Engineering Commons^™

Preparation, Characterization And Evaluation Of Rationally Designed Catalysts By Electroless Deposition, Wen Xiong

Theses and Dissertations

In heterogeneous catalysis, it is a proven factor that the surface-specific activity and the catalyst selectivity strongly depends on the active sites which are determined by the composition, size, and shape of the particle. For structure-sensitive reactions favored by specific surface sites, such as corners, steps, or edges, TOF and selectivity can be greatly changed by the size of catalyst particles since the active site distribution will change with the size of the catalysts. Usually, metal particles are synthesized by two methods in industry, namely precipitation and impregnation, which often exhibit a broad size distribution. The grand challenge of colloidal …

Catalytic Carbon Dioxide Hydrogenation To Methanol/Dimethyl Ether Over Copper-Based Catalysts, Xiao Fan

Doctoral Dissertations

Direct synthesis of dimethyl ether (DME) via CO₂ hydrogenation has received great attention, owing to the global warming caused by CO₂ emission and increasing energy demand worldwide. In this works, three major aspects of bifunctional catalysts development were studied: (1) investigation of the roles of interaction in the CuO-ZnO-ZrO₂-Al₂O₃/HZSM-5 bifunctional catalysts, (2) deactivation and regeneration of CuO-ZnO-ZrO₂-Al₂O₃ with different zeolitic catalysts for one-step CO₂ hydrogenation to dimethyl ether, and (3) study on the enhancement of activity and stability of CZZA/HZSM-5 bifunctional catalysts via the introduction of …

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

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 …

Controlling Selectivities In Heterogeneously Catalyzed Aldol Reactions, Koushik Ponnuru

Doctoral Dissertations

Aldol condensation is an important C-C bond formation reaction in chemical synthesis that finds versatile applications in bulk and fine chemical industries and has the potential for upgrading of biomass to fuels. However, aldol reactions pose a challenge for controlling the product selectivity by forming a mixture of desired and undesired self, cross, and poly-condensation products. Furthermore, a side reaction, the fission of aldol products resulting in an olefin and a carboxylic acid, has garnered attention recently as a route to isobutene from acetone. While a high level of selectivity control is achievable by homogeneous catalysis, selective solid catalysts, which …

Preparation And Application Of Catalysts For The Stereospecific Reduction And Photooxygenation Of Olefins In Continuous Operations: A Novel Method For The Production Of Artemisinin, Daniel C. Fisher

Theses and Dissertations

Over the last two centuries, the discovery and application of catalysts has had a substantial impact on how and what chemicals are produced.Given their broad significance, our group has focused on developing new catalyst systems that are recoverable and reusable, in an attempt to reduce concomitant costs.

Our efforts have centered on constructing a recyclable chiral heterogeneous catalyst capable of effecting asymmetric hydrogenations of olefins with high stereoselectivity. A class of phosphinoimidazoline ligands, developed by researchers at Boehringer-Ingelheim, known as BIPI ligands, have proven efficacious in the asymmetric reduction of alkenes. However, these chiral ligands are homogeneous and coordinated to …

Cobalt-Based Catalysts For The Conversion Of Biomass-Derived Syngas To Ethanol And Higher Oxygenates, Zi Wang

LSU Doctoral Dissertations

Higher oxygenates synthesis by catalytic conversion of synthesis gas are the potential approaches to replace fossil fuels and produce chemicals for pharmaceutical manufacture, detergents and polymer industry. Cobalt-based catalysts are the most promising catalysts to replace noble metal catalysts for producing ethanol, acetaldehyde and higher oxygenates via CO hydrogenation. The formation of higher oxygenates requires active sites that can adsorb CO non-dissociatively and insert to the alkyl intermediate. The hydrogenation of the CO-inserted intermediates yields C2 and C2+ oxygenates. The main focus of this study is to investigate the active site for non-dissociative CO adsorption, and the modification of the …

Electrochemical Reduction Of Co2 On Supported Cu2o Catalysts, Joel Niño Galvez Bugayong

LSU Doctoral Dissertations

We have examined Cu-based catalyst materials that enable the conversion of CO2 to useful products such as fuels and chemical feedstocks by electrochemical reduction. In particular, we compared the electrocatalytic activity of supported Cu2O particles prepared using electrodeposition and wet chemical methods. The particles had cubic structure, ranging in size from 40 nm to 900 nm and consisting of low index planes. We observed significantly different product distribution on these catalysts compared to polycrystalline Cu, specifically for methane and ethylene formation. While Cu particles showed higher faradaic efficiency for methane formation compared to ethylene formation, we observed that Cu2O particles …

Atomic Level Study Of Water-Gas Shift Catalysts Via Transmission Electron Microscopy And X-Ray Spectroscopy, Mehmed Cem Akatay

Open Access Dissertations

Water-gas shift (WGS), CO + H₂ O [Special characters omitted.] CO₂ + H₂ (ΔH° = -41 kJ mol ^-1 ), is an industrially important reaction for the production of high purity hydrogen. Commercial Cu/ZnO/Al₂ O₃ catalystsare employed to accelerate this reaction, yet these catalysts suffer from certain drawbacks, including costly regeneration processes and sulfur poisoning. Extensive research is focused on developing new catalysts to replace the current technology. Supported noble metals stand out as promising candidates, yet comprise intricate nanostructures complicating the understanding of their working mechanism.

In this study, the structure of the supported …

Catalytic Hydrogenation Of Co To Higher Alcohols, Nachal Devi Subramanian

LSU Doctoral Dissertations

The interest in converting synthesis gas to alcohols and oxygenated fuel additives via CO hydrogenation is growing rapidly due to the increasing rise in oil prices. Among the potential end products, ethanol is desirable since it serves as a clean alternative fuel, a gasoline blend, and a hydrogen carrier to supply fuel cells. The high cost and limited availability of the most active/selective Rh-based catalysts has led to the development of base metal catalysts such as modified Cu-based catalysts. Literature suggests that a combination of Co (or Mn) with Cu can facilitate higher alcohol formation by a non-dissociative adsorption of …

Biodiesel Forming Reactions Using Heterogneous Catalysis, Yijun Liu

All Dissertations

Biodiesel synthesis from biomass provides a means for utilizing effectively renewable resources, a way to convert waste vegetable oils and animal fats to a useful product, a way to recycle carbon dioxide for a combustion fuel, and production of a fuel that is biodegradable, non-toxic, and has a lower emission profile than petroleum-diesel. Free fatty acid (FFA) esterification and triglyceride (TG) transesterification with low molecular weight alcohols constitute the synthetic routes to prepare biodiesel from lipid feedstocks. This project was aimed at developing a better understanding of important fundamental issues involved in heterogeneous catalyzed biodiesel forming reactions using mainly model …