active material sintered together into a porous pellet. For one of the electrodes, comparisons were done between using ice-templating to provide directional porosity and using sacrificial particles during processing to match the geometric density …

Kinetics Study Of The Hydrodeoxygenation Of Xylitol Over A ReoX-Pd/Ceo2 Catalyst, Blake Macqueen, Michael Royko, Bradie S. Crandall, Andreas Heyden, Yomaira J. Pagán-Torres, Jochen A. Lauterbach

Faculty Publications

In this study, we elucidate the reaction kinetics for the simultaneous hydrodeoxygenation of xylitol to 1,2-dideoxypentitol and 1,2,5-pentanetriol over a ReOx-Pd/CeO2 (2.0 weight% Re, 0.30 weight% Pd) catalyst. The reaction was determined to be a zero-order reaction with respect to xylitol. The activation energy was elucidated through an Arrhenius relationship as well as non-Arrhenius kinetics. The Arrhenius relationship was investigated at 150–170◦ C and a constant H2 pressure of 10 bar resulting in an activation energy of 48.7 ± 10.5 kJ/mol. The investigation of non-Arrhenius kinetics was conducted at 120–170◦ C and a sub-Arrhenius relation was elucidated with activation energy …

Kinetics Of Photolysis And Photocatalytic Oxidation Of Ammonium Sulfite For Hydrogen Production, Moustafa A. Soliman, Maryam Zakaria

Chemical Engineering

The production of hydrogen via photocatalytic water splitting is one of the most promising technologies for obtaining chemical energy from direct solar energy while maintaining the least possible waste and pollutants. In this paper, we obtain the kinetic parameters necessary for the design of a photoreactor for photolysis and photocatalysis of ammonium sulfite solution. For the case of photolysis, we obtain the kinetics for the effect of changing the pH on the produced amount of hydrogen. For the case of photocatalysis, the intrinsic kinetic parameters of photocatalysis of water splitting reaction of ammonium sulfite and water in the presence of …

Modeling Mass Transfer And Chemical Reaction In Industrial Nitrocellulose Manufacturing Processes, Francis Patrick Sullivan

Dissertations

A series of models are proposed to describe the production of military grade nitrocellulose from dense cellulose materials in mixtures of nitric acid, sulfuric acid, and water. This effort is conducted to provide a predictive capability for analyzing the rate and extent of reaction achieved under a range of reaction conditions used in the industrial nitrocellulose manufacturing process for sheeted cellulose materials. Because this capability does not presently exist, nitrocellulose producers have historically relied on a very narrow range of cellulose raw materials and resorted to trial and error methods to develop processing conditions for new materials. This tool enables …

What Difference Does A Catalyst Make?, Tammy Guthrie, Mike Jackson, Holly Haney

High School Lesson Plans

Students will use different catalysts for the decomposition of Hydrogen Peroxide, to determine if different catalysts affect the energy that is generated during the reaction.

Thermoanalytical Studies On The Decomposition Of Energetic Ionic Liquids, Alan Esparza

Open Access Theses & Dissertations

Hydrazine has been extensively used as a propellant for space applications for more than half a century. However, its hazardous characteristics cause high storage and handling costs. For this reason, the search for alternatives, the so-called “green monopropellants,” is of great interest. Most green monopropellants are mixtures of an oxidizer and a fuel, and several ionic liquids (ILs) have been proposed for this application. Among them, hydroxylammonium nitrate (HAN) and 2-hydroxylethylhydrazinium nitrate (HEHN) are promising oxidizer and fuel, respectively. The objective of the present work was to clarify the decomposition kinetics of both HAN and HEHN, using thermogravimetric analysis (TGA), …

Experimental And Modeling Studies Using Packed Bed Reactors: Liquid Phase Ethylene Production By Hydrogenation Of Acetylene, Humayun Shariff

Doctoral Dissertations

"Gas-phase catalytic hydrogenation of acetylene to produce ethylene, commonly practiced in industries, has green oil formation, which leads to catalyst deactivation and sometimes reactor runaway risks due to high exothermicity. To overcome these issues as well as to increase the selectivity and conversion, liquid-phase hydrogenation of acetylene was investigated in packed bed reactors (PBR) using a commercial catalyst. The reactor performance of two-phase flow PBRs was assessed experimentally complemented by a validated mathematical model at different scales.

The selective hydrogenation of acetylene in the liquid phase over a commercial 0.5 wt% Pd/Al₂O₃ catalyst was investigated in a …

Contemporary Problems In Aerosol Aggregation And Gelation, Pai Liu

McKelvey School of Engineering Graduate Student Theses & Dissertations

Aggregation of nanoparticles in aerosols is a fundamental phenomenon with important implications to diverse fields ranging from material synthesis to pollutant control. The past few decades have witnessed extensive research on investigating the structure and growth mechanism of aerosol aggregates with sizes spanning across several orders of magnitude. This dissertation focuses on some contemporary problems that remain unaddressed in this topical area. Aerosol aggregates in sub-micron regimes, which are formed via the irreversible collision and aggregation of solid nanoparticle monomers, are fractal-like in their morphology. A mathematical description of this seemingly random structure dates to the seminal works by Forest …