Catalysis and Reaction Engineering Commons^™

Production Of Γ-Valerolactone (Gvl) From One-Pot Cascade Transformation Of Furfural Over Pt/Zeolite-Based Catalysts, Jukkapan Saengin

Chulalongkorn University Theses and Dissertations (Chula ETD)

γ-valerolactone (GVL) is a green renewable resource, which can be used as fuel additives, organic solvent in food industries, pharmaceutical intermediates. The direct production of GVL from furfural in a one-pot transformation is highly desirable in order to minimize the use of solvents, the number of unit operations, and the production cost. The cascade reaction was carried out in a single reactor, using a secondary alcohol as the hydrogen donor with acid catalysts (so-called Meerwein–Ponndorf–Verley reaction). In this work, the transfer hydrogenation of furfural with 2-propanal as a hydrogen donor was investigated on various zeolites including of HY with Si/Al …

Electrochemical Reduction Of Carbon Dioxide To Formate On Bi And Bisn Electrodes Prepared By Electrodeposition On Copper Foil, Jutamas Wasombut

Chulalongkorn University Theses and Dissertations (Chula ETD)

In this study, The Bix/Cu electrocatalysts were prepared by electrodeposition of Bi on Cu foil, and the BixSny/Cu electrocatalysts were prepared by electrodeposition of Bi and Sn on Cu foil in deposition solution bath with different Bi3+ ion concentrations of 0.05, 0.1, and 0.2 M (Bi0.05/Cu, Bi0.1/Cu, Bi0.2/Cu), while the Sn2+ ion concentration was constant at 0.025 M (Bi0.05Sn0.025/Cu, Bi0.1Sn0.025/Cu, Bi0.2Sn0.025/Cu). The electrocatalysts were characterized by SEM-EDX, XRD, and XPS and tested in the electrochemical CO2 reduction reaction. The results demonstrate that the Bi concentrations in the deposition bath affect the structure of Bi into different forms, including bulky structure …

Selective Hydrogenation Of Acetophenone To 1-Phenylethanol On Pt/ Tio2 Catalysts Prepared By Pulsed Dc Magnetron Sputtering, Khunarnon Ditsataporncharoen

Chulalongkorn University Theses and Dissertations (Chula ETD)

1-Phenylethanol (PHE) is a high-value chemical with various applications in fragrance and pharmaceutical industries. It is extensively used as strawberry fragrance additives in yogurts and chewing gums and an intermediate of anti-inflammatory drugs such as Ibuprofen. In this study, selective hydrogenation of acetophenone (AP) to PHE was investigated using platinum catalysts supported on different types of titanium dioxide including PC500 (pure anatase) and P25 (anatase mixed rutile). Pt was deposited on the titanium dioxide supports by pulsed direct current magnetron sputtering (PDC-MSD) method with deposition time spent on Pt coating at 3, 6, and 9 minutes. For comparison purposes, Pt/TiO2 …

Electrochemical Reduction Of Co2 To Co On Zn Electrodes Prepared By Electrodeposition Method, Krongkwan Poonbun

Chulalongkorn University Theses and Dissertations (Chula ETD)

In this work, the effect of substrates including Cu and Ti on the catalytic activity of Zn electrocatalysts prepared by electrodeposition method was investigated in the electrochemical reduction of CO2 (CO2ER). As analyzed by SEM-EDX and XRD results, it indicated that the different substrates did not have any influence on the morphologies of catalysts and the conductivity of substrate was the main factor on the CO2ER performance. The effect of Zn precursor concentration in the range of 0.025 M to 0.4 M was further studied on the characteristics and the activity of Zn/Cu catalysts in the CO2ER. . At low …

Effect Of Single Metal Loading On Cao/Al2o3 Pellet Catalyst For Biodiesel Production, Nattawadee Munbupphachart

Chulalongkorn University Theses and Dissertations (Chula ETD)

Biodiesel is a sustainable biofuel mainly derived from transesterification of vegetable oil or animal fat. Transesterification is increasingly being catalyzed by heterogeneous catalysts in recent years. As a result of a high-pressure drop, solid base catalysts in a powder form are not suitable for a continuous process. A pellet catalyst is more convenient, but it has lower surface per volume as well as lower in its catalytic activity for transesterification. This research aims at studying the effect of metal oxides loading on CaO/Al2O3 pellet catalyst for improvement of catalytic activity of transesterification. The 20 wt.% single metal loading of metal …

Methanol Synthesis Via Hydrogenation Of Mixed Co/Co2 Over Mn Modified Cu/Zno/Al2o3 Catalyst, Papawin Tunyasitikun

Chulalongkorn University Theses and Dissertations (Chula ETD)

The purposes of this study are to investigate the methanol synthesis by using mixed CO/CO2 hydrogenation on Mn modified Cu/ZnO/Al2O3 catalyst which is prepared by the co-precipitation method and to investigate the overall energy consumption of methanol synthesis based on experimental results through the simulation process using Aspen Plus V.9. The improvement of catalytic activity is performed by a continuous fixed bed microreactor at 250°C under atmospheric pressure for 5 hours on the stream through hydrogenation of different feed composition of CO2/H2, CO/H2, and CO/CO2/H2, and 24000 ml/gcat∙h of GHSV. The physical and chemical properties of the catalysts are measured …

Performance Of Carbon Nanotubes As Supports Of Nickel-Iron Catalysts For Carbon Dioxide Methanation, Phanatchakorn Mala

Chulalongkorn University Theses and Dissertations (Chula ETD)

Nowadays, an increase in CO2 emission is one of the main reasons of global warming. Many studies have tried to solve the problem by developing catalysts to efficiently convert CO2 into CH4. Herein, bimetallic Ni-Fe catalyst was studied to improve the catalyst activity of Ni-based catalyst which has low activity and is easily deactivated. Carbon nanotubes (CNTs) have been identified as one of the most promising nanomaterials with unique electrical, thermal, and mechanical properties. In this thesis, CNTs was synthesized from eucalyptus oil as a renewable carbon source and then employed as catalyst support material in methanation. Variations of synthesis …

Esterification Of Ethanol And Lactic Acid With Wo3 On Montmorillonite Catalysts For Ethyl Lactate Production, Suthicha Mukjinda

Chulalongkorn University Theses and Dissertations (Chula ETD)

This research aims to study the characteristics, catalytic properties and stability of tungsten oxide (13.5 wt%) supported on montmorillonite (W/MMT) catalysts prepared by using three different calcination temperatures including 375 (W/MMT375), 475 (W/MMT475) and 575 (W/MMT 575) °C. All catalysts were examined in esterification of ethanol and lactic acid at 80 °C. Characterization studies showed that the W/MMT475 catalyst exhibited the highest acidity, followed by W/MMT375 and W/MMT575, respectively. However, from the surface area result, W/MMT375 exhibited the highest surface area, followed by W/MMT475 and W/MMT575, respectively. When all catalysts were tested in esterification of ethanol and lactic acid, it …

Novel Electrochemical Packed-Bed Reactor For Carbon Dioxide Reduction, Suwakul Chaiwarit

Chulalongkorn University Theses and Dissertations (Chula ETD)

Electrochemical reduction of carbon dioxide (CO2) is a promising strategy to recycle CO2 into valuable chemical products. Nevertheless, a conventional apparatus which usually utilizes stack design to maximize its surface-to-volume ratio requires many elements and complicated instruction assembly. The stack design often requires feed streams to flow in narrow channels throughout the cell, which is also constrained by membrane size roughly 1 m2 by current manufacture technology. This research focuses on development of a new type of electrochemical reactor that is suitable for industrial-scale applications. The novel electrochemical packed-bed reactor is designed for the electroreduction to covert CO2 into CO …

Effect Of Molecular Sieve Addition On Methanol Synthesis From Co2 And H2 Through Alcohol Assisted Method Over Cu/Zno Catalyst, Tanawut Boonamnuay

Chulalongkorn University Theses and Dissertations (Chula ETD)

Low-temperature methanol synthesis from CO2 and H2 was carried out using ethanol as catalytic solvent. The alcohol-assisted method reduced synthesis temperature and enhanced methanol yield (35.8%) at 150 oC (5.0 MPa, Cu/ZnO catalyst). However, ethyl acetate and water were generated as byproducts from the reaction. The byproducts formed azeotrope mixture with methanol and led to a complex product purification. Therefore, in this study, molecular sieves (MS) were introduced to adsorb the byproducts. The effect of different MS (3A and 5A) was studied. It was found that MS helped enhancing methanol yield. The highest methanol yield (42.6%) was obtained when adding …

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 …

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 …

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 …

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 …

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) …

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 …

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

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A Facile Route To Synthesize Pt-Wo3 Nanosheets With Enhanced Electrochemical Performance For Her, Peng-Jie Jiang, Yi Lv, Chang-Miao Chen, Hong-Cheng He, Yong Cai, Ming Zhang

Journal of Electrochemistry

Platinum-tungsten trioxide (Pt-WO₃) nanosheets were synthesized on nickel foams (NFs) directly. As great conductive networks, NFs substrates could greatly improve the electrode performance of WO₃. The modified platinum nanoparticles not only enhanced the electron transformation of catalysts, but also increased the active sites for hydrogen evolution reaction (HER). Pt-WO₃/NF revealed a better catalytic activity than WO₃/NFs with a smaller Tafel slope (80 mV·dec^-1) and a lower overpotential of 72 mV at the current density of 10 mA·cm^-2. In addition, Pt-WO₃/NF showed great durability and stability during …