Catalysis and Reaction Engineering Commons^™

Effect Of Cocatalyst Combination In Titanium-Based Ziegler-Natta Catalyst On Olefin Polymerization, Thanyaporn Pongchan

Chulalongkorn University Theses and Dissertations (Chula ETD)

This research focused on effect of cocatalyst types (TEA, TnOA, and TEA+TnOA) on titanium-based Ziegler-Natta catalyst in olefin polymerization both in slurry and gas-phase systems. This study has been divided into four sections. The commercial titanium-based catalyst was selected to investigate effect of reaction temperature and oxidation state of titanium from ESR measurement on slurry ethylene and propylene polymerization in the first and the second parts, respectively. The commercial catalyst with TEA exhibited the highest activity in ethylene polymerization. However, divalent, and trivalent of titanium (Ti2+ and Ti3+) was active in ethylene polymerization to produce more polymer. Stability of Ti3+ …

Structure, Morphology And Composition-Property Elucidation Of Ni–Mo And Ni−Mo−P Nanocrystals For Water Splitting Reactions And Group Iv Alloy And Silicate Nanocrystals For Visible To Near Ir Optoelectronics, Ebtesam Hassan Abuelenein Eladgham

Theses and Dissertations

Abstract

Structure, Morphology and Composition-Property Elucidation of Ni–Mo and Ni−Mo−P Nanocrystals for Water Splitting Reactions and Group IV Alloy and Silicate Nanocrystals for Visible to Near IR Optoelectronics

by

Ebtesam Hassan Abuelenein Eladgham

A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at Virginia Commonwealth University.

Advisor: Indika U Arachchige

Associate Professor, Department of Chemistry

Nanomaterials have gained a great attention because of their unique physical properties with size intermediate between molecular materials and extended solids. They have a large surface to volume ratio and display size tunable physical properties that was not …

Beneficiation Of Coal Using Supercritical Water And Carbon Dioxide Extraction, Matthew Decuir Virginia Commonwealth University Cl

Theses and Dissertations

This work explores the use of carbon dioxide, water, and their mixtures as solvent for the pre-combustion beneficiation of raw coal without using any toxic mineral acids in the temperature range of 200-400℃. The fluid polarity, ionic constant, and supercritical point can be adjusted by H₂O/CO₂ ratio and temperature. Adding carbon dioxide to hydrothermal fluid also increases the ionization by forming carbonic acid. Extractions with supercritical fluids have several benefits including enhanced mass transport, ease of separation and recycle, wide range of extractive capability and tunability, better inherent safety, and in the case of carbon dioxide and …

Catalytic Utilization Of Carbon Dioxide As Renewable Feedstock For Production Of Chemicals And Fuels, Abbas Alaa Jawad

Doctoral Dissertations

"The utilization of CO₂ as a renewable feedstock for producing commodity chemicals and fuels is an interesting challenge to explore new concepts and opportunities in catalysis and industrial chemistry. This sustainable approach not only leads to production of useful chemicals, but also has the potential to mitigate anthropogenic CO₂ emissions to the atmosphere. CO₂ itself is a sustainable and inexhaustibly available carbon source, however, it is inextricably linked to its inherent inertness. It is a thermodynamically stable molecule (ΔG_f = -394.01 kJ.mol^-1) with high oxidation state, hence, reactions of CO₂ must be combined …

Cu-Based Electrocatalysts For Carbon Dioxide Conversion To Value-Added Chemicals, Qingyang Li

Graduate Theses, Dissertations, and Problem Reports (ETD)

Massive usage of fossil fuel has being causing considerable emission of CO₂, which increases the temperature of the planet and greatly threaten human living environment, such as soil degradation, lower agricultural productivity, desertification, less biodiversity, fresh-water reduction, ocean acidification, ozone sphere destruction, etc. A number of technologies are being developed to reduce the CO₂ amount, however, all existing technologies except utilizing CO₂ as a feedstock, are hardly to essentially close the anthropogenic carbon loop. Currently, considering the economy and operability, electroreduction of CO₂ seems to be the most promising strategy to convert CO₂ to …

Review Of Established And Emergent Methods For The Production Of C4 Olefins, James Matthew Koval

Graduate Theses, Dissertations, and Problem Reports (ETD)

Current production of C₄ olefins is dominated by naphtha cracking and butane dehydrogenation, but significant research interest is developing in alternate feedstocks due to an abundance of inexpensive natural gas and bioethanol. The current C₄ olefin production methods are costly, make use of already-depleted petroleum resources, and are often hazardous to workers, which forms the impetus for investigation into alternative methods and assessment of their viability as a future means of olefin production. Methods of natural gas conversion to higher order hydrocarbons are discussed, including Fischer-Tropsch synthesis and oxidative methane coupling, each of which could form the first …

Process Development Of Shale Gas Assisted Lignin And Biomass Reforming Through Novel Reaction Pathway And Catalyst Design To Produce Hydrogen Rich Syngas For Fuels And Value Added Chemicals, Amoolya D. Lalsare

Graduate Theses, Dissertations, and Problem Reports (ETD)

Novel biomass reforming strategy through synergistic co-processing with flare gas (methane and carbon dioxide) was developed at West Virginia University. Hardwood biomass comprised of lignin, hemicellulose, and cellulose is abundant in the US and potentially a sustainable source of hydrogen through extensive reforming and gasification. Ever-increasing shale gas production in the US occasionally leads to flaring owing to stranded production across the US. Achieving biomass co-processing with natural gas about to be flared in such stranded shale plays is the underlying motivation here. A novel reaction pathway was discovered wherein methane and carbon dioxide assisted reforming of biomass could be …

Dynamic Study Of Mo/Zsm-5 Catalyst For Ch4 Dehydroadomation, Hadi Yahya Almusawa

Graduate Theses, Dissertations, and Problem Reports (ETD)

Methane dehydroaromatization (CH₄-MDA) is a highly promising venture for natural gas utilization/exploitation, i.e., direct conversion of methane (CH₄) to liquid aromatics (benzene) and hydrogen. This process is a catalytic reaction and therefore, is subject to all the advantages and constraints of catalysis. This study discussed the structure and reactivity of Mo/ZSM-5 zeolite catalysts and their effect on the active conversion of methane to valuable aromatic products such as benzene: 1) The preparation and characterization of Mo/ZSM-5, which are crucial steps in any catalytic reaction process since a better performing catalyst consequently leads to better outcomes; 2) …

Process Modeling And Techno-Economic Analysis Of Thermo-Catalytic Dimethyl Ether Synthesis And Microwave-Based Aromatics Production Technologies From Shale Gas, Chirag Mevawala

Graduate Theses, Dissertations, and Problem Reports (ETD)

Production of dimethyl ether (DME) and direct non-oxidative methane dehydroaromatization (DHA) to aromatics via conventional and microwave (MW)-assisted processes are investigated in this research. Plant-wide models of the shale gas to DME process with integrated CO₂ capture via direct and indirect synthesis routes have been developed. Optimal parameter estimation, and model validation are undertaken for various sections of the process including the pre-reforming reactor, auto-thermal reforming reactor, DME synthesis reactors, CO₂ capture units and separation sections. A novel DME separation process has been developed for efficient separation of DME, syngas, and CO₂. Plant-wide techno-economic optimization is …

The Potentials Of Faecal Sludge Treatment Using Local Conditioners In Tanzania: A Review, Doglas Benjamin1

Tanzania Journal of Engineering and Technology (TJET)

Worldwide, every day human beings generate millions of tons of Faecal Sludge (FS), which is rich in water, nutrients, energy, and organic compounds. Yet FS is not being managed in a way that permits us to derive value from its reuse, while at the same time, millions of farmers struggle with depleted soils and lack of water. In most of the developing countries, energy for cooking is mainly derived from cutting of trees, either as wood or charcoal. Resource recovery and reuse from FS can create livelihoods, enhance food security, support green economies, reduce waste and contribute to cost recovery …

Transient Electrochemical Surface-Enhanced Raman Spectroscopic Study In Electrochemical Reduction Of P-Nitrothiophenol, Yun Ling, Jing Tang, Guo-Kun Liu, Cheng Zong

Journal of Electrochemistry

P-nitrothiophenol (PNTP) is one of the most common probe molecules studied by surface-enhanced Raman spectroscopy (SERS). The research in electrochemical reduction behavior of PNTP will help understanding the mechanism for the nitrobenzene reduction. In this paper, we used transient electrochemical surface-enhanced Raman spectroscopy (TEC-SERS) to study the SERS of PNTP with cyclic voltammetry and chronoamperometry on gold electrodes. The results show that the TEC-SERS provide a time resolution that equals the transient electrochemical methods, and we concluded that the reaction was so quick that we did not observe the spectral information of intermediate species described in the literatures with a …

Electrochemical Sensor Based On Magnetic Electrode Modified With Magnetic Molecularly Imprinted Nanoparticles Immobilized Hemoglobin For Determination Of Hydrogen Peroxide, Yang Yuan, Jia-Xin Wang, Yu-Hua Cao

Journal of Electrochemistry

In this work, the surface-imprinted technique was used to prepare magnetic hemoglobin (Hb) imprinted nanoparticles, using Fe₃O₄@SiO₂ NPs as the carrier, Hb as the template molecule, and tetraethyl orthosilicate (TEOS) as the imprinted polymer monomer. The nanoparticles had a core-shell structure, with magnetic Fe₃O₄ NPs as the core and Hb imprinted polymers as the shell. Therefore, Hb could be concentrated and fixed on the surface of the magnetic imprinted nanoparticles (MMIPs NPs). Furthermore, MMIPs NPs were immobilized with chitosan (CS) on the surface of a magnetic electrode to constitute Hb enzyme-like biosensor …

Zif-67-Derived Ag/Co-Embedded N-Enriched Mesoporous Carbon For Oxygen Reduction Reaction, Zheng-Ling Di, Jing Zhu, Lei Dai, Wei Meng, Yue-Hua Li, Zhang-Xing He, Ling Wang

Journal of Electrochemistry

Nitrogen-doped porous carbon materials are considered as one of the most promising catalysts for oxygen reduction reaction (ORR). Herein, in order to further improve the activity of the nitrogen-doped porous carbon, Ag/Co bimetal is embedded into nitrogendoped porous carbon to form Ag/Co-embedded nitrogen-doped porous carbon material (AgCo@NC). The AgCo@NC was derived by the wet impregnation of Ag+ into ZIF-67 precursor, followed by chemical reduction and a subsequent pyrolysis process under Ar atmosphere at different temperatures (500 ℃, 600 ℃, 700 ℃). The morphologic characterization shows that the Ag/Co nanoparticles were successfully embedded in the mesoporous carbon framework with abundant nitrogen …

Ionic Liquid Assisted Synthesis Of Porous Carbons From Rice Husk For Supercapacitors, Han-Fang Zhang, Feng Wei, Jian Sun, Meng-Ying Jing, Xiao-Jun He

Journal of Electrochemistry

It is still a challenge to prepare carbon materials with high specific surface area at low cost from renewable resources. Herein, the authors report an efficient approach to synthesize porous carbons (PCs) from rice husk with ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF₆)) as a template and an activation agent. The as-made PCs featured the high specific surface area up to 1438 m²·g^-1. As electrodes for supercapacitors, PCs showed a high specific capacitance of 256 F·g^-1 at 0.05 A·g^-1 in 6 mol·L^-1 KOH aqueous electrolyte and a good rate performance of 211 F·g …

Formulation Optimization Effects On Mechanical And Rheological Properties Of Filled Polysiloxanes, Kevin Mcnay

Electronic Theses & Dissertations

Polysiloxanes are a class of high-performance polymeric materials that are used in a wide variety of applications, including O-rings, gaskets, sealants, coatings, and adhesives. These materials have high temperature resistances as well as flexibility at low temperatures. This is due to the bond between the oxygen and silicon atom, a bond that requires a high dissociation energy to break. However, their elastomers, which can be obtained by crosslinking linear precursors using various crosslinkers, generally exhibit low strength and have poor mechanical properties unless reinforced. Therefore, fillers, additives, UV-stabilizers, and anti-oxidants are often incorporated in order to improve the resulting properties. …

An Investigation Of The Chemistry, Thermodynamics And Catalytic Activity Of Molybdenum Carbides, Shanti Kiran Nayak

Chemical and Biological Engineering ETDs

These studies investigate the chemistry and stability of molybdenum carbides as an electrocatalyst. Due to their unique electronic properties, molybdenum carbides are purposed as electrocatalysts for reaction systems such as hydrogen evolution reaction, bifunctional water splitting and CO oxidation.

In this study, various synthesis processes were utilized to produce different types of molybdenum carbide with varying properties of particle size, surface area and excess carbon. The samples characterized by XRD accompanied by Whole Profile Fitting, Electron Microscopy, Gas Adsorption (surface area) and XPS.

These synthesis processes were refined using fundamental thermodynamic analyses. These analyses highlight regions of stability of different …

A Kinetic And Thermodynamic Model Of Ethylene Dichloride Pyrolysis., Travis J Czechorski

Electronic Theses and Dissertations

Ethylene dichloride (EDC) is a precursor for the production of vinyl chloride (VCM) which is subsequently polymerized to form polyvinyl chloride (PVC). To convert EDC to VCM, EDC undergoes a pyrolysis process in the absence of oxygen at temperatures exceeding 500C. However, process yields are limited by the uncontrolled production of side-products that can degrade the quality of PVC and poison the reactor. Thus, tight process controls and costly separations guided by heuristics and plant operator experience are used to optimize EDC pyrolysis. To improve the process, I have programed a kinetic model of EDC pyrolysis based upon estimations of …

Three-Dimensional Porous Vn Octahedron Catalyst With High Electrocatalytic Efficiency Toward Hydrogen Evolution Reaction, Can Yin, Wei-Wei Fu, Ling Fang, Shi-Li You, Hui-Juan Zhang, Yu Wang

Journal of Electrochemistry

With the rapid development of China’s economy, the demand for energy is increasing, and environmental problems are becoming more and more serious. The development and utilization of highly-clean new energy fuel can effectively alleviate the energy crisis and environmental pollution. Nowadays, exploring high-efficiency, environment-friendly and low-cost catalysts remains the focus of research in the hydrogen evolution reaction (HER). In this research, firstly, we proposed a three-dimensional porous vanadium nitride (VN) with octahedral structure, which was prepared by a calcination treatment method. The VN catalyst showed a good electrocatalytic activity toward HER, involving a small overpotential of 94.0 mV at -10 …

Influences Of Morphology And Nitrogen Doping On The Electrocatalytic Characteristics For Oxygen Reduction Reaction Of Nio/Rgo, Dong Liang, Heng-Yi Fang, Shuo Yao, Jie-Mei Yu, Zhao-Liang Zhang, Zhan-Kun Jiang, Xue-Ping Gao, Tai-Zhong Huang

Journal of Electrochemistry

In this research, the reduced graphene oxide (rGO) supported sheet-like NiO (NiO/rGO) and spherical-like NiO (NiO/N-rGO) catalysts for oxygen reduction reaction (ORR) were prepared. The structures, morphologies and chemical states of the two catalysts were characterized by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The electrochemical catalytic performance of the two catalysts for ORR were investigated by cyclic voltammetry (CV), Tafel, linear sweeping voltammetry (LSV), rotating disc electrode (RDE) and rotating ring disc electrode (RRDE) tests. Electrochemical results showed that the current density and onset potential (about 0.89 V) …

Special Issue: Electrocatalysis And Fuel Cells, Shuangyin Wang

Journal of Electrochemistry

/